Donald L. Wise

EDITED BY
DONALD L. WISE
Northeastern University
Boston, Massachusetts
DEBRA J. TRANTOLO
Cambridge Scientific Inc.
Belmont, Massachusetts
Marcel Dekker, Inc. New YorkaBaselaHongKong

Library of Congress Cataloging-in-Publication Data
Process engineering for pollution control and waste minimization / edited by Donald L. Wise,
Debra J. Trantolo.
p. cm. -- (Environmental science and pollution control: 7)
Includes bibliographical references and index.
ISBN 0-8247-9161-4 (alk. paper)
1. pollution.2.Wasteminimization. I. Wise,DonaldL.(DonaldLee). U. Trantolo,
Debra J. III. Series.
TD191.5.W6 1994
628.5-dc20 93-4601
CIP
The publisher offers discountson this book when ordered in bulk quantities.
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Copyright 0 1994 by Marcel Dekker, Inc. All Rights Reserved.
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PRINTED IN THE UNITED STATES OF AMERICA

Preface
A clean environment is a goal to which we all strive. However, we have been the victims of
severe environmental damage as a result of industrial growth and defense-related
activities. The
damage to our environment is substantially affecting our overall health and welfare. It is a
credit to our human spirit that we remain optimistic and share an enthusiasm about environ-
mental issues.
The numbers of registered wastesites are alarming, and continue to grow daily. No longer
can we casually consider wastean acceptable by-product of our everydayactivities. While the
consumer hasbegun to embrace the concept of waste reductionas, for example,in the practice
of recycling, the large-scaleindustrialconcern has also turned to wastecontrolmethods.
Whether driven by governmentmandate,socialresponsibility,economics, or other forces,
waste control and waste minimization practices are increasingly welcomed.
Process Engineeringfor Pollution Control and Waste Minimization provides an up-to-date
source of technical information relating to current and potential pollution control and waste
minimization practices. Overfifty recognized experts provide an in-depth treatmentof this rap-
idly growing field that draws its resources frommany disciplines. We have deliberately solic-
ited input from governmental,industrial, and academic specialiststo ensure a multidimensional
presentation of the pollution control and waste minimization schemes that are shaping our en-
vironmental outlook.
The text is divided into five parts. It begins with the presentation of general engineering
considerations and the regulatory, ethical, and technical framework within which these pro-
cesses are managed, then enters into specific wastelwastewater pollution control technologies
that are used throughout industry. Models for potential control and minimization techniques are
offered, and industry-specific case studies complete the text. Throughout, we have attempted
to provide a sense that the scopeof waste control and minimizationmay be immense, but it is
not overwhelming.
We trust that this book will provide a contribution to this important field and emphasize
the need for continued progress. One way to better our environment is to eliminate or reduce
iii
iv Preface
pollution at the source. Potentially great benefits await us if we can develop economical, ef-
fective, and efficient solutions to our waste generation problems. All readers of this text will
contribute something to the environment of tomorrow.
Donald L. Wise
Debra J. Trantolo
Contents
Preface iii
Contributors ix
Part I: Engineering Issues In Pollution Control and Waste Minimization
Process Engineering for Pollution Control and Waste Minimization 3
John Hanna and Osawaru A. Orumwense
Selection of Least Hazardous Material Alternatives 17

Alvin F. Meyer
Multiple Approaches to Environmental Decisions 25

Douglas M . Brown
Introduction to Engineering Evaluation for Contaminated Sites 47

David S. Wilson, Alan C . Funk, Ronald G . Fender, and Marilyn Hewitt
Innovative Approaches to Cleanup Level Development 87

Ronald J. Kotun, Richard F. Hoff, Robert J. Jupin, Diane McCauslund,
and Patrick B. Moroney
Designing to Prevent Pollution 145

James Lounsbury
Biochemical, Genetic, and Ecological Approaches to Solving Problems During

171Bioremediation
in situ and Off-site
0. A. Ogunseitan
V
vi Contents
8 Commandments of Waste Management 193

Donald K. Walter
9 A Proactive Approach to Environmental Management: Meeting

allenges
Competitive and Environmental 213
William E. Schramm and Stella S. Schramm
10 HealthHazardsAssociatedwithPollutionControlandWasteMinimization 227
Patrick D . Owens
Part 11: Methodologies of Waste Control
11 Techniques for Controlling Solid and Liquid Wastes 247
Hsai-Yang Fang and Jejhrey C. Evans
l2 Solidification and Stabilization Techniquesfor Waste Control 271

A. Samer Ezeldin and George P. Korj?atis
l3 Soil Remediation with Environmentally Processed Asphalt @PATM) 297

S.M. Testa and D. L. Patton
14 Lead Decontamination of Superfund Sites 311

Ann M . Wethington, Agnes Y. Lee, and Vernon R. Miller
15 A Secure Geologic Repository for Hazardous Waste Residuals 331

Thomas R . Klos
16 Photocatalytic Degradation of Hazardous Wastes 363

M. S. Chandrasekharaiah, S. S. Shukla, J. L. Margrave, and S. C. Niranjan
17 Photocatalytic Oxidation of Organic Contaminants 377

Allen P. Davis
18 Biodegradation of Organic Pollutants in Soil 405

Paul D . Kuhlmeier
19 Siallon: The Microencapsulationof Hydrocarbons Withina Silica Cell 425

Tom McDowell
20 Remediation of Heavy Metal Contaminated Solids Using Polysilicates 441

George J. Trezek
21 Fluidized Bed Combustion for Waste Minimization: Emissions andAsh

Related Issues 467
E. J. Anthony and F. Preto
Part 111: Wastewater Treatment
22 An Overview of Physical,Biological, andChemicalProcesses for
Wastewater 489
Kanti L. Shah
Contents vii
23 FreezeConcentration: Its Application in HazardousWastewaterTreatment 513

Ray Ruemekorf
24 OrganoclaySorbents for Selective Removalof OrganicsfromWater

and Wastewater 525
Steven K. Dentel, Ahmad I. Jamrah, and Michael G. Stapleton
25 Removal of Chromate,Cyanide,and Heavy MetalsfromWastewater 535

Klaus Schwitzgebel and David M . Manis
26 NeutralizationTacticsforAcidicIndustrialWastewater 557
Christopher A. Hazen and James I. Myers
Part Iv:Modeling for Pollution Control
27 IntroducingUncertainty ofAquifer Parametersinto an OptimizationModel 569
Robert L. Ward
28 Application of Total QualityManagement(TQM)Principles to Pollution

Prevention Programs 591
Prasad S. Kodukula
29 PC Software for OptimizingGroundwaterContaminantPlumeCapture

and Containment 597
Richard C . Peralta, Herminio H. Suguino, and Alaa H. Aly
30 HorizontalWellsforSubsurfacePollutionControl 619
George Losonsky and Milovan S. Berjin
Part V Industry-Specific Pollution Control
31 Pollution Control and Waste Minimization in Military Facilities 637
Merrit R Drucker
32 Waste Reduction Strategies for Small Businesses 643

Dan A. Philips
33 Contaminated Soils in Highway Construction 663

Namunu J. Meegoda
34 Management of Waste Compressed Gases 685

Dan Nickens
35 Pollution Control in the Dairy Industry 705

T. Viraraghavan
36 Landfill Gas Collection and Destruction Systems: Evaluating Toxic Emissions

and Potential Health Risk 715
Karnig Ohannessian, Anna Peteranecz,and Thomas Kear
Index 727
This Page Intentionally Left Blank
Contributors
AlaaH.Aly Utah State University,Logan,Utah

E.J. Anthony CANMET, Ottawa, Canada
Milovan S. Beljin University of Cincinnati,Cincinnati,Ohio
Douglas M. Brown TheLogistics Management Institute,Bethesda, Maryland
M. S. Chandrasekharaiah Houston Advanced Research Center,TheWoodlands, T~xas
Allen F? Davis University of Maryland,CollegePark, Maryland
Steven K. Dentel University of Delaware,Newark, Delaware
Merrit F? Drucker Army Management Staff College, Fort Belvoir,Virginia
JeffreyC.Evans Bucknell University,Lewisburg, Pennsylvania
A. Samer Ezeldin Stevens Institute of Technology,Hoboken, New Jersey
Hsai-YangFang LehighUniversity,Bethlehem, Pennsylvania
Ronald G. Fender Environmental Resources Management Group,Exton, Pennsylvania
Alan C. Funk Environmental Resources Management Group,Exton, Pennsylvania
John Hanna TheUniversity of Alabama,Tuscaloosa, Alabama
Christopher A. Hazen MilesInc., New Martinsville, West Virginia
Marilyn Hewitt Environmental Resources Management Group,Exton, Pennsylvania
Richard F. Hoff ChesterEnvironmental,Monroeville, Pennsylvania
Ahmad 1. Jamrah University of Delaware, Newark, Delaware
Robert J. Jupin ChesterEnvironmental,Monroeville, Pennsylvania
ThomasKear OP&L,Inc., San Diego, California
Thomas R. Klos Envirovest Management,Houston, Texas
Prasad S. Kodukula Woodward-Clyde Consultants, Overland Park, Kansas
George F? Korfiatis Stevens Institute of Technology,Hoboken, New Jersey
RonaldJ.Kotun ChesterEnvironmental,Monroeville, Pennsylvania
X Contributors
Paul D. Kuhlmeier Consulting Environmental Engineer,Boise,Idaho

Agnes Y. Lee US.Bureau of Mines,Rolla,Missouri
George Losonsky Eastman Christensen Environmental Systems,Houston, Texas
James Lounsbury National Roundtable of State Pollution Prevention Programs, Silver
Spring, Maryland
David M. Manis EET,Austin, Texas
J. L. Margrave Houston Advanced Research Center,TheWoodlands, Texas
DianeMcCausland Chester Environmental,Monroeville, Pennsylvania
TomMcDowell SiallonCorporation, Laguna Niguel, California
Namunu J. Meegoda New Jersey Institute of Technology, Newark, New Jersey
Alvin F. Meyer A. F. Meyer and Associates,Inc.,MeLean,Virginia
Patrick B.Moroney Chester Environmental,Monroeville, Pennsylvania
Vernon R. Miller U.S.Bureau of Mines,Rolla, Missouri
James 1. Myers MilesInc., New Martinsville, West Virginia
DanNickens Earth Resources Corporation,Ocoee, Florida
S. C. Niranjan RiceUniversity,Houston, Texas
0.A. Ogunseitan University of California,Irvine, California
KarnigOhannessian OPdiL,Inc., San Diego,California
Osawaru A. Orumwense The University of Alabama,Tuscaloosa, Alabama
Patrick D. Owens Tosco Refining Company,Martinez,California
D. L. Patton Applied Environmental Services, Inc., San JuanCapistrano, California
Richard C. Peralta Utah State University,Logan,Utah
AnnaPeteranecz OPdiL,Inc., San Diego, California
Dan A. Philips Pensacola JuniorCollege,Pensacola, Florida
F. Preto CANMET, Ottawa, Canada
RayRuemekorf NIRO,Inc.,Columbia, Maryland
Stella S. Schramm University of Tennessee,Knoxville, Tennessee
William E. Schramm Oak Ridge National Laboratory, Oak Ridge, Tennessee
KlausSchwitzgebel EET,Austin, Texas
KantiL.Shah OhioNorthernUniversity, Ada, Ohio
S. S. Shukla* Houston Advanced Research Center,TheWoodlands, Texas
Michael G. Stapleton University of Delaware,Newark, Delaware
Herminio H. Suguino Utah State University,Logan,Utah
S. M. Testa Applied Environmental Services, Inc., San JuanCapistrano,California
George J. Trezek Greenfield Environmental, Carlsbad, Californiaand University of Cal-
ifornia at Berkeley, Berkeley,California
T. Viraraghavan University of Regina,Regina, Canada
Donald K.Walter US.Department of Energy,Washington, D.C.
Robert L. Ward Ohio Northern University, Ada, Ohio
Ann M. Wethington US.Bureau of Mines,Rolla, Missouri
David S. Wilson Environmental Resources Management Group,Exton, Pennsylvania
_________
*Current affiliation: Lamar University,

Beaumont,
Texas '
Part I
ENGINEERING
ISSUESIN POLLUTION
CONTROLAND WASTE MINIMIZATION
Process Engineering for Pollution
Control and Waste Minimization
John Hanna and Osawaru A. Orumwense

The University of Alabama
Tuscaloosa, Alabama
1. INTRODUCTION
As a part of the material cycle, ores and fossil fuels are extracted from the earth, processed,
and converted into metals, chemicals, and other processed (high value added) materials.
Hence, any expansion in the world economy increases the demand for minerals and metals with
subsequent increases in the amount of waste generated.
Wastes are generated by the mining, mineral processing, metallurgical, and chemical in-
dustries at an estimated annual rate of over 2.3 billion tons. The accumulated solid wastes at
both active and inactive mining sites approach a whopping 30 billion tons [l]. These wastes
include gases, dusts, sludges or solutions, ashes, and a variety of massive solid materials such
as overburden, waste rocks, tailings, and slags that must be disposed of at low cost with a
minimum of environmental degradation.
A large volume of the wastes is normally disposed of at locations close to either the mining
sites or processing plants. Evidence of these can be found in Minnesota, Utah, Alabama,
California, Tennessee, Idaho, Montana, and other states having high mining and industrial
activities.
A significant amount of the tailings is disposed of in impoundments, which range in size
from a few acres to large ponds covering thousands of acres. Wastes from processing plants
pose the most difficult disposal and environmental problems in view of the physical and chem-
ical properties of the wastes as well as the enormous volumes involved, and consequently a
large expanse of land must be used for the disposal [2]. A typical example is the Florida phos-
phate slimes. The overburden and waste rocks with characteristic high contents of pyrite, heavy
metals, and radioactive materials also present potential environmental and health problems.
Unfortunately, most of the mineral processing wastes have been excluded from the Re-
source Conservation Recovery Act of 1976 (RCRA). However, this situation is changing with
the stringent environmental regulations introduced in recent years, which have necessitated that
precautions be taken to both minimize and control waste disposal. Hence, the mineral or metal
3
Orumwense
4 and Hanna
constituents in wastes, whether of little or no economic value, must be amendedfor their en-
vironmental impact or as a source of resource supply.
II. SOURCE OF WASTES

A. Mining and Processing Solid Wastes
Most operations in the extraction and processing cycle generate wastes (refer
to Figure l), but
the extent to which a material can be classified as a waste depends on a number of factors.
These include
1. Sources andvolumesofwasteproduced
2. Potential dangers to health and the environment
3. Long-term reactivity with air and/or water and mobilization to the environment
4. Present disposal practices and alternative disposal methods
5 . Cost of disposal and potential use of the waste
Overburden
Sub-grade mlnerals
RAW MATERINS EXTRACTION
""
I mlnlng, quanylng. dredglng. exploratlon -Slurries

Flnes -
- cI -
I I
Ores. crude 011. coal. etc.
Spoils
I
I I
I Talllngs I
RAW MATERINS BENEFICIATION
--
Sands
"S1urrlea - "
+I
I
mllllng. washlng. concentratJon. upgmdlng Dusts
I
SolUUOns
I I I
Concentrates. refined 011.gas. minerals
I
stags
I Smoke
Fumes
I
Muds
-Dresses
solutlons
-
Resldues
Ash
t
Ingots. plgs. chemicals. energy
$ 1
U Chemlcals Pulp
I
Dust Smoke
-
I 7 MANUFACTURING AND SERVICES
assembly, packing. transportation.energydlstrlb.
I
-- - Fumes
solutlons
Drosses
Grlndlng
"
4'3
Coods and servias CIlpplngS
I
vI
I
I
I
Fumes I
I I Dusts
I --J
I s01uu0ns
I Smokes
Metals. glass.
L- -paper. p~asuc.-
etc.
Figure 1 Mineralwastematerialssupply,utilization,anddisposalsystem.
Process Engineering
Control
for Pollution 5
The following are typical examples of the waste generatedby mining and related process-
ing industries.
It has been reported that in the production of about 1.6 million tons of copper in 1976,
1 billion tonsof materials were processed. This breaks down to684 million tonsof overburden,
264 million tonsof tailings, 5 million tons of slag, 3.3 million tons of sulfur dioxide,and about
100 billion gallons of process water [3].
The iron industry is one source of enormous amounts of waste, since most of the iron
concentrates used in the manufacture of iron and steel are derived from relatively low grade
ores. spically, raw ores assaying25-33% Fe are mined and beneficiated to producehigh qual-
ity pellets assaying 60-65% Fe and 5% Si for the manufacture of iron and steel. About 330
million long tons of iron ore was mined in the United States in 1976, and the amount of wastes
generated was about 200 million tons [4], excluding the slag and dust wastes from the steel-
making step.
Conventional magnetic and gravity separation processing of magnetic and nonmagnetic
taconites of the Lake Superior Region resulted in substantial iron losses of about 20-30% in the
tailing products [5]. On the other hand, the more advanced beneficiation of the tailings from
techniques such as flocculation and flotation processes reduced the iron lost in the rejectsto as
low as 10%. The loss is partly due to the mineralogical compositionof the ores and the grain
size of both iron and gangue. High iron losses are observed for Birmingham red hematite ore,
for instance, because it produces more slimes than taconite ores. This is oneof the factors re-
sponsible for the relatively poor recovery of iron from run-of-mine material and the generation
of large tonnages of wastes, particularly in large-scale beneficiation operations.
The Florida phosphate industry is another sourceof a tremendous volumeof wastes. In the
production of phosphate, the soft minerals in the matrix, particularly clays and the very fine
phosphate aggregates,are dispersed readily in water, forming slimes duringthe hydraulic min-
ing, transportation, and separation steps. These slimes are difficult to recover, and in addition
they impair the beneficiationoperation. About one-third of the phosphate contentof the matrix
is lost in the slimes, which are generally discarded as wastes. The Florida phosphate slimes are
characterized byveryslow settling and trap a highvolume ofwater. Currently, impounded
slimes are stored behind earth dams and pose a serious threat to the environment. The recla-
mation of the land and enormous volumes of water are important for resource conservation and
in order to comply with stringent environmental regulations. The recovery of the phosphate
values discarded in the slime and tailingfractions containing about 30%-40% of the phosphate
present in the mined matrix would enhance the economy of the phosphate industryand expand
the available resources. The impact of this on reducing potential environmental hazards is enor-
mous. The phosphate losses at thecurrent rate of rock production of about 40 million tons per
year includes over 11 million tons of high grade phosphate that is lost in the slimes annually.
Vasan [6] has estimated that about1.5 billion tons of phosphate slimes is accumulated over the
years in dams together with about 4.5 billion tons of water.
The coalmining industry is another sourceof a large volume of solid wastes. The methods
used in the past for cleaning coal were highly inefficient and resulted in high coal losses in
waste streams duringthe mining and washing operations [2]. The washer waste fines are nor-
mally storedin above-ground impoundments. Quitea number of processing plants still indulge
in the practice of discarding coal fines.As a result, about 25% of the coal mined is disposed of
as waste.Based on the current rate of coal production of about 1 billion tons, about250 million
tons of wastes is produced annually, and out of this, about 200 million tons is coarse particles
and 50 million tons is fines. The amountof coal in coarse waste particles is more than 30 mil-
lion tons of carbon per year, while the corresponding amount in the fine fraction is about 30
million tons on an annual basis. The disposal of coarse waste particles is not a serious problem
6 Hanna and Orumwense
in most coal preparation plants,as they are usedas landfill. The fine-size wastes, on the other
hand, are a problem because of the difficulties experienced in dewatering and the characteristic
relatively low structural strengthof fine particles, which prevent fines from being usedas land-
fill [7].
B. Mining and ProcessingLiquidWastes

Effluents from coal preparation plants and drainage from waste disposal sites have a charac-
teristic dark color and have high concentrations of suspended particles that cause not only silt-
ation due to the settling of coarse particles, but also water pollution, both of which have
negative effects on aquatic lives[2,7]. Effluents from coal cleaning plantsand mines are also
reputed to have a great impact on the environment through the phenomenon as known
acid mine
drainage (AMD). This is oneof the causes of the destruction of forestsand vegetation today.
Acid drainage is reportedto be causedby the reaction,between oxygen, water, and iron sulfides
such as pyrite and marcasite. Microorganisms are known to enhance the rate of this reaction.
The most common techniques for mitigating acid drainage are neutralization using either lime,
limestone, soda ash, or caustic soda; reverse osmosis; and treatment involving silicates [7].
These techniques are discussed in detail later. The highly acidic solutions produced dissolve
several heavy metals in the waste pilesor impounded material and become loaded with a host
of environmentally undesirable heavy metal species, sulfates, and other anions.
On the other hand, the water discharged from some mines contains valuable metals such
as copper and uranium that couldbe recovered economically. Copper is usually extracted from
such discharges by either cementation or liquid ion exchange. Mine drainage containing9-12
ppm U,O, is stripped by ion exchange as exemplified by the operation in the Ambrosia Lake
district [8]. The acid mine drainage containing300-600 ppm A1,0, and 10-20 ppm U,O,, on
the other hand, is stripped by a combination of ion and liquid ion exchanges [9].
C.Coal UtilizationWastes
As a result of burning coal in boilersand electric power plants, a large quantityof ash is pro-
duced. The amount of ash generated by power plants in 1977 is estimated to have been about
67.8 million tons, of which 48.5 million tons wasfly ash, 14.1 million tons bottom ash, and the
remainder boiler slag. During that year, about6.3 million tons of the fly ash, 4.6 million tons
of the bottomash, and 3.1 million tonsof the boiler slag,or approximately 21%of the total ash
generated, was recycled in such products as concrete blocks, asphalt, and roofing materials
[lo-121.
D. MetallurgicalWastes
The production of alumina by the Bayer process each year is accompanied by simultaneous
formation of about 7 million tons of red mud that consists of a substantial amount of valuable
minerals and dissolved salts. These wastes are estimated to contain a large amount of caustic
soda, 1.2 million tons of alumina, 1.7 million tons of iron, and about 450,000 tons of titania
[13]. These pose severe environmentaland health hazards.
In steelmaking, over 2 million tons of dust and gases is generated by electric and basic
oxygen furnaces annually. The dust contains a substantial quantity of lead (0.4-2.6%), zinc
(6.3-24.8%), manganese (0.5-5.3%), and copper (0.03-0.27%) in addition to iron [14].
Similarly, in manufacturing stainless steel, a large amount of metals is aslost
wastes. Pow-
ell et al. [l51 estimated that approximately5 million poundsof molybdenum is lost in stainless
steel furnace dust each year.
Control 7
Table 1 Characterization of FoundryDust

Analysis (wt. %)
Toxicity
locationSample cuPb Zn Fe c1 (mg Pb/L)
Alabama 13.52 65.34 3.01 1.10 0.06 530
Ohio 0.50 63.70 6;30 0.58 0.54 440
Michigan 7.50 56.70 5.80 0.30 0.66 764
New Hampshire 0.24 44.70 2.95 0.15 0.40 188
Pennsylvania 0.79 54.80 5.80 460 0.06 1.30
Massachusetts 0.75 65.04 6.86 0.15 0.5 1 6
West Virginia 4.90 78.25 2.40 39 0.61 0.05
A large amount of dust is producedby brass and bronze foundries and secondary smelters
annually in the United States. The baghouse dusts vary in composition, but the main constit-
uents are zinc(40-78%), copper (10-15%), and small amountsof lead and tin. Most of the zinc
is present at ZnO, while the remainder is in the form of brass or bronze alloys. A typical char-
acterization of dust from some foundries is presented in Table1. These wastes are considered
to be hazardous because of the high lead contents.
During the production of elemental phosphorus using an electric furnace, a large amount
of toxic wastes such as sludge, slag, gases, and phossy water are also generated. It is known
that between 5 and 10% of the elemental phosphorus that is produced is left behind in the
sludge. The compositionof the other solid constituentsof the sludge is4040% SO,, 5-15%
CaO, 2-4% Fe,O,, and 2-5% P,O, [16]. In general, the ratio of phossy water and sludge that
are formed to the amount of elemental phosphorus produced is about5: 1. Phosphorus wastes
pose both environmental and fire hazards,and these wastes are producedat a rateof 1.5 million
tons annually.
111. METHODS OF CONTROL AND TREATMENT OF BULK SOLID WASTES

A number of measures are taken to minimize or render bulk solid wastes safe for disposal.
These include the extraction of heavy metals or toxic constituents from the waste materials
using either physical, chemical,or bioremediation techniques.On the other hand, some wastes
are either recycledor used directly, but more often a combination
of these techniques is applied
to achieve maximum process efficiency. The following methods are classified according to the
source of the solid wastes.
A. Copper Mine Wastes

Copper mine wastes are increasingly important because of thelow very
grade of most available
copper ores. Rule and Siemens [l71 have shown that the bulk flotation method is effective in
extracting such metal values as copper, cobalt, and nickel from copper mine wastes with re-
coveries in the range of 54-95%. The primary problem in using the flotation method for this
purpose is the intimate association of the valuable minerals or metals (minor) with the pre-
dominant gangue materials. Consequently, a high degree of fineness is necessary in order to
ensure liberationand subsequent separationof the metal values. However, reagent consumption
is also expected to be high. In most instances, the residues still contain fairly high levels of
valuable minerals or heavy metals and as a result mustbe subjected to further treatment. Pres-
sure leaching or bacterial leaching (bioleaching) is often used for this purpose.
B. IronOre Wastes
In the past, many iron tailing ponds were subjected to gravity concentration[l81 to recover the
iron contents. Jones and Laughlin Steel Corporationin Calmet, Minnesota, is an example of a
company that at one time combined flotation and gravity concentrationfor treating iron wastes
to recover the metal values. The presence of a large amount of slimes and the high impurity
contents of either the initial ores or the wastes impaired the recovery of iron from the wastes.
In contrast, selective flocculation and high-intensity and high-gradient magnetic separa-
tions [l91 are some of the other techniques that canbe used effectively totreat such materials.
Waste materials can also be subjected to reductive roastingand magnetic separation to reduce
the energy required for processing.
C.Phosphate Rock Wastes

Phosphate slimes are known to be not only difficult to recover but also economically unsound.
However, the associated adverse environmental impact necessitates treatment. Laboratory tests
on waste pond materials, low-grade washer products, and some raw Tennessee phosphate ores
have shownthat some of the phosphate can be recovered. Market grade phosphate concentrates
assaying 60-82% P205can be obtained in substantial amounts using the anionic flotation
method [20].
Direct digestion of the phosphate matrix with sulfuric acid is an alternative approach for
the minimization of slime disposal problems.This process producesa simple waste consisting
of gelatinous slime, sand, and gypsum. The composite is a compact sandy cake that could be
used as a filling materialin mined-out areas while about 95%of the P205is recovered as useful
material [2l ,221.
D. Fine CoalWastes
TWO major techniqueshave been proposedfor treating coal wastes. Theseare gravity separation
and flotation [23,24]. The use of Humphreys spirals to treat coal wastes has been established.
Although such treatmentsare capable of yielding high-grade coalconcentrates, the recovery is
relatively low. Also these techniquesare only applicableto feeds withparticle size coarser than
200 mesh. Besides,a substantial amountof the coal is lostin the tailings-about 10-71% [24].
Therefore, techniques thatare suitable for fine particles processing are required to supplement
the spirals in order to improve coal recovery.This has led to the development of a process that
is based on a combination of gravity separation and froth flotation.
In this process, Humphreysspirals are used to recover the coarse coalparticles while col-
umn flotation is employed for the minus 200 mesh size fractions [24]. Mechanical flotation can
also be used in place of spirals to separate the coarse particles. In this manner, both the quality
and the recovery of coal are improved significantly.
Similarly, thepyrite present in the wastes can be removed, and by doing so, acid drainage
problems can alsobe mitigated. It is also possible to employ a bioleaching techniqueto elim-
inate the pyrite constituents from coal wastes. This can be achieved by allowing bacteria to
oxidize the pyrite in coal wastes as feed.
E. Phosphorus Wastes
The methods of treating phosphorus waste include physical, ch’emical, and bioleaching tech-
niques. The physical methods include sizing, sedimentation, centrifugation, cycloning, and
flotation [25-27, 311, while air oxidation, chlorine oxidation, electrolytic oxidation, catalytic
gineeringProcess for Pollution Control 9
oxidation, distillation, CS2 extraction[28-331, and ion exchangeconstitute the chemical meth-
ods. Most of these processes either partially separate or oxidize phosphorus from the impuri-
ties.Therefore, a combination of twotreatmenttechniques is necessary for complete
remediation of phosphorus wastes. Another factor necessitating this methodology is the asso-
ciated low operating costs for such schemes.
A combination of clarification and chlorination techniques has been developed for extract-
ing elemental phosphorus from phossy water [26]. However, the associated residual chlorine
has an adverse environmental impact, and this renders the technique impractical, The ERCO
process is based on the use of nascent oxygen to oxidize elemental phosphorus prior to sub-
sequent separation [33]. Another method uses distillation as the basis for the remediation of
phosphorus from sludges [29]. The high operating costs associated with these methods have
limited their application.
In many cases a major part of the phosphorus wastes are present in the coarse particles.
Anazia et al. [31] have shown that between 26 and 29% by weight of the particles in the tested
sludge samples (obtained from FMC Corporation of Pocatello, Idaho, andthe TVA at Muscle
Shoals, Alabama) are coarse phosphorus particles containing 82-91% P4. It was also demon-
strated in the same study that about61-88% of the coarse phosphorusparticles can be recov-
ered by screening. The fine fractions represent 71-74% byweightof the sludge and assay
5-21% P4. The as-received unsized sludge can also be subjected to flotation to separate phos-
phorus concentrates assaying between 61 and 78%. P4 with a recovery in the range of 71-79%
depending on the characteristics of the wastes. The tailings assayed between9 and 18% P4and
constitute about 59-68% of the sludge [31]. It is obvious, therefore, that the fine fractions or
tailings must likewise be subjected to further treatment using other methods.
The phosphorus remainingin the physical separation rejects can be extracted after air ox-
idation treatment at ambient temperatures. These form the basis for the proposed two-step
method comprising either flotation or screening and conventional air oxidation for the treat-
ment of phosphorus sludges [31].
However, the P4 concentrations in the refuse from the oxidation step can be as much as
4%, which is still high in terms of toxicity. A long air oxidation periodof several days or weeks
may be necessary to achieve 90-95% conversion of P4 to H3P04 at an ambient temperatureof
30°C. Under these conditions the oxidation rate of P4 in water is slow and is influenced by
many factors such as pH, oxygen content, temperature, presence of metal ions, and degree of
dispersion of colloidal material [34]. Therefore, an incomplete conversion of P4 to oxyphos-
phorus compounds occurs during the conventional oxidation process because the reaction ki-
netics appear to be influenced by other factors such as agitation, particle size, and surface
coating [34].
This process has been further developed at the University of Alabama such that the oxi-
dation and conversion of P4 to soluble oxyphosphorus compoundsare enhanced significantly
[32, 351. In the new process, the insoluble P4 is converted to highly soluble and nontoxic com-
pounds thatare easy to extract from the rest of the sludge. This improvement has been achieved
by employing a novel reactor design known as HSAD to expedite the remediation operation.
Thus, depending on the P4 contentof a sludge, an almost complete oxidationof phosphorus is
achieved in about 1-3 hr, and the resultant acid solution can be employed in the manufacture
of either phosphoric acid or fertilizer by-product by neutralization. The chemically inactive
solid waste can be dried and safely disposed of as nonhazardous landfill product. Someof the
results obtained employing this processare given in Table 2.
The advantagesof the HSAD technique includeshort processing duration, high efficiency,
simple configuration, low cost, and applicability to various phosphorus wastes. The process
requires no catalysts, chemical oxidants, or high temperatures [35].
Table 2 mid Results of HSAD West Oxidation of Phosphorus Sludge [32]

Test No. Product
Weight (g) Weight (%) P4 Analysis (%) P4 Removal (%)
~ ~~
1 Solution 50.20 64.60 53.39" 99.97

35.40
Residue 27.51 0.02 0.03
-
Feed 77.71 100.00 34.50 100.00
2 63.44
Solution 49.76 54.35" 99.94
36.56
Residue 26.68 0.05 0.06
Feed 78.44 100.00 34.50 100.00
"Equivalent P4analysis of oxyphosphorus compounds.
F. 'Brass and Bronze Foundries Dust

Baghouse zinc dust is processed by using sulfuric acid leaching and electrolysis or crystalli-
zation to recover zinc and other metals [36,37]. The zinc extractionattainable with this method
is in the range of 89-99%. Basically, the method involves the use of strong sulfuric acid and
intense aeration to dissolve the zinc oxide and metallic copper from the dust. The lead, tin, and
zinc metal alloys present in the dust are not dissolved by sulfuric acid and remain with the solid
residues. The leach residues, which account for 20-50% by weight of the dust and are rich in
a number of metals, can be further treated to extract the metallic components [36]. The preg-
nant leach liquor is subjected to electrowinning to produce metallic zinc. However, the zinc
electrowinning operation is adversely affectedby the presenceof chloride ions or some metals.
Hence, additional measuresare required to eliminate chloride ions andother impurities in order
to produce high-grade metallic zinc. This can render the whole process expensive. Alterna-
tively, the crystallization technique is employed to recover the zinc from the leach liquor as
zinc sulfate salt.
IV. ADVANCEDREMEDIATIONTECHNOLOGY
A. Leaching
The most common method of recovering the metal values from low-grade sources such as waste
dumps or heaps is leaching. Leaching is a process in which a solid material is contacted with
a solvent in order to selectively dissolve some of the components. The objectives of leaching
metals from sludge include the dissolution of the metal valuesfor recycling or subsequent sep-
aration by other methods, to render wastes nonhazardous,or to render wastes amenable to fur-
ther treatment. Leaching is known to account for about 10% of the yearly copper production.
The commonly used leaching agents are sulfuric acid, hydrochloric acid, ferric chloride,
nitric acid, ferric sulfate,ammonia or ammonium carbonate, hydroxide, and microorganisms
such as bacteria, yeast, and fungi.
Unfortunately, many factors concerning leaching such as thesize and heightof dumps and
factors affecting solution percolation andthe kinetics and recoveryof the valuable metals from
the leach of pregnant liquors in general still require detailed studies and information dissemi-
nation. The fact that many of the minerals in wastes canbe recovered inexpensivelyby leaching
implies that some of the problems associated with the disposal of fine wastes canbe alleviated.
Biological remediation of wastes is accomplished by using naturally occurring microor-
ganisms such as bacteria, yeast, and fungi to treat contaminants. Its use is rapidly increasing.
However, the microorganisms requirea wide rangeof macro and micro nutrientsfor their met-
Control I1
abolic activities and growth. The environment is generally poor in the nutrients such as nitro-
gen, phosphorus,andcarbonrequired by the microorganismsforsustenance,andsome
contaminants exhibit a certain degree of resistance to different microorganisms. These are the
primary causeof the slow rate of breakdown of contaminants. Therefore,a successful bioleach-
ingoperationrequiresthegrowth of appropriatemicroorganismsthatcan be inducedby
manipulating conditions suchas the availability of nutrients, temperature, electron acceptors,
and aeration.
B. Precipitation
Precipitation is one of the common means of remediating wastewater. In this method, chem-
icals are used to alter the physical state of dissolved or suspended metals and to enhance sub-
sequent separation using sedimentation techniques. Chemicals such as caustic soda, lime, soda
ash, sodium borohydroxide, sodium phosphate, ferrous sulfide, and sodium sulfides are used
to induce precipitation. It is sometimes necessary to subject wastewater to some form of pre-
treatment such as filtration, destruction or organic matter and cyanides, metal reduction, neu-
tralization, and/or oil separation prior to precipitation.
Some metals as typifiedby hexavalent chromium are difficult to precipitate in the form in
which they occur and must be reduced if the operation is to be successful. Reducing agents
commonly used include sulfur dioxide, sodium bisulfite, sodium metabisulfite, and ferrous sul-
fate. Similarly, to effect sedimentation and subsequent separation of precipitates, flocculants
are sometimes required. Lime,alum, and polyelectrolytes are used for this purpose. The major
characteristics of wastes that have an impact on precipitation operations are the type and con-
centration of metals, amount of total dissolved solids, concentration of residual complexing
agents, and amount of oil and grease present in the wastes.
Metal-laden wastewater resulting from electroplating, pigment manufacture, the photo-
graphic industry, battery manufacture,and nonferrous metal industriesare usually subjected to
precipitation treatment.
C.IonExchange
In the ion-exchangeprocess,metalions in a dilute solution are substituted for identically
charged ions electrostatically bonded to the surface of an immobile solid medium. The solid
medium can be either a naturally occurring inorganic zeolite or a synthetic organic resin. Ion
exchange is a reversible chemical reaction. Therefore,the loaded resin or exchange medium is
placed in a pure solution of appropriate pH and the trapped metal ions are released. This
method is applicable only to liquid wastes or pregnant solutions.
The performanceof the process depends on(1) the concentration and valenceof the metal
constituents, (2) the presence of competing ion species, and (3) the presence of dissolved or
suspended solids and organic compounds. Therefore, the feed toan ion-exchange system must
be subjected to pretreatment. Thismethod results in about 95% metal recovery and high purity
products. This method is fully developed and is used commercially to remove chromium, cop-
per, nickel, cadmium, silver, and zinc from wastewater.
D. ElectrolyticRemediation
Electrolytic cell is the primary device used in electrolytic remediation. It consists of an an-
ode and a cathode immersed in an electrolyte. When an electric current is applied to an elec-
trolyte solution, the dissolved metals are reduced and subsequently deposited at the cathode.
The electrolytic remediation technique isalso known as electrowinning because the metals re-
covered are of high purity. This is one of the most effective methods for remediating chelated
12 Hanna and Orurnweme
metals, which are difficult to retrieve by other techniques. This method has the advantage of
producing metal-laden free sludge, but it is limited to solutions containing a fewtypesof
elements.
Electrolysis can be used to remediate cadmium, chromium, copper, lead, tin, and zinc.
However, such treatments involve a high energy expenditure. Wastes containing copper and
certain other elements must be leached with hydroxides before being subjected to electrolytic
treatment.
A variation of the electrolytic technique known as electrodialysis is obtained when a mem-
brane is placed between the anode and cathode such that the mobility of some ions throughthe
membrane is obstructed. Electrodialysis can be used for remediating wastes from such sources
as gold-, chromium-, silver-, zinc-, nickel-, and tin-plating operations where the ion concen-
tration is low and would not be economical for electrowinning. Most feeds for electrodialysis
treatment must be filtered to remove suspended solids. Besides, pH control is a compulsory
pretreatment measure because of the effect on metalseparation. When electrodes having a high
surface area are employed, metals removalof about 98% can be achieved.
E. MembraneSeparation
The membrane separation method encompasses such techniquesas filtration (microfiltration,
ultrafiltration, etc.), reverse osmosis, and electrodialysis. Thefiltration technique is used after
the sludge hasbeen pretreated for the removal of metals. The techniqueis also usedto pretreat
feeds destined for subsequent treatmentby both reverse osmosis and electrodialysis.
Reverse osmosis and electrodialysis are used to retrieve metalsor plating compounds from
wastewater. The electrodialysis method is described in the preceding subsection. Reverse os-
mosis (RO) systemsare characterized by having a number of modular units connectedeither in
parallel or series or a combination of the two. The applicationof this method to the remediation
of metal-laden sludgeis limited by the pH range in which the membrane can be used. Cellulose
acetate membranes are not suitable for use at pH above 7, while amide and polysulfone mem-
branes can be used in the pH range between 1 and 12. The performance of R 0 systems is im-
paired by the presence of colloidal matter, dissolved organics, and insoluble constituents. It is
recommended that the feeds to R 0 systems be subjected to such pretreatments as pH adjust-
ment, carbon adsorption, and filtration. The method is used commercially to remove brass,
chromium, copper, nickel, and zinc from metal-finishing wastes.
These techniques canbe used to produce effluents with very low metal constituents, pro-
vided, of course, that adequate pretreatmentshave been carried out. Metal removal onthe or-
der of 99% can be achieved by making use of a combination of precipitation and filtration.
F. Evaporation
Evaporation is a simple method for remediationof mixed materials based onthe difference in
volatility. Hence, the concentration of metals is brought about by the reduction in the volume
of the waste. The primary instrumentation used for this purpose includes rising film, flash,
and submerged tube evaporators. Cadmium, chromium, nickel, zinc, copper, and silver from
platingbaths are retrieved in theelectroplatingindustry by using this method.However,
this method of remediating wastes is cost-effective only when a very small volume of waste
is involved.
G. Encapsulation
Soluble silicates and their derivatives are very effective for the stabilization and fixation of
hazardous wastes.Silicates are used in waste treatment becauseof their inherent characteristics
ngineering
Process Control
for Pollution 13
such as alkaline nature (pH 20-14), ability to form gels, and reactivity with multivalent cat-
ions, and because their disposal poses no potential dangerto the environment.
Soluble silicates are polymeric and condense on aging to form anions having a silicon-
oxygen-silicon linkage that are complex and exist in various chain lengths and cyclic struc-
tures. Silicates react with metal ionsto form insoluble amorphous metal silicates. These metal
silicate complexesare insoluble over a large pH range compared with simple metal hydroxides.
This is responsible for the increased resistance to leaching of metals in solidified wastes and is
perhaps the main feature of silicates in waste treatment. Soluble silicates are made by fusing
sodiumcarbonate or potassiumcarbonateandsandinafurnace at 1450°F. Theresultant
nSiO,Na,O compound has silica (SiO,) to alkalinity (Na,O) ratio in the rangeof 1.6:3.9. The
SiO,Na,O ratio has great significancein subsequent useof silica because only compounds hav-
ing high ratios are employed in the manufacture of products such as gels, precipitated silica,
and zeolites and in the treatmentof wastes.
Setting agents commonly used in waste treatment include Portland cements, pozzolanic fly
ashes, and cement or lime kiln dust. The active components in setting agents are such deriv-
atives as the mono-, di-, and tricalcium silicates formed when the agent is mixed with water.
The physical properties and behavior of setting agents are strongly influencedby the calcium
silicate content, as this is directly related to the number and strength of the resultant bonds
formed. Silicates also reduce the permeability by reducing calcium hydroxide inclusion forma-
tion or the presence of voids in the structure of the material. The treatment of hazardous waste
with setting agents can be subdivided into two categories, stabilization and fixation.
Stabilization is a chemical processof transforming a liquid waste into a solid. The setting
agents are mixed with the waste, and when they “set up” or harden, the waste material is
entrapped in the structure. The procedure used in the stabilization operation involves premixing
the waste and setting agents before introducing soluble silicate. The role of silicates in the sta-
bilization process includes the reduction of setting time, decreasing of the permeability, in-
creasingofthecompressivestrength,andreductionofboththeamountofsettingagents
employed and the volume of the treated waste.
Fixation, on the other hand, is similar to stabilization in many respects, but rather than
merely entrapping the wastes as inclusions, the wastesare modified and bonded into a cement-
like matrix. Hence the solubility or leachability of hazardous components is reduced dramat-
ically. In this manner, the toxicity and mobility ofheavymetalwastesarechangedbythe
treatment. The treatment steps involve mixing the waste with cement or kiln dust as a setting
agent and water. Thereafter, a soluble silicate is introduced and mixed thoroughly. The proce-
dure is recommendedif a good result mustbe obtained, and cementmust be used when a waste
is tobe fixed. Portland cement is the most effective setting agent that be canused with silicates
for this purpose. The reason is that during hydration cement produces gels that help to encap-
sulate waste. Lime-based materialsdo not produce a large amount of gels during hydration, so
the amount of bonded wastes is reduced. Therefore, lime-based setting agents should not be
used for waste fixation.
REFERENCES
1. Hill, R. D., and Auerbach, J. L., Solid waste disposal in the mining industry, in Fine Particles Pro-
cessing, Vol. 2 (€?Somasundran, e d . ) , SME-AIME,NewYork, 1980, pp. 1731-1753.
2. Hanna, H. S., and Rampacek, C., Resources potential of mineral and metallurgical wastes, in Fine
Particles Processing,Vol. 2 (F?Somasundaran. ed.), SME-AIME, New York, 1980, pp. 1709-1730.
3. Mineral Trends and Forecasts, US. BureauofMines, 1979.
4. Klinger, F. L., Mineral facts and problems-iron, Bull. 667, U.S. Bureau of Mines, 1976, pp. 525-
545.
5 . Rampacek, C., The impact of R&D on the utilization of low-grade resources, Chem. Eng. Prog.,
February, 57-68, 1977.
6. Vasan S., Utilization of Florida phosphate slimes, Proc. 3rdMineral Waste UtilizationSymp., Chi-
cago, 1972, pp. 171-177.
7. Moudgil, B. M., Handling and disposal of coal preparation plant refuse, in Fine Particles Process-
ing, Vol. 2 (F!Somasundran, ed.), SME-AIME, New York, 1980, pp. 1754-1779.
8. Spendlove, M. J., Bureau of Mines research on resource recovery, IC 8750, U.S. Bureau of Mines,
1977.
9. Ross, J. R., and George D. R., Recovery of uranium from mine waters by countercurrent ion ex-
change, RI 7471, U.S. Bureau of Mines, 1971.
IO. Faber,J.H., Coal Technology Conference, Houston, Texas, 1978.
11. Brackett, G . E., Production and utilization of ash in the United States, Proc. 3rd. Int. Ash Utili-
zation Symp., Pittsburgh, Penna., IC 8640, U.S. Bureau of Mines, 1974, pp. 12-18.
12. Jackson, J., Total utilization of fly ash, Proc. 3rd Miner. Waste Utilization Symp., Chicago, Ill.,
1972, pp. 85-93.
13. Dean, K. C.,Utilizationofminemillandsmelterwastes, Proc. 2nd MineralWaste Utilization
Symp., Chicago, Ill., 1978, pp. 138-141.
14. Dressel, W. M.. Barnard, F! G., and Fine, M. M.. Removal of lead and zinc and the production of
prereduced pellets from iron and steel making wastes, RI 7027. U.S. Bureau of Mines, 1974.
15. Powell, H. E., Dressel, W. M., and Crosby, R. L.,Converting stainless steel furnace flue dust and
wastes to a recyclable alloy, RI8039, U.S. Bureau of Mines, 1975.
16. Slack, A. V. (ed., Phosphoric Acid, Parts 1 and 2, MarcelDekker,NewYork, 1965.
17. Rule, A. R., and Siemens, R. E., Recovery of copper, cobalt and nickel from waste mill tailings,
Proc. 5th Mineral Waste Utilization Symp., 1976, pp. 62-67.
18. Fine, M. M., and Heising, L. F., Iron ore waste occurrence, beneficiation and utilization,Proc. 1st
Mineral Waste Utilization Symp., Chicago, Ill., March 1968. pp. 67-72.
19. Colombo, A. F., Jacobs, H. D., and Hopstock, D. M.,Beneficiation of Western Mesabi Range ox-
idized taconite, RI 8325, U.S. Bureau of Mines, 1978.
20. Lamont, W. E.,etal.,LaboratoryflotationstudiesofTennesseephosphatesinthepresenceof
slimes, RI 7601, U.S. Bureau of Mines, 1972.
21. White, J. C., Fergus, A. J., and Goff, T. N., Phosphoric acid by didect sulfuric digestion of Florida
land pebble matrix, RI 8086, U.S. Bureau of Mines, 1975.
22. White, J. C., Goff, T. N., and Good, I? C., Continuous circuit preparation of phosphoric acid from
Florida phosphate matrix, U.S. Bureau of Mines, 1978.
23. Browning, J. S . , Recovery of fine-size waste coal, Final Rep. U.S.Dept. of Energy, Contract ET-
76-G-01-9005, Univ. Alabama, May 1978.
24. Hanna, J., and Kalathur, R., Recovery of fine size coal from impounded wastes, Miner. Metall.
Processing, November, 174-179. (1992).
25. Fleming, J. D.,Removalofphosphorus,aliteraturesurvey,TennesseeValleyAuthority,Muscle
Shoals, Alabama, 1970.
26. Barber, J. C., Recovery of phosphorus from dilute waste streams, U.S. Patent 4,595,492 (July 17.
1969).
27. Crea, D.A., et al., Recovery of phosphorus from electric furnace sludge, U.S. Patent 3,615,218
(October 1986).
28. Post, L. B., et al., Recovery of phosphorus from electric furnace sludge, U.S. Patent 3,615,218
(October 1971).
29. Holmes, W. S., Lowe, E. J., and Brazier, E. R., Phosphorus distillation, U.S. Patent 4,081,333
(Mar. 28, 1978).
30. Hinkebein, J. A. Recovering phosphorus from sludge, U.S.Patent 3,436,184 (April 1969).
3 1. Anazia, I., Jung, J., and Hanna J., Recovery and removal of elemental phosphorus from electrical
furnace sludge, Min. Metall. Processing, May, 64-68 (1992).
32. Hanna, J., and Jung, J., Phosphorus removal by dispersed air oxidation, Miner. Metall. Processing
November, 200-205 (1992).
Process Engineering
Control
for Pollution 15
33. Deshpande, A. K., Oxidation of phosphorus in aqueous medium, U.S. Patent 3,971,707 (July 27,
1976).
34. Sullivan, J. H., Jr., et al., A summary and evaluation of aquatic environmental data in relation to
establishing water quality criteriafor munitions-unique compounds. Part 3. White phosphorus,Fi-
nal Report, Water and Air Research, Inc., Gainesville, Ha., April 1979.
35. Hanna, J., and Jung,J., Remediation of phosphorus from electric furnace waste streams, Proc. Haz-
ardous Materials Control, HMC-South '92. New Orleans, La., Feb. 26-28, 1992, pp. 34-39.
36. Hanna,J.,andRampacek.C.,Recoveringzincfrombaghousedust, 2nd Annual Environmental
Affairs Conf. of theAmericanFoundrymen's Society, Milwaukee,Wisc.,Aug. 23-24,1989,
pp. 119-126.
36. CommodityDataSummaries,Phosphates, U.S. Bureau of Mines, 1978.
37. Powell, H. E.,et al., Recoveryof zinc, copper and lead-tin mixtures from brass smelter flue dusts,
RI 7637, U.S.Bureau of Mines, 1972.
38. Proceedings 3rd International Symposium, IC 8640, U.S.Bureau of Mines, 1974.
2
Selection of Least Hazardous
Material Alternatives
Alvin F. Meyet
A. E Meyer and Associates, Inc.
Mckan, Virginia
1. INTRODUCTION
A. Summary
This chapter addresses the underlying purposesof accomplishing measures to select the least
hazardous of alternative materials usedor planned for use by industrial and governmental en-
tities. It then discusses the relationship of substitution processes
to other considerations in the
decisionprocess. An overview of someapproaches for selectionmethodsispresented.A
“methodology” originally developed for the U.S. Navy is described, along with examples.
B. Substitution Methods as an Element of Pollution Prevention

1. Substitutionvs.Controls
A longstanding principle of environmental control and industrial hygiene is that the first and
basic consideration in control of hazards is the elimination of the hazardous component, or
if that is not feasible, then the substitution of a lesser hazard[l]. The concept of eliminating
the source or reducing the amount of toxic materials includes in addition to substitution of
materials such other measuresas process or operation2 changes, properdesign of operations,
and housekeeping. The importance of eliminating the need for costly environmental control
measures by substituting less dangerous or less offensive materials also is of longstanding
recognition[2]. Likewise, the economic advantages of industrial waste recovery is not a new
concept.
Nonetheless the primary approachto environmental control, until the late198% was that
of using &‘end of the pipe” control measures. This was primarily in response to the focus of
environmental regulations specifying limits to be metby treatment or other control measures.
In the early 1990s there emerged a steady increase in recognition both in regulatory agen-
ties [e.g., u.S. Environmental Protection Agency (EPA),the Department of Defense1 and in
the private sector that a comprehensive, cost-effective approach to environmental quality in-
17
18 Meyer
cludes source reduction, recovery, and reutilization, with treatment and ultimate disposal as the
last resort. The Pollution Prevention Act of 1990 established these concepts in a national policy
that “pollution should be prevented or reduced at the source whenever feasible.”
II. HAZARDOUS MATERIAL SUBSTITUTION ACTION

A. Statutory and Regulatory Requirements
There are many statutory and regulatory requirements that directly or indirectly create the need
for hazardous material assessment. These include federal statutes and their implementing reg-
ulations or standards, executive orders requiring federal agency compliance, and state and local
codes, standards, and regulations. The Department of Defense (DOD) and the military depart-
ments and agencies have requirements that implement the federal mandates and some require-
ments that predate them.
1 . Federal Codes, Standards, and Regulations
The primary federal statutes and their implementing regulations regarding environment, safety,
and health are the Clean Air Act, Resource Conservation and Recovery Act (RCRA), Clean
Water Act, Safe Drinking Water Act, Toxic Substances Control Act (TSCA), Emergency Plan-
ning and Community Right to Know Act (EPCRA), Pollution Prevention Act of 1990, Occu-
pational Safety and Health Act (OSHA), Hazardous Materials Transportation Act, and the
National Environmental Policy Act (NEPA). These acts taken together impose a need to ex-
amine the feasibility of using materials that are less hazardous, are less costly, or impose fewer
administrative or other regulatory compliance resource requirements.
2. Possible Application of Department of Defense Methodologies
A Risk Assessment Code (RAC) procedure was developed by the Department of Defense in the
early 1960s [3]. Initially, it was designed to provide a means of ranking hazards associated with
new weapon systems. Subsequently, the procedure was adapted in 1981 to rate occupational
safety and health deficiencies.
In its simplest form, the procedure provides a rating scheme based on a matrix to estimate
the severity of effects of the hazard and the probability of occurrence, with the results stated as
a risk assessment code. The range is from RAC 1 (catastrophic impact) to RAC 5 (negligible)
(see Table 1). The later (1981) procedure, which is still in use, includes a cost effectiveness
index and an abatement priority ranking.
The revised procedure takes into account, with a numerical algorithm, such circumstances
of exposure and resultant effects as the OSHA Permissible Exposure Limits (PEL), number of
employees involved, effects of exposure (ranging from death to minimal lost time, disease, or
injury), and duration of exposure. It is firmly established in the military services procedures for
evaluating and prioritizing occupational safety and health hazard abatement requirements.
The RAC schemes deal primarily with chemical and safety hazards ratings, with no con-
sideration for environmental ramifications. Recently there has been an increased focus on the
environmental aspect of hazardous materials use on the decision-making process. Unlike the
long history of chemical and safety hazards rating schemes, there are no universally accepted
systems for environmental hazards and risk acceptance. One possible method is a European
model, described below.
3. A European Method for Priority Selections and Risk Assessment
A study requested by the European Community Commission to provide a practical approach for
priority setting among existing chemicals was prepared by Sampaolo and Binetti [4]. Using this
Least Hazardous Material Alternatives 19
Table 1 Risk Assessment Code Rating Schemea

Mishap probability (MPC)
Hazard Severity
(HHSC) A B C D
I 1 1 2 3
I1 1 2 3 4
111 2 3 4 5
IV 3 4 5 5
aInterpretation of HM selection Risk Assessment Code:
RAC 1 = high risk (imminent danger of life or property; possible civil or
criminal action)
RAC 2 = serious risk (may result in severe injury or illness on or off site,
potential for major damage to environment, and resulting notice
of violation)
RAC 3 = moderate risk (may cause few illnesses or injuries or significant
property damage or environmental impact on or off site)
R A C 4 = low risk (can result in only minor impact on or off site or only
violation of a standard without damage)
RAC 5 = negligible (insignificant impact)
model, an individual property or a number of properties of a given chemical can be evaluated

and then ranked with those of other substances. This flexibility allows for evaluating different
relationships. For example, one might want to compare only the intrinsic properties with re-
spect to direct personal exposure in a particular circumstance or with respect to environmental
exposure. Certain chemicals might have different relative rankings for these two categories.
This model offers a number of advantages: The system is simple and flexible enough to be
adapted to different and specific needs (i.e., personal exposure to general exposure, risk from
domestic exposure vs. professional exposure, etc.). It is a self-improving system because new
information can be input and the result can be refined further. This model uses three sets of
parameters to evaluate risk and the priority of a given chemical: assessment of intrinsic prop-
erties, risk assessment or potentiality, and priority assessment.
Intrinsic Properties. Intrinsic properties of a substance are based on the set of physicochem-
ical , toxicological, and ecotoxicological properties that are considered fundamental (or intrin-
sic) to the first evaluation of the substance. Each element of the intrinsic property (e.g.,
molecular weight under the physicochemical category) is assigned a numerical value that cor-
responds to its level of danger. From this information a score is developed for each intrinsic
property, which also addresses the availability or nonavailability of the data. These intrinsic
properties are considered additive and determine the intrinsic danger of the substance inde-
pendently of external agents or factors that may influence it.
External Factors. Risk assessment or potentiality includes not only the intrinsic danger of a
substance but also the external factors that can influence the danger. These external factors in-
clude the quantity of the substance on the market, the plurality of possible exposures, and the
size of the risk population. As an example, a substance may be highly dangerous, but if it is not
on the market it will not pose any effective risk, and thus its intrinsic risk will be minimal.
Priority Meusurement. Priority assessment involves both the known or presumed danger of
the chemical and the degree of the lack of knowledge of the substance’s properties. A priority
measurement can be made by calculating the ratio of the weighted figures for properties with-
out data to those figures with available data. Both the risk assessment and priority assessment
parameters can affect the intrinsic properties of a substance by multiplying or canceling them.
20 Meyer
111. LIFECYCLE AND MANAGEMENT CONSIDERATIONS

A. LifeCycleConsiderations
Regardless of the methodology usedin rating hazardous properties of a material, the selection
process for the “least hazardous” involves more than environmental, safety, and health con-
siderations. In addition to assessmentsto determine the least harmful material based ona haz-
ardassessment(suchasthealgorithmdescribed later in this chapter), there are major
considerations that must be carefully assessed.
1. BasicFeasibilityandEngineeringConsiderations
A fundamental question that should be addressed is: Does the substitute perform adequately for
its intended use? This requires determination of the following:
1. “Favorable” vs. “adverse” effects on required performance of the material(s) in produc-
tion, operations, and maintenance situations.
2. Creation of new or different hazards (suchas substitution of a less toxic material witha fire
hazard potential for one that is highly toxic but has a low hazard or no hazard).
3. Durability and life cycle times to failure (as with a low volatile organic compound(VOC)
paint that may or may not last as long in a very hot or very cold climate).
4. Maintainability of equipment involved in using a substitute.
5. Possible process or equipment changes that may be needed.
6. Environmental and/or OSHA controls required even if it is the lesser hazard.
2. LifeCycleCostConsiderations
There are costs and benefits associated with the engineering and feasibility considerations that
need to be assessed. In addition, there are many other costs associated with the life cycle of
hazardous material. That life cycle extends from the time of concept through procurement,
storage, use, and disposal. It is beyond the scopeof this chapterto do more than highlight such
costs. It is also beyond its scope to describe the economic analyses required to evaluate the
relative costs and benefits of two or more candidate materials for selection. Among the many
costs that should be taken into account in the selection process are those shown in Table 2. A
very useful guide for comparing alternatives is the EPA Pollution Benefits Manual [5].
The EPA Pollution Benefits Manualprovides for a financial analysis approachto compare
alternatives for pollution prevention. It involvesa four-tier cost analysis from which economy
feasibility of alternatives can be evaluated. The four tiers are as follows:
Tier 0,Usual costs. The alternatives are identified, and all normal costs associated with each
are determined. These include investment (depreciable capital, expenditures), operating
costs, and operating revenues.
Table 2 Life Cycle HazardousMaterialsCostsandCost

Avoidance Considerations
Acquisition Safety
Supply and storage Hazard/risk assessment
Use ENEIS
Waste treatment Permits
Other disposal Personal protection
Emission control Medical monitoring
Inventory control Spill prevention and control
Engineering/process controlkhange Regulatory overhead
Training Liability
Least 21
Tier l , Hidden Costs. These include such investments as monitoring equipment, protective
equipment, control technology, and operating costs such as reports, monitoring training,
and medical costs.
Tier 2, Liability Costs. Included are penalties, fines, and future liabilities.
Tier 3 , Less TangibleCosts. These include costs such as those associated with labor
relations,
and public relations.
The results of the tier analyses are thenincorporatedintocostsummariesandfinancial
worksheets, which result in an assessment and/or comparison of any cost savings for each al-
ternative. This procedureallowsforcomparison of relative costs and benefits of selected
alternatives.
B. Management Decisions and Actionsfor Selection of Least

Hazardous Material
1. DrivingForces
The basic driving forces for managementto consider in the selection of less hazardous mate-
rials, in addition to regulatory requirements, include the life cycle cost considerations dis-
cussed above and such needs as planning for new products or processes (or changes to existing
ones), avoidance of new and long-term liabilities, and the possible benefitsof participation in
such voluntary programs as the U.S. EPA Industrial Toxics Project (ITP). Other benefits in-
clude improved employee and community relations.
2. “Closing the Loop”
Once decisions are made for substitution, a large number of follow-on actions are needed.
These include planning for phase-out
of the existing in-usematerials, development of new spec-
ifications and technicaldata documents, trainingof personnel, provision of any necessary con-
trols, and compliance with any new permit or similar requirements.
W. DESCRIPTION OF METHODOLOGY
A. Overview of the Navy Substitution Algorithm
The hazardous material substitution algorithm developed for the U.S.Navy also had wide PO-
tential for selection or substitution of least hazardous materials in civilian applications [6].
1. The NavyModel
The hazardous material substitution algorithm is sufficiently flexible that it can either serve as
a preliminary screeningto identify the most likely candidatefor further study or become a part
of a much more detailed and sophisticated decision model. In the first instance, the model
would be useful to an industrial or commercial concern or to a military installation comparing
materials proposedby vendors as substitutesfor existing materials not conforming to regulatory
requirements. The second application would be for screening as part of an in-depth decision
process for changes to production operations, or comparison of newly synthesized materials for
possible large-scale application throughout a major industry. For maximum utility, the Navy
model is adaptable to either simple manual computations or computer applications.
2. Description of the Algorithm
The algorithmis used to assign numerical “points” for various hazard descriptor elements such
as toxicity, duration of personnel exposures, number of persons exposed, related medical ef-
fects, fire and explosion potential, requirements for personal protective equipment, anda lim-
ited assessmentof environmental impact and control requirements. These latter include volatile
22 Meyer
organic chemicals, EPA Reportable Quantities, and EPA’s List of Lists materials (40 CFR
302,4) among others.
The “points” assigned are totals that providea numerical score anda risk assessment code
(RAC). This provides for determination of a hazardous material selection factor (HMSF),
which allows for materials to be compared with one anotherin numerical terms. The resultcan
then be used as an entry point into the foregoing overall decision process.
The input data are readily available. Principal among these are the Material Safety Data
Sheets (MSDS) required by 29 CFR 1910.1000, OSHAPermissible Exposure Limits (Table 2
29 CFR 1910.100), and EPA Publication 56014-90-011“Title 111 List of Lists.” The RAC pro-
cedure is based on a commonly used system safety analysis method (MIL-STD-882), and the
basic approach to the “point” algorithm is the previously described DoD system for rating
occupational, safety, and health hazards.
B. Understanding the Basis for the “Points”

The following brief information providesan understanding of the basis for selecting the range
of numerical values for the algorithm’s points.
1. Toxic Effects
The evaluation should include the frequency and duration of possible worker exposure. This
includes whether the material presents toxic hazardson brief, short-term exposures associated
with high concentrations and accidental releases or primarily causes harm from extended ex-
posure to relatively low concentrations. Materials that are irritants
skin or sensitizers or that are
suspect or known carcinogens, teratogens, or mutagens require special attention even if the
projected quantities are small.
In many instances, the MSDS will only summarize the toxicity data of the individual com-
ponents of the mixture andwill not provide information concerning specific toxicological stud-
ies on the material itself. In such cases, judgments will have to be based on consultation with
such approved sourcesas the Navy Environmental Health Center. Attention also must be given
to any information indicating that the material is a known skin sensitizer or possesses allergenic
properties. A suggested source of reference regarding toxic hazards is the National Institute of
Occupational Safety and Health (NIOSH) Pocket Guide to Chemical Hazards available from
the US. Government Printing Office.
2. Characteristics
Physical Characteristics. Materials with a high vapor pressure are more likely to be easily
dispersed into the environment than those with lower vapor pressures. Those with low flash
point and low boiling point (flash point lower than 73°F and boiling point below 100°F) are
extremely hazardous froma fire and explosion viewpoint compared with those with flash points
greater than 100°F. Liquids with specific gravities less than 1.O present fire-spreading hazards
because such materials float on water. A “toxic material” with a high vapor pressure is more
of a hazard in a confined work area than one with the same toxicproperties but a much lower
vapor pressure. This is because the higher vapor pressure will afford a greater risk of room
atmospheric contamination.
ChemicalCharacteristics. Wheremixtures are involved, it is importanttounderstandthat
those that include aromatic organic chemicals are generally more toxic (and often pose greater
fire and explosion hazards) than those classed as aliphatic chemicals. Among the chemical
characteristics that must be considered are stability, reactivity with other chemicals (forexam-
ple, is the material an oxidizer or corrosive?), and solubility, not only in water but in other
media.
Least 23
Circumstancesof Exposure. In addition to the specifics of probable work areas, questions on

the distribution of material throughout theweapon system life cycle or on-shore activity need
to be considered. Localized use (in a single work area) of a material determined to be highly
hazardous presentsa different setof concerns with respectto approval decisions than those that
apply to a material with moderate hazard potential that is widely used. Among the consider-
ations that should be examined are size of the work force or number of persons at a work site,
present and/or needed engineering or other controls, and work area environmental conditions
that affectthe hazard (temperature, humidity, the presence of other chemicalsthat may be syn-
ergistic or additive, etc.). During a general review and evaluation
of a proposed material, ques-
tions need to be examined with respect to the interactionof the proposed material with others
already approved and its use in the system or work areas and with nearby operations. For ex-
ample, it would be a mistake to approvea new cleaning solvent with a high vapor pressure and
low flash point for use in shops in which arc welding is conducted.
EnvironmentalImplications. The potential for hazardous waste (HW) generation and com-
pliance with various federal, state, and local codes, standards, and regulations must be eval-
uated. Insomegeographical areas, regulationson useand/or release of volatileorganic
compound air pollutants are very severe and may require special controls if a material is ap-
proved. Similar concerns must be examined with regard to air quality and water permits. Be-
cause of the, widevariety ofsuch requirements,the “points” used in thismethod are
simplified. More detailed ratings may have to be developed by the user for some analyses.
V. CONCLUSIONS AS TO UTILITY OF THE METHODOLOGY

The hazardous material substitution algorithm developed for the U.S. Navy has been tested
extensively and found to be a useful first screening tool.It also fills the need for a wide variety
of applications in the civil sector. As indicated earlier in this chapter, itis only one element of
the decision process.
It is also essential to note that although one goalmay be the elimination of hazardous ma-
terials that affect people or the environment, in many instances complete elimination is not
feasible. The selection method, and other considerationsin the decision process, provide fora
rational and cost-effective determinationof the most suitable material. As stated by EPA (Pol-
lution Prevention 1991, EPA 21P-3003) and the Pollution Prevention Act of 1990, when pol-
lution cannot be prevented, reduced at the source, or recycled, it “should be treated in an
environmentally safe manner . . . and disposal or other release to the environment should be
employed only as a last resort and should be conducted in an environmentally safe manner.”
ACKNOWLEDGMENTS
This chapter is based in part on AFMA-TR-91001, Development of Guidance for Selection/
Substitution of Less Hazardous Materials, for the U.S. Naval Supply Systems Command, un-
derUSAFcontractF3361589-D-4003,Order16,A. F. MeyerandAssociates,Inc.with
Engineering-Science, Inc. Publication rights to this chapter are retained by the U.S. Govern-
ment. Copies of the basic technical report canbe obtained from Defense Technical Information
Center.
REFERENCES
1. Patty, F. T.,IndustrialHygieneToxicology, Vol. 1 , Inter-SciencePublishing Co., Chicago, 1948.
2. Meyer, A. F., Jr., Engineeringbiotechnologyinoccupationalhealth, Trans. Am. Soc. Civil Eng.,
121: Paper No. 2798 (1956).
24 Meyer
3. U.S. Department of Defense, Deparfment of Defense Occupational Safety and Health (OSH) Pro-
grams, DODI 6055.1A. 9 Sep 87.
4. Sampaolo, A., and Binetti. R., Regulatory Toxicology and Pharmacology, Vol. 6, 1986.
5. U.S. EnvironmentalProtectionAgency, Pollution Benefits Manual, October1989.
~ 6. U.S. Navy, Naval Supply Systems Command, Development of guidance for selection substitution of
less hazardous materials, Tech. Rep. AFMA-TR-91001. 1992.
3
Multiple Approaches to
Environmental Decisions
Douglas M. Brown
The Logistics Management Institute
Bethesda, Maryland
1. THE IMPORTANCE OF DECISION MAKING

It would be difficult to overstate the importance of the environment as a policy issue. Aside
from the ecological implications of decisions in many “nonenvironmental” policy fields, en-
vironmental policies have impacts on other policyfields. The recent controversy over whether
protecting the spotted owl should weigh more or less heavily than protecting the jobs of timber
industry workers is not going to be solved here. The important thing is to realize that envi-
ronmental policies, often considered to be based on scientific analysis, must include consid-
eration of nonscientific issues such as fiscal realities, economic growth policies, and cultural
values. Even race has surfaced as an issue in this field [l].
Because of the weakness of the current state of the art in fundamental measurability of
environmental policies, an appreciation of the impact of such policies can only be hintedat by
using other proxy measures. While environmentalactivists prefer to see environmental protec-
tion as a universally superior good not subject to such comparisons,the fact is that protective
activities incur costs. Whether theyare continuing expenses or just investments that will result
in lower costs later on is a matter of interest, but it does not relieve societyof the obligationto
pay the bills until the investments mature.
In the end, all policy costs are experienced by society’s consumers and taxpayers. Indi-
vidual firms, of course, can be punished with criminal sanctions or forced into bankruptcy over
environmental breaches; but as a rule governments and entire sectors of industry simply pass
the costs along in the form of coerced tax hikes or industry-wide price hikes. Thus, neither
government or industry (in a wide sense) “pays” for environmental protection except to the
extent that when consumers or taxpayers find themselves with no more money to spend, the
popular taste for government or the industrial product may evaporate.
Those who believed thatthe 1970s’ Great Society programsor the 1980s’ defense buildups
nearly achieved this national policy bankruptcy point should look closely at the environment.
The cost to the taxpayer of dealing with environmental problems is expected to exceed 6%of
25
26 Brown
the Gross National Productby mid-decade. That is the size of the entire defense budget during
the peak of the Reagan buildup. Simply cleaningup known hazardous waste sitesat federally
owned facilities is expected to cost over$125 billion [2], with the figurebeing adjusted upwards
every year. Newly recognized threats are being discussed that will only add to the potential size
of this burden[3,4]. In addition, consumers will bear anadditional burden. Some of this burden
is hidden in the priceof consumer goods, as those private-sector firms that continue in business
rather than declaring bankruptcy either pay for required cleanups, self-insure against the need
to clean up in the future, or develop new processes to avoid becoming a party to a future
cleanup. In some cases, businesses will choose to go out of business rather than risk personal
or corporate liabilities of staggering proportions. At the least, this will reduce the number of
choices available to consumers, and at the worst, employees will be thrown out of work and
further impact on other taxpayers.
All in all, there are compelling fiscal and social reasons for ensuring that our very real
environmental problemsare identified and dealt with in prudent and responsible ways. Money
spent on the environmenteither directly by governments on behalf of consumersor indirectly
by consumers through higher prices chargedby producers as a result of regulations, cannot be
spent on other worthy causes such as consumer and national savings and debt reduction, urban
issues, transportation networks, and national security: whatever your policy preferences are,
environmental spending competes with it. And, if not properly thought out, environmental pol-
icy can compete with itself. For instance, the EPA has spent years convincing the public that
toxic wastesites are a tremendous sourceof health risks and must be dealt with promptly what-
ever the cost. The publication of the Unfinished Business report [4] requires the EPA to re-
educate the public that in its new view many other threats are more risky; EPA competes for
funding for those higher risks against an established, costly effort that the EPA itself estab-
lished and plansto continue.
A micro version of the same argument canbe made at the level of the individual producer
facility. Statutory responsibility or not, an organization cannot devoteso many resources to en-
vironmental protection that it can no longer afford to remain in business. Environmental ac-
tions, even where deemed socially worthy, must compete for funding with other programs, and
where the available funding does not cover all perceived needs, then environmental spending
itself must be prioritized. In short, for regulator, policy analyst, and facility manager,a sound
basis for making environmental decisionsis essential to the development and effective execu-
tion of a holistic, complex, and credible program for the protection of health and resources.
While some may argue for a policy based strictly on scientific evidence, others argue for en-
vironmental policies based onemotion, and yet others argue thatthe costs of delay on the one
hand and regulation on the other are socially destructive, environmental managers are faced
with a situation where something hasto be done that will satisfy all sides without bankruptcy.
Thus, while decision theoryis not the cornerstone of environmental science, it may well be the
keystone of environmental management.
II. ENVIRONMENTALROLES
Environmental threatsare produced and dealt with by organizations whose missionsare broader
than simply protectionof the environment. Environmental agencies, however, havethe mission
of ensuring that producers do not forget their environmental responsibilities. Those responsi-
bilities are to the third player in this process: the public. Through the political process, the
public caused an environmental policy to be put in place to protect healthand the environment,
and at the grass-roots level the public maintains oversight onthe specific actions of both reg-
Environmental 27
Management
Table 1 PolicyRoles
Characteristic
PolicyviewpointSinglefocus on narrow Complete operation with Does not generally under-
portion of environ- environment as part of stand or get involved.
mental issues. the whole.
Mission
pollution
Prevent
all
and Produce products and Seeks products and
punish all polluters. pay for environmental protection.
protection.
Objectives
Focus
resources
worst
on Minimize resource drain. No perceived threat is
threat. acceptable.
Resources
Cleanup costs do not Cleanup costs are taken Pay in either case,
detract from primary from funds otherwise through taxes or
mission. available for mission. prices.
Approach Extract payment for Focus on avoidance, then Passivity until aroused;
pollution. cleanup. then paranoia.
Policy effect Deters, does not repair, Avoids, evades, or re- Suffers consequences.
problem. pairs problem.
ulators and producers. The differencesin the roles of regulators, producers, and the publicare
summarized in Table 1.
The most familiar enforcement agency is a police department. It has a single focus on a
statutory area (in thiscase, public order). The primary responsibilitiesare (preferably) to deter
crime or, when that fails, toseekoutandapprehend criminals, which itself deters further
crimes. In addition to fines levied through the punishment process, such departments may col-
lect fees to recoup their costs of doing business, thereby reducing the burden on their budget
(and, in theory, on the taxpayer).
Frequently, however, there is no payor, either because the guilty party hasnot been appre-
hended or because the enormityof the crime makes financial restitution, even with damages,
unacceptable or so high as to be unpayable. Such cases, which are the norm more than the
exception, make it necessary for the department to absorb the cost of enforcement; but such
expenses are budgeted for and appropriated over and abovethe cost of normal operations, not
at the expense of those operations. We expect them to deter and apprehend, not to repair, the
problem of crime. In those few jurisdictions where victim compensation is considered, it does
not come out of the police operating budget. It is not generally expected that the enforcer will
have to police itself (although such occasions do arise, and have arisen in most of our major
cities over the past 15 years, and are generally poorly handled).
In some jurisdictions, we see a cooperative enforcement approach [5]: “community po-
licing” or the “cop on the beat,” tomatch the environmental metaphor witha police example.
Nonetheless, thosecooperative approaches are part of an overall enforcementstrategy; the reg-
ulator coaches the producer toward compliance rather than taking over the operating respon-
sibility itself. Finally,we expect the police to focus on the worst
problem-catching murderers
rather than staking out shoplifters.
The producers have a completely different set of responsibilities, the foremost of which is
the factthat they must continue on with their production task in order to survive; environmental
issues are a secondary concern. When a cleanup does become necessary, the producer must
pay, and its payment comes out of its normal operating expenses. To some degree, consumers
will absorb someof this cost, but in general, passing on too much of the cost will simply drive
28 Brown
the producer out of business (unless the producer happens to be a government agency). With
limited discretionary funding available for environmentalrestoration, then, producers need to
accomplish as much as possible with the resources they have.
Normally, government regulatory agencies act as enforcers. Once enforcement has oc-
curred, however, one is faced with the need to restore the situation. Then, and especially in
the case of the Superfund, the government becomesa “producer” and needs to act and think
like one.
Finally, there is the public. The public tends to be easily excited over health and safety
issues, although a much smaller (but more active) group maintains vigilance overnon-human
health and natural resources, anda very small groupis both active in and knowledgeable about
global ecology issues. Inaddition, the public is concerned aboutjobs, general economic issues,
property values, and the quality of life in communities. Thus, the public concerns tend to be
more diffuse than the single focus enjoyed by enforcers and producers. Because of that dif-
fuseness, the public seldom speaks with a coherent voice, which makes it easier for activists
and extremists on all sides of an issue to misrepresent or override the public will.
While the federal government’s National Environmental PolicyAct provides processes for
public involvement, as do a number of state statutes, there is at present no real requirementto
go along with public preferences as long as the pro forma requirementsare met. Thus, on any
given decision, the public can be and often is ignored. The more this happens, of course, the
more the public comes to see the regulator as well as the producers as its enemy, especially as
these parties will be on different sides at different times.
Given this disparity in roles, it may come as no surprise that there are different per-
spectives on what the general objectives of the environmental effort shouldbe. Ihave identi-
fied seven primary goals; others may exist. While most of them appear desirable, at least
in isolation, they are not all consistent. They are presented here in no particular order; indeed,
the ordering process itself is one of the most important facets of the environmental decision-
making process.
Risk. Eliminate risks to human health and the environment.
Cost. Engage in environmental projects that achieve organizational objectives without posing
an unacceptable risk to the organization’s economic competitivenessor viability.
Time. Accomplish objectives rapidly, if in fact there are risks to the environment and espe-
cially to our health.
Acceptability. Satisfy publicandorganizationalexpectations. All environmentaldecisions,
whether takenby public or private organizations, occur underthe observation of a political
structure and still remain consistent with the organization’s own value system.’
Deterrence. Ensure that environmental offenders, and particularly the worst offenders, are
caught and prosecuted.
Administration. Minimize the debate over the intent and application of environmental laws
and regulations.
Practicality. Develop policy alternatives that are executable, compromising the ideal to max-
imize what can be accomplished.
If the budget is unlimited, decision making or prioritization is unnecessary: one Simply
does everything that is wanted as soon as it is feasible to do so. However, increasing sophis-
tication in regulations and increasing effectiveness of environmental compliance efforts are
‘This objective was titled“Politics” in earlier work [l]. Some managers objectto the idea that “politics” intrudes on
the pristine pursuit of public and ecological health but feel quite comfortable with the need to tolerate public value
systems. “Acceptability” seems less threatening.
Environmental Management 29
Table 2 DecisionApproaches
ndition Knowledge
Multiple-rule
solution;
(one-rule)
Universal
Certainty
solutions (e.g., cost-benefit)
Statistical uncertainty
Static Expected value
Dynamic Simulation
Outcome uncertainty Aspiration level
Subjective decisions
Minimax
uncertainty
Total
allocation
Political
combining to produce requirements estimates for environmental work that are increasing ex-
ponentially. For federal agencies alone, workingoff existing project requirementsand dealing
with a number of pending interagency agreements with the EPA or stateagencies could require
three- to fivefold increasesin current environmental spending, even assuming that the historical
inflation of environmental costs can be controlled. But as soon as we say that some projects
will have tobe delayed to meet more reasonable funding expectations, the question of priorities
emerges: which projects should be delayed, and why?
In short, under reasonable resource conditions, not all of these objectives can be accom-
modated in full simultaneously. A blind emphasis on speed usually wastes money. A total focus
on scientifically assessed risk may be impractical if the necessary science is incomplete. Ad-
ministrative simplicity may be translated into rigidity, resulting in the carrying out of regula-
tions blindly, resulting in large costs with no appreciable improvement in the environment. And
so on. It is in just such cases-multiple, conflicting objectives-that the use of decision meth-
odologies is needed.
111. DECISION-MAKINGMETHODOLOGIES
This chapter is not intended as a single referencefor explaining the details of decision theory.
Such textsare available-indeed required-in every college’s management course work.’This
chapter proposes rather to explain why decision analysis is needed in environmental decisions
as much as any other.
In general, decision-making methodologiesare selected based on the degree of uncertainty
surrounding a condition or situation; Table 2 shows that alignment.
A.
Certainty
Under the condition of certainty, we know eachof the outcomes; it is simply a matter of choos-
ing the programthat benefits us the most. In that case, there is a universally superior solution
or decision rule. Even where such a rule is deemed to exist, it must be tested to determine its
universality and the existence of underlying rule structures, which may require reversion to a
more complex decision approach. Forinstance, the accepted rule may be that projects that re-
duce the most human health risks will take priority over all others.The real world presents us
%ere are too many such texts to list, and each university has its own preferred texts. Each manager has, or should
have, several. On my bookshelf, perhaps the most frequently used is Fleischer’s Engineering Economy [6]. Others
include Lapin’s Quanrirarive Methods for Business Decisions [71, Quade’s Analysis for Public Decisions [g], and
Douglas’s Managerial Economics [9].
30 Brown
with resource constraints, not necessarily limited to constraints on ready operating funds: the
total capacity of administrative, technical, industrial,capital, and labor resources formsan ef-
fective obstacle to unlimited activity levels.Given a clear goal and normal capacity constraints,
the basic rule can be expected to meet a quick challenge: if two projects are equally effective
in risk reduction but there are not enough resources to accomplish both, anothercriterion must
be applied as a tie-breaker. And, as a result of limited resources, at some point the residual
funding may be adequate only for a low-cost but also low-priority project while a higher pri-
ority but more expensive activity must be forgone.
Given a high degree of certainty, we know all potential cases and all potential outcomes
(and the relationships between the two). Then rule-based decisions are the appropriate solu-
tion to ensure that the best possible outcome is achieved from each possible situation. The
decision makers can incorporate multiple factors simply by adding more complex rules, but
in a rule-based system the rules cannot be waived.Norshould there be anyreasonto do
so, because all possible cases and outcomes can be predicted and the best course of action
identified.
Generally, we do not have such perfect information. Nonethelessmany environmental de-
cisions are based entirely on methods that address certainty. This occurs for two reasons: the
real information is unknown or the real information is too complex to be usedin its full detail.
When the real information is unknown, decision makers should apply appropriate decision
approaches under uncertainty, suchas those displayed in Table2. However, environmental de-
cisions are frequently made by bureaucracies (governmental organizationsor large industries)
that do not subscribe to subjectivity or political acceptability as an explanation for how deci-
sions were reached [lo]. Thus, where the real information is too complex to be analyzed ef-
fectively (as is often the case), managerssimplifyittoits essentials [ll]. If a modewill
describe the behavior of a natural phenomenon adequately(e.g., saying thatthe prevailing wind
is at 5 mph from the east, when in fact over the courseof a year it blows from mostdirections
at various speedsfor some periodof time), and if the resulting policiesdo not appear to be too
badly flawed, the approach is validated in terms of the value of the time and effort requiredof
the manager. Indeed, contrast this behavior with the warning to remain consciousof the value
of perfect information issued later in this chapter.
Again, however, true certainty seldom prevails.And in acting “as if,” we are simply mak-
ing assumptions: takinga mode to be the only possible outcomerather than the most frequent
one. The real situation may take oneof four alternative forms, representing increasing degrees
of uncertainty. Statistical uncertainty means that wehave a good idea of what might hap-
pen and that we have some probabilistic statements of how, when, or how often. Technically
speaking, this is called decision making under conditions of risk, but because of the extensive
use of the word “risk” in the environmental sense of a threat, I have called it statistical un-
certainty instead.
B. StatisticalUncertainty
When statistical uncertainty exists, we must use our statistical knowledge to make decisions
“as if” the outcome were to be as predicted by the probabilities, with appropriate consider-
ation for the fact that it might not. This is basically done using an expected value approach,
which some of you may know as a weighted average approach.
Rule-based approaches become meaningless ifwehave uncertainty, because we do not
know what situation exists or which rule should be applied. Despite the masses of data col-
lected to support science’s continuing assault on the mysteries of the ecosystem, we remain
extremely uncertain in our understanding both of the system as a whole and of most of our
Environmental Management
31
individual “facts.” There is actually nothing wrong with an uncertain situation; in fact, our
economic system and our national security systems function tolerably well under admitted un-
certainty. The Apollo missions reached themoon and returned safely under conditions of un-
certainty. Decisions under uncertainty are quite possible: the recognition of uncertainty simply
requires some adjustments to our decision pattern. Indeed, the bulk of decision theories address
this uncertainty directly, either in factoring in the possibility that multiple outcomes may occur
(through weighting) or through safety factors.
The more serious error is to conduct business under uncertain conditions as if there were
no uncertainty. Unfortunately, in many cases, environmental policies have been devised and
implemented in exactly that manner.For instance, one of the primary“rules” that dominated
implementation of the Superfund program was the “worst-first”rule, under which priority of
effort was givento the most hazardous known contaminated sites. Thisrule was implemented
through a detailed process resulting in a numeric score that was deemed at the time to be some-
how a measure of the site’s risk. As detailed site investigations were pursued, it began to appear
that in many cases the scores did not reflect risk at all [12]. Part of the reason for this is that
the scoring system used is mathematically skewed so that the worst are probably not first[13].
Subsequently, the EPA issued a revision of its scoring systems, but EPA is refusing to rescore
the sites now found on the National Priorities List. Although the reasonsfor that decision are
more related to politics and face saving, it forms a good example of the fact that under uncer-
tainty the desired or statistically most likely outcome may not in fact occur.
In addition to using expected value methodologies to overcome statistical uncertainty prob-
lems, the technique for calculating the valueof perfect information is one with which all en-
vironmental decision makers should be familiar (at least in concept). The specific equation is
not particularly relevant, because there is often no “variance” (one of the terms in the perfect
information equation) in environmental data, which tend to be highly site-specific.But a great
portion of the funds in environmental activities are expended on “just one more round of test-
ing,” a round that generally proves as inconclusive as the original round.
There are a numberof activities that are worthwhileof themselves but very much subject
to the question of perfect information. Facility managers are asked to comb large tracts of land
looking for endangered species that might be there but often are not. Products are banned or
consigned to expensive disposal programs because they might be dangerous. Although protec-
tive measures are laudatory, all environmental professionals (whether they are regulators, fa-
cility managers,or taking the public’s perspective) need to be conscious of the fact thatat some
point enough is enough. Part of any action discussion should be an explicit understanding of
what “enough” is, what (specifically) is expectedto be gained by achieving “enough” as op-
posed to some lower level of effort, and what the costs and other implications of getting to
“enough” will be.
C. DynamicUncertainty
Many managerial texts address uncertainty as if it remained constant, albeit unknown. In the
environmental world, things do not remain the same. Technology advances or is discovered
to be ineffective, regulatory requirements change, the ecosystem changes, and specific activ-
ities evolve. Additionally, many decision theory models assume a single decision, even if a
protracted and complex one. Environmental compliance activities often do not fit this mold.
They occur within a continually evolving process where the outcomeat any point is dictated
As a result, more complex mod-
only inpart by the objective facts of the original circumstance.
els than the basic decision tree are needed to deal with the statistical uncertainty facedby en-
vironmental managers.
32 Brawn
As an example, compliance requirementsfor wastewater treatment facilities have changed

only superficially over the past two decades. Therefore, techniques of static statistical analysis
are useful when looking at a large population(the view enjoyed by the EPA of a large number
of wastewater plants, for instance) because the baseline for sucha view has been well estab-
lished and changes slowly. And EPA-level decisions, because of the mission of regulation and
enforcement, addresshow to regulate entire populations andhow to scan those populations to
identify recalcitrants.
For a single facility, the domainof most environmental managers, this aggregate informa-
tion is of little value. Decisions are not made on how to comply; that has already been spelled
out. Generally, they are not made on whether to comply. The question is how to maintain the
operation in compliance with no deficiencies, or at least as few as are practical, in the face of
any number of unpredictable events.
The ability to comply with regulatory requirementsis only partially a result of the original
adequacy of a plant’s technical design (the only static aspect of the operation). Much more
important are a myriad of specificcircumstances arising, or not arising, onanygiven
day. What is needed is a model of the entire system in operation, from water flow produc-
tion to effluent disposal, so that each point wherea problem might occur can be identified and
dealt with.
Even wherea violation may occur, itdoes not follow that an enforcement action will result.
That too isa dynamic process, dependentin part on theplant’s record from the past, on team-
building efforts by the regulated facilitystaff, on the sheer coincidence of inspection scheduling
on days when the facility does or does not suffer a reversal of fortune, and on whether or not
the facility has implemented anyof the improvements recommendedby the regulators on their
previous visits.
This situation, in which the probabilistic variables themselves vary over time, can only be
addressed by simulation tools. Such tools can represent the running of a scenario over multiple
iterations to represent the effects of the passage of time or to try out the effect of assigning
different probabilities to variables.Thus, in addition to the decision trees and contingency ta-
bles often found in managerial textbooks, simulation techniques must be employed.
Generally, managerial texts restrict their discussion (if any) of simulations to the Monte
Carlo technique. This does providea very powerful tool. However, even in its most basic form
it requires recomputationof known equations in a number of iterations, which effectivelyde-
mands automated tools. As simulationsare being applied to increasingly challenging problems
in industry and commerce, the computational power of simulations is being enhanced with
graphics to provide comprehensibility to problems and solutions thatwould otherwise be noth-
ing but piles of computer printout.
For environmental purposes,which tend to address problemsan order of magnitude more
complex than industrial process modeling, dynamicsimulations that incorporate visual effects
are needed both to complete a reasonably accurate representation and to enable the functional
manager to see what the computer is trying to communicate. Itis also important to understand
that elaborate graphical presentations, even though they may be very data-intensive, are not
useful to a rational decision processunless they canbe used to develop relationships among the
data. High-end geographic information systems generally display informationin multiple lay-
ers, making it accessible to intuitive analysis. They may provide a database management sys-
tem that permits the display of selected information, but usually they have no capacity for
mathematical analysis.
Simulation tools are very rarely found in environmental use, despitetheir obvious utility.
One reason is the complexity of environmental issues,which often forcesa long tool develop-
Environmental 33
Management
ment time. Also, the policy system under which simulations are developed (asmany withother
areas of environmental activity) allows for endless researchand refinement rather than prod-
uct fielding.
Another reason is that a circular logic is in place. There is understandable reluctance at the
EPA to certify any software products that have not been thoroughly validated by the EPA. How-
ever, the experience of many producers with the EPA’s unwillingness to accept anyway but the
EPA way has made them wary of attempting to present EPA with any new products or ap-
proaches, and warier still of investing in the creation of newsuchways until the EPA approves
the product for general use. As a result, managerial innovation is restricted.
The final reason is that formany environmental managers on the job today, the computer
remains a fearsome tool. But the very complexity of environmental issues and the increasing
cost of environmental solutions will soon make an effective decision-making process depen-
dent on the ability to exploit the
power of automation. More familiarity with the use, applica-
tions, and abuse of computers in general and simulations in particular is requiredof environ-
mental professionals.
D. OutcomeUncertainty
Outcome uncertaintyis technical talk that means basically we have no idea of whether, how, or
when things might happen, although we may be able to make some guesses as to what the
things that might happen are. Under outcome uncertainty, we are forced into more subjective
decision-making processes. The “aspiration level” approach [6] is seldom acknowledged but
frequently seen. In such an approach, not having confidencein predictions of what may hap-
pen, and finding the risk unacceptable, we decide t6 guard against the worst possible event.
Thisislikethe U.S. defensestrategy:anuclearattack by theformerSovietUnion
wasalwaysconsideredextremelyunlikely,butthepotentialdamagethatsuchanattack
could cause was so great that we spent enormous sums protecting ourselvesas best we could
from such an event, even though we knew that by doing so many other needs would simply
have to go unaddressed. The present worst-first policy is also an aspiration-level policy: it as-
sumes that we know little about costs and remedies of cleanups, but we believe that we have
identified the worst situations and we are committed to removing those situations, beginning
with the worst.
Even under such conditions, however, cost-’benefit considerations are at work, although
less obviously; they are squeezed in through the back door using the potential for public outrage
as the vehicle. We accepted the cost of the defense programas necessary in conceptand gen-
erally affordable. And our national policy is to save endangered species. However, where a
human community must give up its current livelihood in order to save a species (as is threat-
ened in the effort to preserve the spotted owl habitat), the regulation enters the political arena
where the EPA may win or it may lose. The contest willbe presented to the public on the one
hand as preservation of the quality of human life in preference to unproven allegations of harm
to what is onlyone of millions of species, and on the other hand as preservation of defenseless
creatures against greedand callousness. The essence of this argument is the cost-effectiveness
of the effort: is the public willing topay the price for a particular environmental project?
Another methodof dealing with uncertainty is subjective decision making using group pro-
cesses. There are any number of approaches available, from public meetings and roundtables to
expert opinions eitheras individual contributionsor controlled through a Delphic process.An
example of the weighting of subjective preferences is seen in the U.S. Department of Energy
(DOE) approachto its overall capital facilities investment strategy[14]. Successful results (as
34 Brown
proven by the subsequent accuracy of the predictions) have been experienced with using an
even more structured approach known as the analytical hierarchy process (for instance, our
work on community fiscal impact analysis [15]). TheEPA has begun looking into that process
in its negotiations withthe U.S. Department of Energy over howDOEwill conduct its cleanup
operations [16]. The process in a nutshell is that stakeholders and/or experts cometo agreement
over the relative significance of factors taken two at a time;at the end of making many such
comparisons, the relative significance of each of the factors can be mathematically arrayed into
a numerical weight table.
Another perfectly valid approach under uncertainty is problem avoidance, an extreme form
of the minimax principle in which we minimize the maximum cost without much concern for
probable benefits. If the issues and the costs are imperfectly defined, or if the impact of the
events (including enforcement) is seen as unlikely or highly arbitrary, the whole system may
not be worth worrying about. It is probably cheaper to be dragged intocourt from timeto time
than to go around solving problems that may not exist. In our view,is thisprecisely the strategy
in place among many producers today. We have named it “problem avoidance,” although one
could also characterize it as foot dragging or passive resistance.
E.TotalUncertainty
The final possible approach, under total uncertainty (if we have little confidence in the risk
data or the cost data), is to simply allocate the available funds on some arbitrary or politi-
cally acceptable basis and hope for the best. That division may occur on a social basis or
on a geographical basis,and there are some suggestions that this is exactly what is occurring,
either deliberately or as a consequence of the problem avoidance strategy. However, using
similar arguments to achieve the opposite result (as in the present enthusiasm over racial equity
in environmental issues) is analytically no more pure than the original failure. The approach
is not covered as fully as others in this text because such issues are not amenable to environ-
mental management and because there is some evidence that, at least in the Superfund pro-
gram, fundsdo flow to higher scoringsites [17]. However, the environmental manager must be
aware that such a schoolof thought exists and that when skillfully used it can awaken powerful
political pressures.
W. HOW CERTAIN IS ENVIRONMENTAL SCIENCE?

The range of approaches notedin Section I11 varies according to the amount of certainty that
or there would be no need for so many approaches.
is attached to the situation. Clearly, it varies
In this section, we briefly consider some of the issues that lend uncertainty tomany cases.
Each of the major objectivesto be accomplished is still subject
to considerable controversy.
Research needs to be applied in each of those areas if we are to move forward effectively in
managing the environment andto move from the imaginary certaintyof acting “as if” (when
really acting under outcome uncertainty if not total uncertainty) to at least acting under sta-
tistical Uncertainty. The following brief summary is provided hereto allow the environmental
manager a glimpse of all that we do not know.
A. Risk
The definition of chemicals as hazardous is done through a series of separate environmental
of threat. In many cases, two chemicals have over-
regulations, and there is little comparability
lapping effects levels: the question becomes whether it is worse to die immediatelyor to get
Environmental Management35
lung cancer. In such cases, how do we establish “worse”? Even when we stick with a single
chemical class, there is a great deal
of doubt as to what risk, if any, a regulated material poses.
While the chemical data are confusing and contradictory (see, e.g., reference 18, from which
the original Hazard Ranking System (HRS) factors were derived,or reference 19), we cannot
always rely on the accepted approximation systems: current measurement systems (the original
and revised HRS) cannot be shown to approximate risk. In our earlier paper [13], we showed
that the original HRS was mathematically inconsistent, leading notto the potential but to the
actuality of score inversion. While the’revised system corrected several glaring deficiencies of
the original system, there are enough departures from the generally accepted threat-pathway-
dose-receptor paradigm to raise doubts as to whether risk is related to cost under the revised
scoring scheme.
B. Cost
Given a reasonably accurate description of the problem, a reasonably accurate cost estimate
should be possible for the engineering cost of the remedy.A common criticismof current mod-
els is that they are usually off by 50% or more and usually understate the final cost. This is
partly because of the lackof data points, partly a resultof inaccurate input, and partly dueto
the continuing ballooning of legal intervention costs. However, it should be noted that a 50%
error may be less than the current errors in risk estimation.
C.
Time
Time has interesting impacts on environmental decision making thatto need be explored. Time,
for instance, is tied to risk issues. Givenlow risks now and high long-term risks, or moderate
transient risks now, how do we choose? What about the tendencyof pollution problems to ex-
pand over time?
Time has extensive impacts on the cost side of our decision model. What does the slope of
the environmental learning curve look like? What is the real rate of environmental inflation,
and can it be separated into its components: engineering, legal, procedural, and so on? Even
more significantly, what would be the most appropriate way to integrate the concerns into a
decision model, even if the answers were known?
D. Acceptability
A great deal of work remains to be done in the integration of legitimate political and public
concerns into the decision process. If political distribution of benefits is a real show-stopping
issue, how can that be integrated into a decision process in an open manner so that it can be
assigned a proportionate role?Is the distribution of pollution problems consistent with indus-
trialization and hence with population density, and does this ensure an acceptably proportionate
share in the program?How do we distinguish between self-interested “NIMBY-ism” and valid
public safety issues, or does it not really matter?
E. Deterrence
Generally, deterrence is achieved through a combinationof other objectives: effective defini-
tion of the risk factors, approaches that maximize the benefits of compliance, and a smooth
administrative process that makes apprehension more likely. A great deal of research is going
on today on the question of the right amount of fees to charge polluters.
Less research addresses
the questionof how to make producers stop polluting altogether and what the costs of checking
on it are.
36 Brown
F. Administration
Research into the other bureaucratic goal-administrative smoothness-would be well served.
The primary attraction of the “as-if‘’ approaches are that they are very easy to administer.
HRS, for instance,is self-operated by polluters or agency contractors;sites simply go on a list.
No effort has to be expended by the agency on the messy questions of cost, time, risk assess-
ment, and so on; all of that is up to the polluter. From the producers* perspective, problem
avoidance has advantages administratively because one hasto fund only whatever the agency
requires, so there is little need for decision making and a good probability that the major ex-
pense of restoration canbe spread out overan almost indefinite period of time. But the primary
reason for such behavior is that the process required to do anything else is so convoluted that
it is not worththe cost. The simple actof declaring that a site should not be listed as dangerous
becomes a very expensive process. Research is needed to address the valueof each of the ex-
isting steps of the process and todetermine whether it is possible to design a less cumbersome
administrative process with less reliance litigation
on that still protectsthe interestsof the agen-
cies and the producers.
G. Practicalities
Practical problems include the capacityof the environmental industry to handlethe workload,
the availability of technology, the capability of project managers to handle projects above a
certain size and speed, and the limited experience at all levels with actually executing many
types of environmental activities.
There are plenty of other practical issues within the scope of today’s feasible actions. Are
existing contract vehicles adequate? To what standards should contractors be held, and how
effectively can they be managed? What are the lessons learned from past programs, andhow
are they being disseminated? Answersto any of these questions would improve the process of
planning and executing environmental cleanup.
V. DECISION APPROACHES AND ENVIRONMENTAL OBJECTIVES

We noted earlier that there are several possible objectives for environmental programs and the
people and organizations charged with carrying out those programs.How do the approaches we
have discussed meetthose objectives?
Table 3 compares the major approaches in terms of the objectives of the environmental
program. The table shows a plus sign where the approach enhances that objective, a minus sign
where it detracts from an objective, and a zero where it has no effect.
The single-rule approach (exemplifiedby the Superfund worst-firstrule) addresses the risk
and acceptability issues by focusing onthe worst cases. In ignoringcertain other objectives, the
single-rule case in particular engenders a number of practical problems. Most notably, ignoring
cost issues results in a number of cases of self-protective evasion by responsible parties. In
addition, an oversimplified approach ignoresmany other practical limitations, such as the ca-
pacity of the environmental industry to undertake many projects or the availability of reliable
technology with which to do the work. And it ignores the value of time in terms of inflation,
opportunity costs, and continued public exposure to hazards.
More recent policies (if not many efforts) have focused on maximizing risk reduction[20],
a multiple-rule policy based on both risk and cost. Cost as a consideration at least forces in-
direct considerationof some unspecified issues. Effectively performed cost estimates will need
to consider practicality andthe value of time, as a minimum. Such policies will necessarily be
Environmental 37
Management
Table 3 Decisions and EnvironmentalObjectives

Static
Multiple
(expected
Aspiration
Single
Subjective
mle
rule value) Simulation
weighting
level Maximin Politics
Risk reduction + + + + +- - - -
cost - + + + 0 +- 0
Time - + + + - 0 +
Acceptability + 0 0 + + + 0 +
Deterrence + + 0 + + 0 - -
Administration + + - 0 +- - - -
Practicalities - + + + + + 0
Key: +, enhances: - deqacts; 0, no impact.
more complexto administer and may, because of their complexity, be less acceptable. Indeed,
in the chart shown in Table 3, the multiple-rule-based approach appears almost ideal, with
many pluses and no minuses. But this assumes that the rules can be developed in such a way
as to enhance the objective, in short, that we are operating with certainty, which as we have
noted above is usually not the case at all. '
Operating under statistical uncertainty,we find that a more detailed understanding of the
variables should result in a more targeted approach to the problemto be solved; thus risk, cost,
time, and practicality are well addressed. The added complexity of the approach makes it less
acceptable until it proves its worth. Likewise, deterrence may be stronger after the approach
has been proved but will initially be poorer than a straightforward policy until it proves effec-
tive. And of course such a policy will always be complicated to administer.
Introducing the dynamic aspect of uncertaintywould be a policy disaster without the ap-
propriate tools. While an academic case might be made for the power of formal automated
modeling and simulation in enhancing almost every objective except administration, the lack of
appeal of a massive computer printout (often the only form of output available) would make it
untenable to either politicians or bureau executives. However, given the right tool (a powerful
simulation engine with an attractive graphic interface), this method becomes very useful. The
scoring in Table3 reflects this latter case. The effectiveness of a good simulation can helpto
account for practical constraints and can maximize risk reductions while minimizing time and
money spent. This also maximizes the policy's deterrent effect. Effective graphics can make
the conclusions more acceptable to both politiciansand the public, and a well-programmed tool
will ease the administrative taskby making the decision rationale cleareror perhaps providing
a recommendation.
So, why is everybody not using such tools? As noted earlier, the EPA often refuses to en-
dorse them, and wisely so because the state of the science is such thatone can barely be said
to be operating under statistical uncertainty. A case of outcome uncertainty is more often
the case. Earlier, three typical approaches were noted under outcome uncertainty. The worst-
first policy is an aspiration-level choice if we confess that not much is known about risks or
that we care little for costs. This has the principal advantage of addressing the mission di-
rectly: every effort will be expended to meet it. This may also be well accepted until it starts
to cost too much, which in the case of the environment it will. In fact, in every way, its
strengths and weaknesses (as shown in Table3) parallel those of the single-rule-based decision;
indeed it differs only in that the single rule assumes that the outcome is known, whereas the
aspiration level accepts the risk that the outcome may not transpire but feels it to be worth
guarding against.
38 Brown
Environmental management today is taking a close look at subjective decision making.

The principal vehicle for this in recent efforts has been the analytic hierarchy process (pairwise
comparisons). In addition to being used with some success (in terms of acceptability to activists
and regulators alike)at the state level, it is under development now between DOE and EPA. It
maximizes participationearly in the processby the groups that most delay action through legal
and regulatory maneuvering. Because all parties have an opportunity to participate in the
decision-making process, and a properly designed process will leave few completely disgrun-
tled, all are co-opted into the solution. Those few who continue their challenges will have lim-
ited credibility given the ecumenical composition of those who have agreedto the solution. In
addition, the process can create a rule-based framework with which to make decisions, giving
the illusion of a quantitative universal solution under certainty.
This capability also presents the biggest trap presentedby the method. As a rule, the pro-
cess is conducted in conjunction with computer programs to present the questions, record the
opinions, and perform the weighting calculations. The programs sell themselves with a pleas-
ing and simple interface that encourages their use by novices, but the comparison structure
must be set up very carefully. This has often been overlooked, with the result that the com-
parisons are inherently flawed.
Even where the analysis is properly performed, the illusion of quantified objectivity re-
mains. Decisionsby subjective processes necessarily mean that objective information is lacking
or inadequate. The form placed on the structure simply provides a facade of quantifiability. In
fact, however, the process is structuring a political decision, made in this case by consensus
among expertsor activists rather than duly elected or appointed authority. While there is noth-
ing wrong with that, it is important to recognize it for the political process that it is. In short,
subjective decisions maximize political acceptanceand basically admit a lack of hard knowl-
edge in other areas, especially the core objective.
Finally, within outcome uncertainty, there is the minimax approach, principally repre-
sented in environmental policyby problem avoidance. This approach is characterized by con-
tinually seekingnew facts while making temporary investments to control the spread of definite
risks. Since nothing is actually accomplished by this, the final cost of a solution is unaffected,
and becauseof the tendency for environmental problems to diffuse themselves that cost may be
much higher althoughthe payment date is set further into the future. The primary positive out-
puts of delay are that it can be given an acceptable facade, through continuing studies (espe-
cially ifnobody isconcernedaboutcosts), and itminimizestheopportunitycosttothe
organization, which is free to go about its business with minimal budgetary impact. In terms
of our objective function, problem avoidance deals with neither risk nor effectiveness, but in a
perverse sort of way it does keep an eye on costs, at least in current years, by simply refusing
to do the needed work.
Finally, there is the straightforward political approach. As far as we know fromthe limited
studies available, thisis seldom seen (environmental equity authors might differ with that state-
ment). An arbitrary decision by an administrator has the same effect. In suchcases, the basis
for the decisionrules is very different from thosewe have noted so far and is unlikely tomax-
imize any value except political acceptability.
VI. APPLICATIONS OF THE DECISION MODELS

In the remainder of this chapterwe review five applications of decision theoryto a single en-
vironmental problem: investment decisions. Those applications are the use of a singlerule and
the use of multiple rules under certainty, the useof an expected value approach in a dynamic
statistical uncertainty mode, and the use of public opinion under uncertainty. However, the
Environmental 39
Management
state of management science within the environmental field is such that only decisions under
certainty can be reviewed in any detail: the other approaches are still being considered but do
not as yet represent any official policy.
A. Certainty
The first cases to be analyzed use rules to solve the capital allocation question. Theobjective
of this exercise is to conduct remediationwork on a group of toxic waste sites that exceeds our
ability to pay. One approach is to use a single rule: worst-first. Under that rule, all available
resources will be focused on the site posing the worst risk to public health. Remaining funds
will be applied to the next-worst site, and so on.
An aIternative approachappliesmultiple rules, or at least a morecomplexrule.In
this case, the rules are that all available funds will be devotedin sequential priority to the site
where the risk reduction per dollar is the maximum. Once work ona site is started under this
formula it must be finished. Thisrule is called the “results-first” rule [l]. The situation to be
addressed is displayed in Table 4, where a third approach is also displayed for convenience.
That approach, problem avoidance, is in a way a rule-based approach (do the minimum nec-
essary for as long as possible) but, as was described earlier,is a manifestation of an approach
under uncertainty.
1. Applying the Rules to a Hypothetical Problem

Table 4 shows a notional five-site universe given a budget of 100 money units (call them mil-
lions of dollars, if you will). It provides the agreed risk (in whatever units) posedby each site
and the estimated cost to restore each. Additionally, the table shows the cost of “doing noth-
ing” at each site:these are the costs of the minimum essential security measures,studies, mon-
itoring, and so on (not to mention legal fees) that must be carried out even when no action is
possible or desired.
Under the worst-firstapproach, only the site risk needbeknown.Wewould attempt
to fund site A first; with luck, the sumof the studies over the next 12 years would result
in a partial resolution of the problem, but it is more likely that at the end of the period we
would have to spend another 800 units of money to execute the remedy (requiring several
yearstoaccomplish, at a rate of 100 unitsperyear).Meantime,nothing else could have
been accomplished because the balance of our funds each year (20 units) is insufficient to
remediate the next site, B. Note also that remediation at either site C or E, which could have
been completed with the residual funds, willnotbeaddressed because these sites are not
“worst first.”
Table 4 Example of Approaches”

Project Risk Cleanup cost Risk/$ Avoidance cost
A 100 800 0.12 80
B 70 35 2 8
C 60 20 3 3
Db 40 80 0.5 40
E 20 4 5 1
Total budget available = IOO/yr.
bPmject D is already under way.
Source: Brown et al. [l].
40 Brown
The table shows the risk reduction per dollar ratio, which isthemeasureneededfor
a results-first decision. This is quite simply the risk dividedby the cost. There is one twist to
this: project D was already started, andwe assume that 40 money units has already been
expended on it. That is, its total cost was originally greater than 80 units and so its ratio was
evenlessthanone-half.Unfortunately, we haveauniqueenoughsituation at Dthatsim-
ply keeping it alive through studies is up to one-half as expensive as finishing it up (a situation
that occurs more frequently than one might think). Using results first, we see that the best risk
reduction per dollar gives the highest ratio, making our order of preference E, C, B, D, and
then A. Withthis preference, wesee that within our budgetwe can complete projects E, C, and
B. We also have 41 units left over to fund some of the work at A and D. By the end of the
second year we would have completed all the sites except A, and we would be left with the
same problem as in the worst-first case-the inability to restore A-except that while only be-
ing 2 years further behind at A (which had not really gone anywhere anyway), we have com-
pleted all our other work and in the process we may have learned something abouthow to deal
with site A.
Problem avoidance would require us to fund studiesat all sitesand to finishD, since work
there was already started and it is too much trouble to stop. In either case, we do not have
enough money to do the full studies requiredat A, so we skimp along on whatwe do have after
funding everything else. This does happen in practice, since the durationand scope of tests and
studies are fairly arbitrary and highly negotiable. The result of this strategy is that site D,
which offers one of the lowest returns in risk reduction per dollaras well as being a relatively
low ranking site, is the only one cleaned up, because every year the entire budget is consumed
in studies. After4 years, we have spentas much in studiesat site E as we will eventually spend
in cleaning it up-another event that is not infrequent in reality. Witness the fact that most
of the sites removed from the National Priorities List have not been the “worst” sites that
should have been first, but rather sites that proved after ofyears expensive studiesto have posed
little risk.
2. ApplyingRealData
Setting up Table 4 for illustrative purposeswas easy enough butmay be considered to be mis-
leading. Would the superiority of a results-first approach be demonstrated with real data?An
analysis was performed using the scoring data from1600sites containedin the EPA’s National
Priorities List Technical Data Files database, and estimated remediation costs were extracted
from the 523 then-existing records of decision (RODs).The result was a joint database of 412
unique sites with cost data (some RODs are for operable units within sites or are updates of
earlier RODs). These data are acknowledged to be less than perfect. Aside from the fact that
the HRS score may not really be a measure of risk, in some cases the factor valuesmay have
been improperly assigned during the site assessment and scoring processes. The costs are quite
fluid. More important, itis not always clear in the ROD whether data the for operable units are
cumulative or separate (one can sometimes get enough of an impression to know that either is
used on occasion), so that the decision to add to or replace the previously recorded cost is
subject to error.
The model uses an arbitrary cleanup budget ranging from 1 to 3 billion dollars per year
over a 30-year period, reflecting the reasonable expected range of Superfund appropriations
(presently being scaled back from of $5
$2 billion). In addition, no more than an arbitrary limit
million per year maybe spent onany one site; this limitation was designed to preventmodel the
from miraculously fixing a complex site suchas Commencement Bay or Rocky Mountain Ar-
senalinoneyearwithamassiveinfusion of cash.In fact, theenvironmentalprogram
Environmental Management 41
Table 5 ResultsUsing NPL Data

Worst-first
Results-first
Results
ratio
Sites cleaned 5 69 1 41
HRS points reduced 365 2,877 8:I
Total risk reduction including 5,608 69,989 12:1
time effect
Source: Brown et al. [l].
has shown someof the same tendency to throwaway money underoverstimulation aswas seen
in the Defense Departmentin the 1980s: sometimes thereis a limit to how much money one can
spend wisely in a given period. Finally,the model recognizes the continuationof risk incurred
by failure to remediate.
Because of the funding limitby time period, and because of the life-cycle risk approach,
the model requires an iterative solution based on the initial decision rules. It is important for
environmental managersto note, however, that this relatively complex calculation canbe (and
was, for this exercise) accommodated with plain old dBase 111 Plus rather than using a more
complex simulationtool. The working of the model is described in more detail in reference 1.
The simulation determined which projects were to be funded in each year using the one-
rule and multiple-rule methodologies. The results are shown in Table 5 . Clearly, a more so-
phisticated rule system that acknowledges the effect of realistic constraints (i.e., resource
limitations) outperforms onethat adheres more closely tothe original goal.
One might argue that for the specific sites we have selected, the HRS scores do not rep-
resent risk and do not represent toxicity or time effects. However, the purpose of this analysis
is not to show how many HRS points can be cleaned up or what strategic approach is superior.
Rather, it is to point out that effective management depends on effective identification of ob-
jectives, requirements, resources, and constraints. The use of tools because they are simpler
(such as a one-rule system)will often be less productivethan the use of tools that more closely
reflect real conditions. The manager’sjob is to identify the relevant aspectsof any decision and
to ensure that all aspects are properly considered.
B. StatisticalUncertainty
The rule-based system just described was fairly complex, even when operating with the as-
sumption of certainty. Incorporating probabilities or ranges of values into such a model as the
multiple-rule model would require automated systems support. There are many models in ex-
istence that assist in the solution of particular problems. There are few, however, that provide
information to a manager before an event occurs.The EPA’s CAMEO model may be the best
known; designed for emergency response use, it can be used for “what-if” analysis under se-
lected circumstances. (Contact theUSEPA Office of Solid Waste and Emergency Response in
Washington, DC., for additional informationon CAMEO.) Even with CAMEO, however, the
situation needs to be specified quite closely.
Other “screening” models have been produced under various development initiatives by
the EPA and by private vendors; those models generally addressa specific pollution mode (air,
soil, surface water, or groundwater) and usually address fate and transport issues rather than
providing impact analyses. In addition, many site-specific models have been developedfor in-
dividual environmental projects,and in a number of cases those models have been placed inthe
42 Brown
public domain in case they may be found useful. In other words, there are literally hundreds of
dynamic models available; some address known
a situation over time,and some aremuch more
s~phisticated.~
What is needed is a simulation capability that can portray sources and receptors and model
pathway behavior. Unfortunately,at present the Geographic Information System (GIS) systems
that contain the needed data cannot be interfaced with the programs that replicate the pathways.
Some systems development is under way that may help in this area [21]. The requirement is for
a system that will represent the behavior not of a single site, but of a typical environmental
situation with multiple potential sources and receptors. Such a model must include the possi-
bility that currently contained sources may fail, must allow for changes to be made to reflect
proposed upgradesor corrective actions, and must be able to correlate these activities to costs.
Finally, the systemmust be visually interpretable and preferably simple to use. These require-
ments will not be simple to meet, which is why there are no such systems today.
C. Outcome Uncertainty
It was demonstrated earlier that the problem avoidance (minimax) strategyis self-defeating in
environmental operations because in many cases it costs almost as much to do the minimum
(once the effectof time is considered) as it does to go ahead and take careof the problem. We
have also seen, thanks to the “worst-first” model under certainty, that aspiration-level ap-
proaches (which may be expressed as “just do it”) may well fall apart when faced with the
reality of resource or capacity constraints. In fact, the very insistence on mission focus at the
expense of realism results in less of the actual mission being accomplished than in the more
realistic multiple-rule or expected value approach.
This leaves the subjective decision-making approach. This method of analysis is receiv-
ing increasing attention. Two effortsaddressingcapitalfacilitiesdemonstratedifferentap-
proaches. The first is theEPA’s effort to develop policies for DOE facilities. EPA DOE’Sand use
of such an approach was encouraged by the successof earlier efforts in developing underground
storage tank replacement strategies at the state level, with New Mexico being the leader in
this regard.
1. AnalyticHierarchy
The analytic hierarchy process(AHP), often known as “pairwise comparison,” works by con-
sidering all of the factors involved in reaching a decision and comparing their relative im-
portance in that decision. For instance, when trying to select an item of equipment, one
may consider purchase cost, reliability, and efficiency. Then these elements are compared.
One could just assign weights directly; AHP assumes that effective quantitative judgments on
these qualitative issues wouldbe illusory. Instead, the participants are asked to assess the rel-
ative importanceof one factor over another. Based on the amount by which one element is said
to be more important than another, a weight is established (unseen to the participants) for each
factor. Factors can be tiered: thus, each factormay have subordinate indicators (in the example
above, reliability may be assessed in terms of both manufacturer’s advertised mean time to
failure and the corporate experience with similar machines, with one rated more heavily than
the other).
’A helpful referenceis the USEPA Informution Resources Directory, publishedby the Information and Resources Man-
agement Division of the USEPA. My copy is document number OPA 003-89. March 1989, but newer versions may
subsequently be published under different document numbers.
43
The apparent simplicity of the AHP method is deceptive.It leads people who are not very
familiar withit to attempt its use, and because the result is produced by the computer to three
decimal places it has the aura of authenticity.
But if the factors are improperly constructed, the
result willbe meaningless. While the computer can assess the technical consistency of the rank-
ings with each other based on the pairwise comparisons, it cannot answer whether the com-
parisons were meaningful. The best test of structure is to ask the same question the software
asks; using the example above,“In assessing whatequipment to buy, which is more important:
reliability or flciency?” If the sentence with the blanks filled in seems nonsensical, the struc-
ture may be improper. Another indication of a problem with the structure of the model, or a
lack of general understanding of the issues, is the finding of generally very high or very low
scores (near 0% and 100% weighting) for numerous factors.
In theEPA’s implementation of the Risk Information System (RIS), the major factors were
health impacts and environmental impacts. Tiered beneath these were various intervals within
which pollution would be expected to arrive. These in turn were constructed in terms of the
individual and population risks, which in turn had three layers of other indicators. In early
efforts, the panels returned numerous zero-weight responses; where decision trees have only
two branches, eliminationof one branch renders the decisiontree useless. To the EPA’s credit,
they recognized the problem this created and went back to review the model structure; at the
time of writing, the revision has not been published.
This servesto reinforce the point made earlier in offering multiple decision models: not all
will work in every situation. When the model doesn’t work, one has to make assumptions to
develop the best possible outcome. Criticalto that process, of course, is to recognize the fact
that assumptions have beenmade.
2. WeightingWithoutAHP
An alternative formulationof the same problem came from DOE‘SResource Allocation Support
System (RASS) project. In this case, DOE did not use the AHP approach, electing instead to
rate the need for facilities based on a series of scales, each scale having a weight of its own and
the raw data being used to construct the scales being weighted within each scale.
Raw data supplied by local managers to describe their proposed project were converted to
scales presented as “letter grades.” The siting strategy considered four primary factors: cost,
health issues, the volume of waste that an alternative could handle, and the degree to which the
alternative complied with applicable regulations. An extensive amountof preparation would be
required to obtain the raw data needed to make the system work. However, it was not intended
as a detailed engineering analysisas much as a first-tier estimate to allow general project de-
cisions and funding allocations tobe made.
This process in still in the pilot project phase, and a report on the results is not yet avail-
able. The item that environmental managers should consider in using such a system is whether
it is in fact appropriate to the problem to be solved. The difference between the RASS appli-
cation and the AHP-based RIS application is that RIS attempted to capture nonquantifiable
values and norms (the relative significanceof carcinogenic and noncarcinogenic pollution, for
instance). RASS deals exclusively with highly quantifiable values (waste tons, costs, etc.).
Considering that the compliance question is really fairly irrelevant,as no facility will be per-
mitted that does not comply with all applicable regulations, one could ask whether the objec-
tive function could have been simplified to maximize the waste or risk reduction (as was
demonstrated in the “results-first” model) without need the for a weighting system that distorts
the true dimensional valuesof the data. Nonetheless, the RASS approach is a relatively com-
plete attack on a multifaceted problem and is worthy of consideration as an approachto solving
environmental problems.
44 Brown
VII. CONCLUSION
This chapter does not answer any questions about the environment. has,Ithopefully, stimulated
a number of questions about how decisions are madeand what basis is offered for those deci-
sions. Environmental managers needto understand the full range of tools available for decision
support. More important, they need to understand the degree to which the way in which the
objective is stated caninfluence the choice of decisionapproachandhence the solution
adopted. And they need to be aware of the strengthsand limitations both of the decision meth-
ods employed and of the data used to support those decisions.
Few decisions will ever satisfy all parties involved in such a complex and controversial
policy area as the environment. Elaborate mathematical proofs, eye-catching simulations, or
cutely worded weighting scales will neither improve the decision nor overcomethe reluctance
of an opponent to concede that a position has some merit. But a better understanding of the
premises used to arrive at a decision can ensurethat discussions of the decision are based on
the same understandingof the problem,an essential first step in arriving at a sustainable public
policy decision.
ACKNOWLEDGMENTS
This chapter represents a significant advancementfrom, but nonetheless capitalizes onmany of
the frameworks and concepts found inan earlier article [l]. The permissionof Hazardous Ma-
terial Control to reproduce major portions of the text of that article are gratefully acknowl-
edged.
REFERENCES
1. Brown, D. M., Dienemann, P. F.,and Kline, R. C., Results first: an enhancement of the worst-first
approach, Hazardous Mater. Control, 5(4): 20-33 (1992).
2. Hembra, R. L. (U.S. EPA), The need to establish environmental priorities, presentedat the South-
eastern Conference on Public Administration, Am. Soc. Public Administration, Charlotte, N.C.
Oct.16,1991.
3. U.S. Environmental Protection Agency,Comparing Risks and Setting Environmental Priorities, Of-
fice of Policy, Planning and Education (PM-220). August 1989.
4. U.S. Environmental Protection Agency, Unfinished Business: A Comparative Assessment of Envi-
ronmental Problems, 1987.
5 . Hawkins, K. and Thomas, J. (eds.), Enforcing Regulation, Kluwer-Nijhoff, Boston, Mass. 1984.
6. Fleischer, G. A. Engineering Economy: Capital Allocation Theory, Wadsworth, Belmont, Calif.,
1984.
7. Lapin, L. L., Quantitative Methodsfor Business Decisions, 2nd e d . , Harcourt Brace Jovanovich,
NewYork,1981.
8. Quade, E. S., Analysis for Public Decisions, 2nd ed., North-Holland, New York, 1982.
9. Douglas, E. J., Managerial Economics: Theory, Practice and Problems, 2nd ed., Prentice-Hall,
Englewood Cliffs, N.J., 1983.
10. Weber, Max,c. 1922, Economy and Society: An Outline of Interpretive Society, edited and translated
by G . Roth and K. Wittich, 2nd e d . , University of California Press, Berkeley, Calif., 1955.
11. Simon, H. A., Administrative Behavior, 3rd ed., Free Press, New York, 1976.
12. Doty, C. B.andTravis,C.C., Is EPA's national priorities list correct? Environ. Sci. Technol.,
24( 12): 1778-1780 (1990).
13. Brown, D. M.,and Kline, R. C., Are the worst first? A review of national priority list sites, Proc.
Region VI Conf. Am. Soc. Public Administration.Dayton, Ohio, 3 Oct. 1991, pp. 87-104, Political
Science Department, Univ. Dayton, October 1991.
45
14. U.S. Department of Energy, Objectives, scales and scoring instructions for a pilot study of waste
management's resource allocation support system (RASS), draft, U.S. Dept. of Energy, German-
town, Md., June 1992. Contact Mr. Kevin Donovan of DoE for more information on the status of
the RASS study.
15. Moore, W. B., Brown, D. M., and Hutchinson. R. A., Updatedfiscal impact analysisfor the Naval
Submarine Base, Kings' Bay, Georgia, LMIRept.No.FF'605R1,LogisticsManagementInst.,
Bethesda, Md., December 1986.
16. Walsh, W., Susel, I., and Ronayne, A., Setting risk-based priorities: a method for ranking sites for
response, Proc. HMCRI R&D Conf. Anaheim, Calif., February 1991, HMCRI, Silver Spring, Md.,
1991, pp. 112-123.
17. Hird, J. A., Superfund expenditures and cleanup priorities: distributive policiesor the public inter-
est? J . Policy Anal. Manage., 4455-483 (1990).
18. Sax, I. N., Dangerous Properties of Industrial Materials, 5th ed., Van Nostrand Reinhold. New
York, 1979.
19. Weiss, G . , Hazardous Chemicals Data Book, 2nd ed., Noyes Data Corp., Park Ridge, N.J. 1986.
20. Fiorino, D. J., Can problems shape priorities? The case
of risk-based environmental planning, Pub-
lic Admin. Rev. 50( l): 82-90 (1989).
21. Brown, D. M., Integrated environmental management: a GIS system you can afford, Proc. HMC
Superfund 92 Conf. (Hazardous Materials Control and Research Institute), Washington, D.C., Dec.
1-3.1992.
4
Introduction to Engineering Evaluation
for Contaminated Sites
David S. Wilson, Alan C. Funk, Ronald G. Fender, and Marilyn Hewitt

Environmental Resources Management Group
Exton, Pennsylvania
1. CHARACTERISTICS OF ENVIRONMENTAL CONTAMINANTS

There are literally thousands of substances that can contaminate the environment. In some
cases, this contamination is related to natural conditions and is thus a “background” condi-
tion. Most often, however, environmental contaminants are related to human activity. Current
regulatory programs governing contaminated sites generally focus on a class of contaminants
called hazardous substances. These regulated substances have been identified by the United
States Environmental Protection Agency (USEPA) on the basis of their relative toxicity in the
environment. Many other substances may be released to the environment; some are unregu-
lated, and others may be regulated by agencies other than the USEPA.
Any given contaminated site is usually characterized by one primary contaminantor suite
of contaminants related to activities conducted at the site. This contaminant profile is often
referred to as the site “fingerprint.” Once this fingerprint hasbeen established by general en-
vironmental sampling and comprehensive chemical analysis, detailed studies of the site are
generally focused on the fingerprint compounds.
The contaminants present at any given site are highly dependent on the natureof the ac-
tivities at the site. For example, at chemical industry manufacturing facilities, a varietyof or-
ganic compoundsmay be present, whereasat a facility that does substantial electroplating, the
contaminants may be principally heavy metals. The electronics industry and metal products
industry will also commonly be characterized by the presence of organic solvents as environ-
mental contaminants. A wood-preserving operation, by contrast, would be characterized by
phenols and creosote-related compounds. A commercial hazardous waste disposal facility could
be characterized by any combination of organic and inorganic contaminants. A municipal waste
disposal landfill is generally characterizedby some amount of organic compounds and metals,
but mostly by liquid leachate containing organic acids, iron, and ammonia from the decom-
position of trash and garbage.
Environmental contaminants are generally divided into three classes:
47
48 Wilson et al.
Organic Compounds. These are human-produced compounds that do not occur naturally in
the environment to any significant degree.
Inorganic Compounds. Heavy metal ions are the principal concerns. Although these are nat-
urally occurring elements, human activity tends to concentrate them to levels that have
higher potential toxicity than natural levels. Other contaminants such as the anions chlo-
ride and sulfate are also inorganic contaminants. Inorganic contamination can also result in
environmentally unacceptablepH levels in the environment at some sites.
Biological. The principal concerns for biological contaminants are bacteria and pathogens as-
sociated with sewage. These are not generally concerns at contaminated sites related to
industrial or disposal activities.
A brief summary of the nature of common organic and inorganic contaminants follows.
A. Organic Contaminants
The USEPA divides organic contaminants intoclasses related to chemical characteristics that
drive required analytical methods. These classes are discussed below.
Volatile Organics
By far the most common environmental contaminants are volatile organic compounds (VOCs).
This is due to their presence in petroleum hydrocarbons that are widely used as fuel in our
society (gasoline, fuel oil, etc.) and to the almost universal use
by American industryof volatile
organic solvents for degreasing during manufacturing operations. Volatile organics are also
used as raw materials in some industrial processes, such as those of the pharmaceutical indus-
try. Table l presents USEPA's Target Compound List for VOCs.
Volatile organic compounds are characterized principally by their high vapor pressure, that
is, their tendency to volatilize to the gaseousstate at standard temperature and pressure. These
compounds are also characterizedby relatively low levels of water solubility, generally froma
few hundred parts per million 1% in water. However, due to toxicological characteristics, these
solubilities, although limited, are significant in terms of potential environmental and human
health impact. A third majorcharacteristic of volatile organic compounds is their specific grav-
ity. Those compounds without chlorine atoms tend to be lighter than water and therefore will
float. Compounds that have been chlorinatedare generally heavier than water and will sink in
water under the influence of gravity. This characteristic is very important in the dynamics of
migration of VOCs in the environment.
Chlorinated aliphatic compounds are among the most common environmental contami-
nants. These are the Compounds that have been most commonly usedby industry as degreasing
solvents. The principal compounds of concern are tetrachloroethene, which is used in industrial
applications and as commercialdry cleaning fluid; trichloroethene, widely used for metal de-
greasing; l,l,l-trichloroethane, also widely used for metal degreasing; and methylene chlo-
ride, whichhas a variety of industrialuses,includingitsuseastheprincipalsolvent for
decaffeination of coffee and for wood-stripping operations.
Of these compounds, trichloroethene, also knownas TCE, is perhaps the most ubiquitous
and notorious. Depending upon environmentalconditions, this compound undergoes reductive
dehalogenation to form dichloroethenes,and finally vinyl chloride, the most toxic of the chlo-
rinated aliphatic compounds. These chlorinated compounds are heavier than water and thus
tend to sink under the influence of gravity in water systems.
Also very common in the environment are aromatic compounds, which are used as sol-
vents and are present in petroleum products. Perhaps the most common class of these aromatics
is referred to as the BTEX series-benzene, toluene, ethylbenzene, and xylene. These com-
Evaluation
Engineering forSites
Contaminated 49
Table 1 TargetCompoundlAnalyteList
Volatiles
~~ ~~
Acetone 1,2-Dibromo-3-chloropropane 2-Hexanone

Benzene 1 ,ZDibromoethane Methylene chloride
Bromochloromethane 1 ,2-Dichlorobenzene 4-Methyl-2-pentanonelMIBK
Bromodichloromethane 1,3-Dichlorobenzene Styrene
Bromoform 1 ,4-Dichloroethane 1,1,2,2-Tetrachloroethane
Bomomethane/methyl bromide 1.1-Dichloroethane Tetrachloroethene
ZButanone/MEK l ,2-Dichloroethane Toluene
Carbon disulfide 1, I-Dichloroethene 1,1,1 -Trichloroethane
Carbon tetrachloride cis-l ,2-Dichloroethene 1,1,2-Trichloroethane
Chlorobenzene trans- 1,2-Dichloroethene lkichloroethane
Chloroethane 1 ,ZDichloropropane Vinyl chloride
Chloroform cis-l ,3-Dichloropropene Xylenes (total)
Chloromethane/methyl chloride trans- 1,3-Dichloropropene
Dibromochloromethane Ethylbenzene
Semivolatiles
Acenaphthene p-CresollCmethylphenol Indeno[ 1,2,3-cd]pyrene
Acenaphthylene Di-n-butyl phthalate Isophorone
Anthracene Dibenz[a,h]anthracene 2-Methylnaphthalene
Benzo[a]anthracene Dibenzofuran Naphthalene
Benzo[b]fluoranthene 3,3’-Dichlorobenzidine o-Nitroaniline
Benzo[k]fluoranthene 2,CDichlorophenol m-Nitroaniline
Benzo[ghi]perylene Diethyl phthalate p-Nitroaniline
Benzo[a]pyrene 2,CDimethylphenol Nitrobenzene
bis(2-Ch1oroethox)methane Dimethyl phthalate o-Nitrophenol
bis(2-Chloroethy1)ether 4,6-Dinitro-o-cresol p-Nitrophenol
bis(2-Ethylhexy1)phthalate 2,CDinitrophenol n-Nitrosodiphenylamine
CBromophenyl phenyl ether 2,4-Dinitrotoluene n-Nitrosodi-n-propylamine
Butyl benzyl phthalate 2,6--Dinitrotoluene 2,2‘-0xbil( I-chloropropane)
p-Chloroaniline Di-n-octyl phthalate Pentachlorophenol
p-Chloro-m-CreSOl Fluoranthene Phenanthrene
2-Chloronaphthalene Fluorene Phenol
2-Chlorophenol Hexachlorobenzene F‘yrene
CChlorophenyl phenyl ether Hexachlomyclopentadiene 1,2,4-Trichlorobenzene
Chrysene Hexachloroethane 2,4,5-TrichlorophenoI
o-Cresol/2-methylphenol Hexachlorobutadiene 2,4,6-Trichloropheno1
PesticidesPCBs
Aldrin Dieldrin Aroclor 1016
a-BHC Endosulfan I Aroclor 1221
p-BHC Endosulfan I1 Aroclor 1232
y-BHC (Lindane) Endosulfan sulfate Aroclor 1242
&BHC Endrin Aroclor 1248
a-Chlordane Endrin aldehyde Aroclor 1254
y-Chlordane Endrin ketone Aroclor 1260
4,4’-DDT Heptachlor Toxaphene
4.4”DDE Heptachlor epoxide
4,4‘-DDED Methoxychlor
50 Wilson et a!.
Table 1 (Continued)
Inorganics
~ ~~ ~ ~ ~ ~~~
Nickel Aluminum Cobalt

Antimony
de, Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
pounds are present in refined petroleum products, principally in gasoline, and are thus found
widely distributed through the environment due to leaking subsurface gas tanks and surface
spills and discharges of petroleum products. In pure form they are also used by certain indus-
tries as raw materials and/or solvents. These compounds, being unchlorinated,are lighter than
water and therefore float.
Semivolatile Organics
Semivolatile organicsare by-products of many types of industrial and nonindustrial processes.
Table 1 shows the USEPA's Target Compound List of semivolatile compounds. Examples of
common compounds found in the environment are phthalates (used as plasticizers), polynu-
clear hydrocarbons (PAHs) (produced by the combustion offossil fuels), and phenol com-
pounds (which havemany industrial applications inthe chemical industry andare used as wood
preservatives).
The characteristics of semivolatile organic compounds includelower vapor pressure than
the volatile organics. These compounds are therefore of low volatility and tend to exist in the
solid or liquid state at standard temperature and pressure. They may be present in the envi-
ronment either in liquid form or in some cases solidparticulate form (e.g., PAHs in soot pro-
duced by incompletecombustion in residential wood stoves). Many semivolatileorganic
compounds are heavier than water in their liquid state and thus will tend to sink in water.
In general, semivolatile organics alsohave relatively low solubility in water. Phenol com-
pounds are the general exception,with solubilities in the tens ofparts per million range; PAHs,
by contrast, have solubilities limited to the low parts per billion range.
Pesticides and PCBs
Pesticides and polychlorinated biphenyls (PCBs) are also semivolatile compounds. They are
lumped togetherby the USEPA on the basis of similar analytical protocol requirements. These
compounds have been found to be fairly ubiquitousin the environment at very low levels (i.e.,
low parts per million to parts per billion). Table 1 shows USEPA's Target Compound List of
pesticides and PCB compounds of concern. Pesticides enter the environment through both ag-
ricultural use and heavy historical residential use for pest control and weed control. PCBs, on
the other hand, have had principally industrial applications. Because of excellent heat resis-
tance properties, PCBs were used for many years in electrical transformers and as hydraulic
fluids in heavy equipment.
PCBs were generally dissolved in oil for their application. The manufactureof PCBs was
halted by the USEPA in the 1970s. They have been almost completely phased out of use in the
United States today.
Pesticides may enter the environment either in particulate form as powdersor dissolved in
solvents. In their liquidform, pesticides are usually lighter than water, as they tend to be dis-
Evaluation
Contaminated 51
solved for commercial application in BTEX solvents. PCBs are also lighter than water when
present at percent levels or less in oil; however, pure PCB liquids are heavier than water.
Perhaps the most controversial semivolatile organic compounds are dioxin and its related
compounds, the furans. Dioxin is principally a by-product of the manufacture of certain other
substances, the most well known processes being the production of defoliants such as Agent
Orange, and the bleaching of paper in the commercial paper industry. Dioxinand furans can
also be produced as combustion by-products of some organic materials. Small amountsof di-
oxin have been found to be present in uncontained emissions from municipal waste incinerators.
As these compoundsare by-products of other processes, they are not found in concentratedor
pure form; rather, they may be found in a wastewater effluent stream, in media affected by
incinerator emission fallout, or as contaminants in certain waste streams produced from the
manufacture of other substances.
B. InorganicContaminants
As previously noted, inorganic contaminants are naturally occurring substances that can be-
come concentrated in the environment due tohuman activities. The principal contaminants of
concern in the environment are theheavy metals. Metals on the USEPA's Target Analyte List
are listed in Table 1.
Heavy metals are of relatively low vapor pressure and are thus effectively nonvolatile at
standard temperature and pressure. However, some of them, for example, lead and mercury,
become very volatile at elevated temperatures. This is very significant to environmental engi-
neers considering thermal treatment techniques for wastes or contaminated media containing
such metals.
In addition to the more toxic heavy metals, less toxic metals such as iron and manganese
are common environmental contaminants. These metals in particular can create difficulties for
environmental engineers in water collection and treatment systems at contaminated sites. In
addition, salt ionsin solution (e.g., calcium, sodium, magnesium, and potassium chlorides and
sulfates) are often present at contaminated sites.At some sites, theremay be elevated levelsof
nutrient compounds (i.e., nitrogen and phosphorus compounds). Both the salts and nutrients
present significant difficulties and costs for environmental engineers when they must be re-
moved from water.
C. Summary
In summary, of the thousands of substances that can contaminate environmental media, the
USEPA has developed a list of hazardous substances that are of primary concern. Volatile or-
ganic compounds, semivolatile organic compounds, and inorganics, principally heavy metals,
are the classesofhazardous substances commonly dealtwith by environmentalengineers
at contaminated sites. The following discussion addresses the occurrence of these classes of
compounds in various environmental media and the implications for remediationof contami-
nated sites.
II. CHARACTERISTICS OF CONTAMINATED MEDIA

The media that may require remediationat any given contaminated site may include waste ma-
terials that were disposed or of spilled in the environment, soils contaminated either directly
by
spillage and discharges of liquids or indirectly by infiltrating contaminated water, groundwater
contaminated either directly by nonaqueous-phase liquids (NAPLs) or by contaminants in so-
lution, surface water containing nonaqueous-phase liquids and/or contaminants in solutionor
52 Wilson et al.
suspension, and air,which may transport contaminated dustor Contaminants in gaseous form.
Each of these media is described briefly in this section.
A. Waste Materials
There are a great variety of types of waste that can cause environmental contamination. Some
of the materials commonly encounteredare listed below.
LiquidChemicals. Raw materials,waste,and/oroff-specliquidchemicals mayhave been
spilled at a site, disposed of in bulk on the ground, or placed in containers such as drums
or tanks. Such spillage or disposal can contaminate soil, groundwater, and surface water.
Thus, these types of waste may have to be remediated either as bulk materials still in con-
tainers or as constituents absorbed in soil or water.
Solid Materials. Solid waste materials are usually residuals generated by a manufacturing or
treatment process. Examples include sludgesfrom treatment of electroplating wastewaters
and refinery sludges containing oilsand BTEX compounds. Sludges to be remediated ei-
ther may be very low in solids content or may have been dried to essentially solid form.
These typesof materials m often found in drums or are present as precipitates in treatment
or holding lagoons that must be remediated. Other types of industrial solids may include
set organic resins, powders, and materials such as slag or mine spoils.
MunicipalSolid Waste. This class represents materials disposedofin municipallandfills.
Older landfills requiring remediation commonly contain principally household refuse, usu-
ally mixed with at least some wastes generatedat industrial facilities. Low levels of haz-
ardous substances may be present in leachate from these landfills, originating both from
industrial disposal and from the disposalof household products containing hazardous sub-
stances. Interestingly, codisposal of industrial and municipal wastes at many such landfills
has resulted in biodegradation of most hazardous organic compounds. Also, the essentially
neutral pH of municipal landfill leachate does not favor migration of heavy metals from
many landfills. Thus, at many such facilities, the principal problemis leachate containing
iron and ammonia and having a high biological oxygen demand.
B. Soil
Contaminated soil must be remediated principally for two reasons:
1. Potential adverse health affects on humans and/or animals coming into direct contact with
the contaminants
2. The fact the contaminants in soil often provide a continuing source of contamination to
underlying groundwater and/or surface water
The degree to which soil at a site has been contaminated is dependentupon the nature of
the disposal activities, the quantity of materials disposed of, and the chemical nature of those
materials. When selecting a remedial action forsoil, several key characteristics of that material
must be taken into consideration:
1. Soil grain size and cohesiveness. It is generally much easier to extract contaminants from
a permeable sandy soil than froma low permeability clay soil.
2. Organic carbon and clay content. Certain classes of contaminants, such as heavy metals,
PAHs, PCBs, and pesticides, readily adhere to soils that have either high organic carbon
content or significant cation-exchange capacity relatedto clay mineralogy. Other contam-
inants, such as the volatile organics, have very low absorption coefficients on soil mate-
rials regardless of organic carbon or clay content.
Evaluation
Contaminated 53
3. Soil moisture content. This can be an important factor both for handling soils during ex-
cavation and for treating soils, either in situ or after excavation. For example, effective
removal of VOCs from soilby volatilization, either in situ or above ground, depends on the
rate at which the soil can be dried and disaggregated.
4. BTU content. If soils are to be incinerated, the BTU content is important to determining
the feed rate to the incinerator. Since most soilsare very low BTU materials, the degreeto
which the contamination itself contributes BTUs is often thekey factor.
Another very important factor, unrelated to the soils themselves, is the required cleanup
levels for the contaminants of concern. Where very low cleanup levels (generallylow ppm to
ppb levels) are required, it is fairly unrealistic to expect that in situ technologies will reach
those levels. Although significant contaminant massmay be removed (for example, by soil va-
por extraction of volatile organics or in situ biodegradation of biodegradable organics), these
methods will not generally achieve verylow cleanup levels. This is due to the heterogeneityof
the subsurface environment,which prevents in situ processes from effectively reachingareas all
of contamination. Excavation and carefully planned above-ground treatmentof soils, although
they can become very expensive, are generally required to meet very low cleanup levels.
C. Groundwater
Remediation of groundwater requirestwo key components:
1. Interception and/or collection of the contaminated water in the subsurface
2. Treatment of the contaminated water that has been intercepted and/or collected
Interception and/or collection of the contaminant “plume” is designed by a hydrogeologist or
hydrologist with assistance from geotechnical engineers. The hydrogeologist must determine
aquifer characteristics such as mechanisms of flow, directions of flow, extent of the contam-
inant plume, aquifer permeability, and subsurface stratigraphy in order to design a collection
system. For example, selection of collectiodinterception technologies such as pumping wells,
interception trenches,barrier walls, and potentialfor in situ treatment are all highly dependent
upon the aquifer characteristics.
Full remediation of contaminated groundwater to cleanup levels below regulatory stan-
dards cannot generallybe achieved with existing technology. The degreeto which contamina-
tion can be removed from an aquifer system depends upon two main factors:
1. The nature of the contaminants released-their degree of solubility and the aquifer mate-
rial’s absorption capacity for them.
2. The nature of the release. If water materials or contaminated soilsin the unsaturated zone
are not completely removed,they will serve as continuing sourcesof contamination to the
groundwater below.If liquids were released in sufficientquantity to physicallyreach
the groundwater table in free form, then either a light nonaqueous-phase liquid (LNAPL)
or a dense nonaqueous-phase liquid (DNAPL) willbe present in the groundwater system.
LNAPLs can be well defined in many hydrogeologic systems and removed to a significant
degree. However,DNAPLs migrate downwardbeneath the water table, in response to
gravity, along natural pathsof permeability contrast withinan aquifer. It is commonly dif-
ficult if not impossible to track the migration of all DNAPLs. In addition, if found, they
cannot usually be completely removed.
Groundwater that is collected for treatment above groundis usually readily treatable using
well-developed, proven treatment technologies. However, common pitfalls for recovery/treat-
ment systems are the effects of iron and manganese on those systems. Iron and manganese are
54 Wilson et al.
often presentat contaminated sites at elevated levels,either naturally or related to the sitecon-
tamination. Well screens, trenches, and treatment systemsin media may be fouled by corrosion
andlor bacteria related to iron and manganese. This can greatly affect operation and mainte-
nance requirements andcosts for groundwater remediation facilities.For this reason, it is im-
perativethatthese characteristics of thegroundwater be determinedbeforerecoveryand
treatment systems are designed.
To assess the potential forin situ treatment, thecharacteristics of an aquifer must be well
defined. To date, in situ treatment of groundwater has been limited becauseof the limited bio-
degradability of many compounds and heterogeneitiesin the subsurface aquifer materials.The
one exception to this generality is the use of biological degradation in homogeneous uncon-
solidated permeable aquifers where nonchlorinated petroleum product contaminants are present.
D. SurfaceWater
Direct discharges of contaminants flowing to surface water are dispersed rapidly; therefore,
remediation of surface water problems usually requires that the source of the contaminationbe
mitigated. Direct treatment of surface water at contaminated sites is not commonly required
except in the case of a large-scale emergency spillage.
At a contaminated site, surface water is generally affected via three pathways:
1. Contaminants in solution or suspension inrunoff
2. Discharge of contaminants via the groundwater system
3. Contaminant accumulation in bottom sediments, providing a continuous source of release
of soluble contaminants intothe surface water
Remediation of surface water requires knowledge of the mass balance of contaminant input
from these various sources.Only then can the proper combination of runoff and erosion con-
trols, groundwater interception, and/or sediment treatment and removal be selected for meeting
surface water cleanup requirements.
Due to the low solubilities and high adsorption coefficients, contaminants such as metals,
PAHs, pesticides, and PCBs can accumulatein bottom sediments. Volatile organics, and some-
times metals, can enter surface water in solution via groundwater. Oils and other NAPLs can
also be discharged directly into surface water via groundwater.
E. Air
Air quality issues at contaminated sites are generally associated with two potential concerns:
(1) airborne dust emission containing semivolatilesor metals, and (2) direct gaseous emissions
of volatile organics by volatilization from othersite media. These pathways are sometimes of
concern under ambient site conditions, that is, at the existing unremediated site. This is par-
ticularly true if heavy surface soil contamination is present and there is little or no vegetation
to prevent fugitive dust emissions fromoccurring. It also may be true where NAPLs discharge
from subsurface via seepsor to surface water bodies.
Even more commonly, however,these two pathways are of concern during remedial action
itself. Excavation of soils, movement of heavy equipment, and exposure of volatile contami-
nants deep in the subsurface by excavation can create air emission problems during remedia-
tion. Also, emissionsmay be created by treatment processes. For example, any air stripping of
volatile organics will result in the generation of gaseous state compounds that may require
treatment. Soil vacuum extraction systemsfor volatile organics commonly require treatmentof
the air stream, usually by carbon absorption or fume incineration. The use of heat for treating
environmental mediamay also result in the emission ofsuch substances as volatile metals,
PAHs, dioxins, and furans. The potential emissions depend upon the natureof the contaminants
at the site and the nature of the treatment method selected.
Evaluation
Engineering for
Sites
Contaminated 55
F. Summary
In summary, media requiring remediationat contaminated sites most commonly include waste
materials, soil, groundwater, surface water, and air. The
characteristicsof the media themselves
as well as the characteristics of the contaminants present must be well known before effec-
tive remedial measures can be taken. The degree to which remediation of the site is practical
is often a function of the degree of cleanup desired or required. Removalof trace levels
of environmental contaminants from environmental media is often beyond the means of avail-
able technology.
111. REGULATORY STANDARDS FOR SITE REMEDIATION

To mitigate risks to human health and the environment andto define levels for cleanupof ex-
isting contaminated sites, the USEPA and state regulatory agencieshave established standards
for environmentalmedia discussed respectively in Sections I and 11. Because the list of chem-
ical parameters subject to regulatory standards is extensive, our presentation of standards is
limited to some of the most common contaminants in environmental media. These contami-
nants and the applicable standards are listed in Tables 2-5.
The standards discussed herein include those from federal regulations suchas the Federal
Drinking Water Criteria (FDWC) and the Resource Recovery and Conservation Act (RCRA)
action levels. As an example of state regulatory standards, New Jersey cleanup standards are
included because they are some of the most stringent and most recently updated cleanup cri-
teria. At the time of writing, the New Jersey standards were proposed but not yet promulgated
as law. However, NewJersey hasbeen using the proposed standards for guidance on all ongoing
and proposed cleanups.
A. SolidWastes
The standards for cleanup of solid wastes will,in most cases, be the same as the standards for
cleanup of contaminated soils(see Table 2). Handling of solid wastes is dependenton whether
they are classified as hazardousor nonhazardous. They may be classified as hazardous on the
basis of being a listed waste (per 40 CFR 261 Subpart D) or on the basis of being hazardous
by characteristic (per 40 CFR Subpart C). Characteristics of hazardous wastes include ignit-
ability, corrosiveness, reactivity, and toxicity, as defined by the results of standard tests. In
particular, the Toxicity Characteristic Leaching Procedure (TCLP) is currently used to char-
acterize the toxicity of waste.If the waste is classified as hazardous, it
will usually trigger land
ban restrictions (LDRs), which call for treatment of the wastes to RCRA cleanup levels prior
to disposal at an RCRA landfill and within 90 days of removal using the RCRA best demon-
strated available technology (BDAT) or other technologies capableof reaching the same goals.
B. SoilsandSediments
Table 2 presents RCRA and New Jersey soil standards. RCRA action levels dictate when a
corrective measures study (CMS) is to be performed to evaluate solutions for a site cleanup.
RCRA cleanup levelsare determined ona case-by-case basisby USEPA based on potential risk
to human health and the environment.
When determining levels of constituents in soils, it is important to examine the natural
levels (i.e., background concentrations)of constituents forthe area being investigated. Possible
sources of interference that can produce elevated background conditions mayinclude run-
off from roadways (which can contribute lead and other metals, semivolatile compounds, and
56 Wilson et al.
Table 2 SoilandSedimentStandards
New Jersey cleanup standardsb
Subsurface
Nonresidential
ResidentialRCRA
soil soil
surface
soil
surface
levels'
action
mg/kg) Parameter (mag)
~
Arsenic 8.00E + 01 2.00E + 01 2.00 + 01

Benzene 3.00E + 00 1.30E + 01 1.00E + 00
Benzo[a]pyrene' - 6.60E - 01 2.50E - 01 1.00E + 02
Cadmium 4.00E + 01 1.00E + 00 1.00E + 02
Chlordane 5.00E - 01 - - -
Chromium 4.00E + 02(Cr6) - - -
4,4-DDT 2.00 + 00 2.00E + 00 9.00E + 00 1.00E + 02
Endrin 2.00E + 01 1.70E + 01 3.10E + 02 5.00E + 01
Lead 1.00E + 02 6.00E + 02 -
Lindane 5.00E - 01 5.20E - 01 2.20E + 00 1.00E + 00
Nickel 2.00E + 03 2.50E + 02 2.40E + 03 -
PCBs 9.00E - 02 4.50E - 01 2.00E + 00 1.00E + 02
Selenium - 1.00E + 00 1.00E + 03 -
Tetrachloroethylene - 1.00E + 01 9.00E + 00 3.70E + 01 1.00E + 00
Toluene 2.00E + 04 1.00E + 03 1.00E + 03 5.00E + 02
Trichloroethylene 6.00E + 01 2.30E + 01 1.00E + 02 1.00E + 00
1,1,1 -Trichloroethane 7.00E + 03 2.10E + 02 3.80E + 03 5.00E + 01
Vinyl chloride - 2.00E + 00 7.00E + 00 1.00E + 00
Xylenes 2.00E + 05 3.60E + 02 6.30E + 03 1.00E + 01
Zinc - 1.50E + 03 1.50E + 03
'USEPA, ECRA Corrective Action Proposed Rules; FR30798/27 July 1990.
bNJDEPE Cleanup Standardsfor Contaminated Sites-Proposed Rule; N.J.A.C. 7:26D NJ Register 3 February 1992.
CBenze[a]pyrene (BaP) is presented to be representative for semivolatiles.
chlorides), roof drains (semivolatiles), and small amounts of debris on the ground surface (a
small piece of plastic can result in a positive result for phthalates).
C. Groundwater and Surface Water

Table 3 presents FDWC (40CFR 141 et al), RCRA, and New Jersey water standards.As with
soils and sediments, runoff from roadways can cause interferences with surface water results
and some groundwater results. Other possible interferences include septic tanks, sewer lines,
and water lines, which can sometimes contribute chloroformand lesser amounts of other or-
ganics that canbe formed during the chlorination of surface water for municipal water systems.
One common pitfall is useto municipal waterfor drilling and installing a monitoring well with-
out testing the municipal water along with other background samples. Many false positives for
chloroform have been overlooked thisway.
D. Air
Since theearly years of air quality management, air qualityrules and regulations inthe United
States have been based on a set of air quality standards known as the National Ambient Air
Quality Standards,or NAAQS. The NAAQS represent a maximum concentration or "threshold
Evaluation
Contaminated 57
Table 3 GroundwaterandSurfaceWaterStandards
Federal drinking water criteria New Jersey
standards
cleanup
RCRA
MCUj levelsg
action
MCL for Class IIA GWh
Parameter
(m@.)) (mg/kg)
m
(&
)$ (mg/L)
Amnic - 5.00E - 02" 5.00E - 02 8.00E - 03
Benzene OBOE + OOb 5.00E - 03b 5.00E - 03 1.00E - 03
Benzo[a]pyrene' OBOE + 00" 2.00E - 04d - 2.00E - 02
Cadmium 5.00E - 03' 5.00E - 03' 5.00E - 03 4.00E - 03
Chlordane O.WE + 00" 2.00E - 03' 3.00E - 05 5.00E - 04
Chromium 1.00E - 01' 1.00E - 01' 5.00E - 02 (CR6) 1.00E - 01
4.4-DDT - - 1.00E - 04 1.00E - 04
Endrin 2.00E - 03d 2.00E - 03d 2.00E - 03 2.00E - 03
Lead OBOE + 00' 1.50E - 02' 1.50E - 02 1.00E - 02
Lindane 2.00E - 04' 2.00E - 04' 2.00E - 04 2.00E - 04
Nickel - - 7.00E - 01 1.00E - 01
PCBs 0.00E + 00" 5.00E - 04' 5.00E - 06 5.00E - 04
Selenium 5.00E - 02' 5.00E - 02' 5.00E - 02 5.00E - 02
Tetrachloroethylene OBOE + 00" 5.00E - 03' 7.00E - 04 1.00E - 03
Toluene 1.00E + 00" 1.00E + 00" 1.00E + 01 1.00E + 00
Trichloroethylene OBOE + 0Ob 5.00E - 03b 5.00E - 03 1.00E - 03
1,l ,l-Trichloroethane 2.00E - O l b 2.00E - Olb 3.00E - 00 3.00E - 02
Vinyl chloride O.WE + 0Ob 2.00E - 03b 2.00E - 03 2.00E - 03
Xylenes 1.00E + 01' 1.00E + 01' 7.00E + 01 4.00E - 02
Zinc - - - 5.00E + 00
'USEPA, National Primary and Secondary Drinking Water Regulation; FR 5956924 December 1975.
bUSEPA, National Primary and Secondary Drinking Water Regulations; FR 256 90/8 July 1987.
'Benzo[a]pyrene (BaP) is presented to be representative for semivolatiles.
dUSEPA, National Primary and Secondary Drinking Water Regulation; F R 31776/17 July 1992.
'USEPA, National Primary and Secondary Drinking Water Regulation; FR 3526/30 January 1991.
'USEPA, National Primary and Secondary Drinking Water Regulation FR/7 May 1991.
WSEPA, RCRA Corrective Action Proposed Rules; FR 30798/27 July 1990.
hNJDEPE, Cleanup Standards for Contaminated Sites-Proposed Rule; N.J.A.C.7:26D NJ Register 3 February 1992.
level" of a pollutant in the air above which humans or the environmentmay experience some
adverse effects. The actual threshold levelsare based on years of epidemiological,health, and
environmental effects research conductedby the USEPA.
The USEPA has developed twotypes of NAAQS: primary standards, which are set at lev-
els that are designed to protect the public health, and secondarystandards, which are designed
to protect the public welfare (such as vegetation, livestock, building materials, and other ele-
ments of the environment). TheNAAQS differentiate between the effects from short-term ex-
posureandthosefromlongertermexposure to air pollutants. Thus, there are short-term
NAAQS based on l-hr or 8-hr average concentrations and long-termNAAQS based on annual
concentrations.
Because the NAAQS representnumerical criteria, the reports inwhich the USEPA
presentsinformation on thedevelopment of an NAAQS are called criteria documents.
The pollutantsfor which the USEPA hasdeveloped standards are thus known as criteria
pollutants.
58 Wilson et al.
Table 4 National AmbientAir Quality Standards

Primary Secondary
NAAQS
Averaging NAAQS
period
pollutant
Criteria (pg/m3) @@m3)
PM10 (particulate
matter) Annual 50 50
24-hr 150 150
SO2 (sulfur dioxide) Annual 80
24-hr 365 -
3-hr - 1,300
NO, (nitrogen
dioxide) Annual 100 100
Ozone 1-hr 235 235
CO (Carbon monoxide) 8-hr 10,Ooo 10,Ooo
l-hr 40O
, oo 40,Ooo
Lead 1.5 1.S
The USEPA has establishedNAAQS for six compounds sincethe concept of NAAQSwas
established in the CAA amendments of 1970. Table 4 lists these six criteria pollutants and
their standards.
In Table 4, the NAAQS concentrations are expressed in terms of micrograms per cubic
meter (pg/m3);however, you will sometimes see them expressed in terms of parts per million
(ppm). This table also presents some additional information regarding thecriteria pollutants.
IV. SUMMARY OF REMEDIAL ENGINEERING TECHNOLOGIES

This section presents the identification and evaluation of many available remedial engineering
technologies for various environmental media. This presentation is not intended to be compre-
hensive, but it can serve as a general summary of common remedial technologies. The tech-
nologies are grouped into the following broad categories:
No Action. Monitoring and inspection technologies that do not contribute to actual remedi-
ation of site conditions.
Institutional Actions. Indirect methods of reducing exposure to site hazards.
Containment. Physical isolation of solid waste, groundwater, and/or other affected media.
Removal. Physical removal of solid waste, groundwater, and/or other affected media.
Treatment. Alteration of solid waste, groundwater, and/or other affected media to reduce the
toxicity, mobility, or volume of site constituents.
Disposal. Placement of solid waste, treatment residuals, and/or affected media into a secure
disposal facility, or discharge of treated water to the environment.
If site remediation is required, two or more technologies may be used in combination to
provide a comprehensive approach to site cleanup. An example of combining technologies
would be the use of a treatment technology to reducethe toxicity and volume of affected ma-
terial combined with a containment technologyto reduce the mobility of residual constituents
in the treated product.
Remedial technologiesare identified for each of the categories listed abovefor the various
environmental media found at contaminated sites. The identified technologiesare then evalu-
ated to present some of the major advantages and disadvantages associated with each one.
Where appropriate, specific data to be collected to facilitate further evaluation andselection of
a remedial technology are also presented.
c
Engineering Evaluation for
Sites
Contaminated 59
Table 5 Notes on the Criteria Pollutants

PM 10 is composed of solid particles, less than 10pm in diameter, that are small enough to be inhaled
by humans. The particles can be composed of any number of compounds, from road dust to heavy
metals, depending on the source.
Sulfur dioxide(SO,) is a compound formed both naturally and by the combustion of fossil fuels. Exposure
to higher concentrations ofSO, can cause respiratory problems for some people. When combined with
water, SO, forms sulfur compounds that are one of the main components of acid rain.
Nitrogen dioxide (NO,) is another compound formed by the combustion of fossil fuel that contributes to
the formation of both acid rain and smog. NO, is one of several nitrogen oxide (NO,) compounds
present in the atmosphere. The NAAQS is established for NO,, but NO, is more commonly measured.
Ozone itself is not emitted directly into the air but rather is formed through a series of complex physical
and chemical reactions in the atmosphere. Therefore, discussions about the criteria pollutant ozone
often focus on a group of gaseous pollutants known as volatile organiccompounds or VOCs, which are
carbon-based, organic compounds that tend to evaporate into the air easily. Solvents, cleaners, and
paints are among the hundreds of compounds in use that contain VOCs. In the presence of sunlight,
VOCs and other chemical compounds, including NO,, react to form ozone.
Carbon monoxide (CO) is a colorless, odorless, and tasteless gas that occurs naturally in the atmosphere
and is also formed in the combustion of fossil fuel.
teud (Pb) is a common metal that is released into the atmosphere from a number of sources, including
burning of leaded fuels. Lead has the lowest NAAQS, since exposure to low levels can present health
problems.
A list of the technologies presented in this section and the applicable environmental media
is presented in Table 6. A brief description and evaluation of the potentially applicable tech-
nologies identified in this section are presented in Table 7 . A summary of the major data re-
quirements identified for each technology is presented in table 8.
A. No ActionTechnologies
“No action’’ implies that no remedial actions are to be conducted on the media of concern.
Actions such as groundwater monitoring and site inspections are included as no action tech-
nologies because theyare intended to detect changes in site conditions rather than to actually
remediate existing contamination.
Monitoring
Description. Long-term, periodic groundwater and/or surface water monitoring to detect
changes in site conditions, such as the migration of constituents in groundwater, due to natural
processes.
Evaluation. Although groundwater monitoring does not reduce site constituents, it is a
proven method of detecting changes in site conditions and is commonly required as a compo-
nent of remediation.
Site Inspection
Description. Long-term, periodic site inspections to detect visible changes in site con-
ditions due to natural processes.
Evaluation. Although site inspections do not reduce site constituents, they are effective
for identifying visible changesin site conditions andare commonly requiredas a component of
remediation.
60 Wilson et al.
Table 6 Potential Corrective Measure Technologies and Applicable Environmental Media

Applicable Media
~ _ _ _ ~
Technology Solid waste Soil Sediment Groundwater Surface water
No Action
Monitoring X X X X X
Site inspections X X X X X
Institutional Actions
Physical barriers X
Deed restrictions X X
Containment
Storm water controls X X X X
Capping X X X
Vertical barriers X X X
Filter barriers X X X
Subsurface drains X X X
Removal
Excavation X X
Dredging X
Recovery wells X
Interceptor trench X
Vacuum extraction X X X
Treatment
Air stripping (soil) X
Biological (soil) X
Asphalt batching
Soil flushing X
Stabilization X
Incineration X
Air stripping (water) X X
Biological (water) X X
Chemical precipitation X X
GAC adsorption X X
Ion exchange X X
Oxidation-reduction X X
Steam stripping X X
Filtration X X
Neutralization X X
Off-site water treatment X X
Disposal
On-site landfill X X X
Off-site landfill X X X
Surface water discharge X X
Reinjection X
Evaluation
Contaminated 61
Table 7 Summary of Potential Corrective Measure Technologies

Technology
No Action
Monitoring Long-term periodic Detect changes in site Does not reduce con-
groundwater and/or conditions. Monitor stituents. Long-term
surface water moni- effectiveness of correc- expense.
toring. tive measures.
Site inspections Long-term periodic in- Can help detect changes D o e s not reduce con-
spection of the site. in site conditions. En- stituents. Long-term
sure continued effec- exposure.
tiveness of corrective
measures.
Institutional actions
Physical barriers Physical barriers such Reduce risk of expo- Periodic maintenance
as a chain-li& fence sure to site constituents and inspection re-
or vegetation around by restricting site acquired. Does not re-
waste areas. cess. Reduce risk of duce constituents.
site disturbanceby un-
authorized intruders.
Deed restrictions Legal limitations placed Reduce hypothetical Restricts future usability
on future property risks from future land of the site.
and/or groundwater use and/or ground-
use. water use. Reliability
is dependent upon con-
tinued enforcement.
Containment
Storm water Improve storm water Reduces the potential May require some
controls drainage by regrad- for erosion of cover- waste disturbance.
ing, vegetation, soils. Can reduce
swales, or pipes. infiltration of water
and migration of
constituents.
Capping Construction of a soil Minimizes surface wa- Does not reduce con-
or multilayer cap to ter infiltration and constituents. Could
contain waste areas. stituent migration. restrict future
Reduces risk of contact development at
with waste. Reduces the site.
watedwind erosion.
Subsurface vertical Low-permeability verti- Reduces mobility of Could disturb adjacent
barriers cal subsurface barrier constituents and subse- wetland areas. Effec-
to groundwater flow quent risk of exposure. tiveness could be
such as a slurry wall. Could increase the ef- low. Relatively high
fectiveness of ground- cost.
water recovery.
Filter barriers A subsurface wall or Could reduce cation Effectiveness is not
surface blanket of concentrations in proven. Could
glauconitic sands groundwater. Could require periodic
with a high capacity reduce migration of replacement.
for adsorbing metal constituents without
cations. affecting wetlands.
62 Wilson et al.
Table 7 (Continued)
cription Technology
Subsurface drains Subsurface drain or Can be used to lower Limited effectiveness.
trench upgradient of groundwater levelsto Could require signifi-
disposal facilities to below waste levels to cant disturbance of
reroute clean ground- reduce groundwater the site for construc-
water. infiltration and con- tion.
stituent migration.
Removal
Excavation Removal of solid waste Required for subsequent Treatment and/or dis-
and/or affected soils. treatment and/or disposal Would be re-
posal of solid waste. quired. Risks
Removes potential associated with waste
sources of constitu- excavation and trans-
ents from the site. portation.
Dredging Removal of affected Reduces potential risks Dredged material would
sediments from water associated with af- require disposal and
courses. fected sediments. may require treat-
Reduces potential ment. Dredging ac-
for migration of con- tivities would disturb
stituents and risk of aquatic life and could
exposure. increase constituent
migration.
Groundwater recov- Collection of affected Reduces potential mi- Requires long-term
ery wells groundwater with gration of constitu- operation and main-
recovery wells. ents via groundwater. tenance. Site condi-
Facilitates ground- tions must be
water treatment. suitable for this
technology to be
effective.
Interceptor trench A subsurface trench to Reduces potential mi- Requires long-term
facilitate groundwater gration of constitu- operation and main-
collection. ents via groundwater. tenance. Site condi-
Facilitates ground- tions must be
water treatment. suitable for this tech-
nology to be effec-
tive. Economically
limited to shallow
depth.
Vacuum extraction Extraction of VOCs Effective for the recov- Not effective for recov-
from pore spaces in ery of VOCs from ery of heavy metals.
soils. soils. Does not re- Requires high poros-
quire excavation of ity and low moisture
waste or affected content. Requires air
material. treatment.
Treatment (soil/waste)
Air stripping Mechanical screening of Effective for there- Not effective for heavy
soils to increase ef- moval of VOCs from metals or semivola-
fective surface area. soils. Implementation tiles. Air emission
is fairly easy. Proven controls would be
technology. required.
Engineering Evaluationfor Contaminated Sites 63
Table 7 (Continued)
Technology Advantages Disadvantages
organic
Biological
Breakdown
of Effective for the re- Not effective for re-
constituents by mi- moval of many or- moval of heavy met-
croorganisms. ganic solvents and als. Effectiveness can
petroleum hydro- be lowered by a num-
carbons. ber of site conditions.
Asphalt
batching
Reuse of petroleum Beneficial reuse of af- Limited to certain types
hydrocarbon- fected media. Rela- of constituents. Ap-
containing soils in tively low cost. plicable only for
asphalt pavements. coarse-grain soils.
Regulatory agencies
may restrict applica-
tions.
Soil flushing In situ injection of Proven to be effective Unrecovered solution
flushing solution to for the removalof can contribute to
facilitate collection heavy metals. Does groundwater degrada-
of constituents. not require waste tion. Only practical
excavation. for a limited range of
soil conditions.
Stabilization Stabilization of constit- Proven to be effective Increases waste vol-
uents by mixing with for reducing the ume. Not effective
stabilizing agents. leachability of heavy for volatile organics.
metals. Can be con- Does not destroy
ducted in situ. constituents.
Readily available.
Incineration Combustion of organic Proven effective for the Does not destroy heavy
constituents with destruction of organic metals. Residual ash
high-temperature oxi- constituents. Would may require further
dation, on-site or remove constituents treatment before dis-
off-site. from the site. posal. Very expen-
sive.
Treatment (water)
Air stripping Removal of VOCs from Effective for the re- Not effective for the
liquids with an air- moval of VOCs from removal of heavy
stripping column or water. Easily imple- metals. Air discharge
other mechanical mented and well permit would be re-
facilities proven. quired. Air treatment
may be required.
Biological Breakdown of organic Effective for the re- Not effective for re-
constituents by moval of many or- moval of heavy met-
microorganisms. ganic solvents. als. Effectiveness can
be lowered by a num-
ber of site conditions.
Chemical Alteration of pH to re- Commonly used for the Recovered sludge may
precipitation duce the solubility of removal of metals require treatment.
constituents and facil- from water. Proven Not effective for re-
itate precipitation. effectiveness. Could moval of organic
be used in combina- constituents.
tion with other treat-
ment technologies.
64 Wilson et al.
Table 7 (Continued)
cription Technology
GAC adsorption Passing a waste stream Well suited for the re- May not be effective
through activated moval of VOCs, and for all site constitu-
carbon to remove has some effective- ents. GAC unit re-
constituents by ad- ness for mercury requires regeneration
sorption. moval. Readily and/or disposal.
available and well
proven technology.
Ion exchange Removal of toxic metal Proven effective for May not be cost-
ions from waste removal of heavy effective. Spent re-
streams. metals. agent solutions may
require treatment.
Oxidation-reduction Alteration of waste Could be effective for Appropriate reactions
stream to reduce tox- the removal of mer- must be determined.
icity or solubility or cury from waste May not be effective
to create a waste that streams or affected for some combina-
is easier to handle. waters. May be appli- tions of constituents.
cable to the organic
constituents at the
site.
Steam stripping Use of superheated More effective than air Not effective for the
steam to stripVOCs stripping for less vol- removal of heavy
from water. atile organics. More metals. Stripped ef-
cost-effective than fluent may require
air-stripping for high- treatment before dis-
VOC concentrations. charge.
Filtration Removal of suspended Proven effective for the Not effective for dis-
solids by passing removal of suspended solved constituents.
through a porous solids. Could be used Filter backwash
medium. in combination with would require treat-
other treatment tech- ment.
nologies.
Neutralization Adjustment of pH to Easily implemented and Limited effectiveness.
reduce corrosiveness well proven. Rela-
and acidity. tively inexpensive.
Could be used in
combination with
other treatment tech-
nologies.
Off-site water Treatment of affected Off-site facilities exist Off-site treatment may
treatment water at an off-site for the treatment of a not be practical for
treatment facility. wide variety of con- large volumes of
stituents. A new waste. Some risks
treatment facility involved with waste
would not have to be transportation.
built. Best for small
quantities of liquids.
Evaluation
Contaminated 65
Table 7 (Conrinued)
Technology
Disposal
On-site
landfill
Placement
treated
of or Could provide for se- Construction would
untreated wastes in a cure containment of involve high costs
secure disposal facil- wastes and/or treat- and site disturbance.
ity on site. ment residues. Long-term mainte-
nance would be
required.
Off-site landfill Transportation and dis- Reduces mobility of Limited off-site landfill
posal of untreated constituents and sub- capacity. Potentially
waste or treatment sequent risk of expo- high costs. Potential
residues at an sure.Removes long-term liability.
approved off-site constituents from the Untreated materials
landfill. site. Increases poten- may be restricted
tial for future use of from land disposal.
the site.
Surface water Discharge of treated Proven means of dis- NPDES permit would
discharge water to an existing posing treated water. be required. Periodic
surface water body. Surface water body is sampling and mainte-
readily available. nance would be re-
quired.
Reinjection Injection of treated wa- Has been proven to be May not be practical in
ter into the ground effective. low-permeability
through injection aquifers. Ground-
wells or infiltration water modeling may
galleries. be required. Could
increase constituent
migration.
B. InstitutionalActions
Institutional action technologies reduce potential exposures to site constituents by indirect
methods rather than by containment or treatment of the affected media. Institutional actions
include physical barriers and deed restrictions.
Physical Barriers
Description. Physical barriers provide an easily implemented, low-cost method for re-
stricting pedestrian and animal traffic across areas of concern, thus decreasing
the potential for
exposure to site media or damage to on-site storageor containment structures. Physicalbarriers
could range from chain-link security fencing to closely grouped rows of obstructive vegetation.
Periodic inspection and maintenance would be required to maintain the integrity of the barrier.
Evaluation. Physical barriers do not reduce site constituent levels, but they canbe effec-
tive for protecting human health andthe environment by preventing exposureto affected media.
Deed Restrictions
Description. Deed restrictions place legal limitations on future property use. These re-
strictions can prohibit future property and/or groundwater uses that could result in increased
exposure to site constituents. Deed restrictions can be easily implemented, but their effective-
ness is dependent upon continued enforcement.
66 Wilson et al.
Table 8 Potential Corrective Measure Technologies and Applicable Data Requirements

Required data items"
No Action I
Monitoring
Site inspections
Institutional Actions
barriers
Physical
restrictions
Deed
..
Containment
Storm
water
Capping
barriers
controls
Vertical 0
.
Filter barriers * I l 1 . 1 .
Subsurface drains
Removal
Excavation
Dredging
Recovery wells
Interceptor trench
.
Air stripping (water)

Chemical precipitation
GAC adsorption
Ion exchange
Oxidation-reduction
Steam stripping
Filtration
Neutralization
Off-site water treatment
Disposal
landfill
On-site
Off-site landfill
.
Surface water discharge
Reinjection
Evaluation
Contaminated 67
Table 9 Description of Data Items

Topographylsetting Groundwater chemistry(Conr.) Soil physical properties(Cont.)
Ridges Conductivity Settlement potential
Valleys Dissolved oxygen Soil index properties
Hills Nutrients Erosion potential
Surface water bodies Chemical oxygen demand Soil chemical properties
Forests Total organic carbon PH
Wetlands Constituent concentrations Organic content
Drainage patterns Heavy metals Sorptive capacity
Buildings Source area characterization Ion-exchange capacity
Vegetation Location Constituent types
Climatological data “ypeldesign Constituent concentrations
Evaporation Operating practices and Surface water characteristics
Evapotranspiration history Location
Temperature Physical condition Elevation
Wind speed and direction Age Area
Precipitation Method of closure Depth
Atmospheric pressure Type of wastelclassification Velocity
Relative humidity Volume/extent Width
Regionallsite geology Constituent chemical properties Inflowloutflow
Geologic units PH Temperature
Strata Molecular weight Seasonal fluctuations
Strike and dip Hydrolysis Flood plain
Folding Chemical class Stream cross sections
Faulting Viscosity Surface water chemistry
Depositional history Solubility PH
Soillrock types Oxidation/reduction Total dissolved solids
Aquifer characteristics potential Total suspended solids
Hydraulic conductivity Vapor pressure Biological oxygen demand
Porosity Sorption Alkalinity
Grain size distribution Biodegradability Conductivity
Saturated and unsaturated Photodegradability Dissolved oxygen
zones Chemical transformations Nutrients
Attenuation characteristics Migration potentiall Chemical oxygen demand
Extent leachability Total organic carbon
Depth Constituent physical properties Constituent concentrations
Thickness Physical form Heavy metals
Potential migration pathways 5pe Sediment characteristics
Rechargeldischarge areas Temperature Depositional area
and amounts Density Thickness
Aquifer leakagelinteractions Boiling point Grain size distribution
Groundwater Flow Soil physical properties Density
Water level contours Soil classification Organic carbon
Vertical and horizontal flow Grain size distribution Ion exchange capacity
TidaVseasonal influences Soil profilelstratigraphy PH
Man-made influences Permeability Constituent extentlvolume
Groundwater chemistry Density Horizontal and vertical extent
PH Porosity in waste
Total dissolved solids Moisture content Horizontal and vertical extent
Total suspended solids Infiltration in soil
Biological oxygen demand Storage capacity Horizontal and vertical extent
Alkalinity Mineral content in sediments
68 Wilson et al.
Table 9 (Continued)
Constituent extent/volume Contituent migration (Cont.) Potential receptors (Cont.)
(Cont.) Horizontal and vertical Ecology
Horizontal and vertical migration rate Endangered species
extent in groundwater Factors influencing 'Iteatability Study
Horizontal and vertical migration Bench-scale tests
extent in surface water Potential future movement Residual characteristics
Total volume Potential receptors TCLP
Concentration profiles Age Waste samples
Constituent migration Location SoiYsediment samples
Horizontal and vertical Use Water samples
migration direction Population
Evaluation. If enforced, deed restrictions can be effective in reducing the potential for
disturbance of affected site media.
C.
Containment
Containment technologies reducethe potential for direct exposure to site constituents and the
potential for their migration by physically isolating the affected media or wastes.
Storm Water Controls
Description.Stormwatercontrolssuch as surfaceregrading,increasedvegetation,
drainage swales, and drainpipes can be used to improve the drainage of surface water away
from waste disposal facilities such as landfills and impoundments. Improved drainage can re-
duce the potentialfor erosion of cover materials, reduce infiltration of surface water, and min-
imize the potential for ponding of surface water.
Evaluation. This technology can be effective for reducing the potential volume of leach-
ate produced by infiltration of surface water. Surface water controlsalso minimize erosion and
subsequent migrationof constituents.
Data Requirements. Data needs include: topography (extent of wetlands, existing drain-
age patterns, drainage area), soilphysical properties (erosion potential), andclirnatolog-
ical data.
Caps and Liners
Description. Capping is a common containment technology thatis used to prevent direct
contact with wastes, reduce the infiltration of surface water and subsequent leaching of con-
stituents, prevent erosionof waste materials, and control surface runoff. Low-permeability caps
such as clay caps and multilayer capsare the most effective caps for waste containment. Mul-
tilayer caps typically consistof an upper vegetative layer underlainby a drainage layer, an im-
permeable synthetic membrane liner, and a low-permeability clay layer and are usually more
effective than clay caps at restricting surface water infiltration.
Evaluation. This technology is one of the most common technologies for the contain-
ment of hazardous waste, and it has been proven to be effective. Multilayer caps are appro-
priate for improving waste containment and reducing the potential for leaching of constituents.
Data Requirements. Data requirements include topography (extent of wetlands, surface
slopes, vegetation conditions), climatological data, source areacharacterization (extent, depth,
and volume of waste), constituent chemicaland physical properties, and soil physical proper-
ties (infiltration, permeability of existing covers and waste, bearing capacity
of waste, potential
settlement).
Evaluation
Contaminated 69
Vertical Barriers
Description. Subsurface vertical barriers (e.g., slurry walls, membrane walls, grout cur-
tains, sheet piling) can contain land-disposed wastesby restricting the lateral flow of ground-
water through the waste, thereby reducing the potential for migrationof constituents into the
groundwater. Vertical barriers can also allow pumping within the contained area without sig-
nificant water level drawdown of nearby water bodies (rivers, lakes, etc.).
Evaluation. Vertical barriers have been used successfully in a number of waste contain-
ment applications. Vertical barriersare most effectiveat shallow depths and when they canbe
keyed (or tied) into a confining substratum that can restrict the flow of groundwater beneath
the barrier. Because vertical barriers restrict the flow of groundwater, they can impact nearby
ecosystems such as wetlands, rivers, and streams.
Data Requirements. Data requirements include topography (extent of wetlands), aquifer
characteristics (physical propertiesof confining layer, Columbia Aquifer profile, discharge rate
to surface water), groundwater flow (depth to water table, groundwater flow rates and direc-
tion, hydraulic gradient), and constituent extent and migration.
Filter Barriers
Description. A verticalwallfilterbarrier or ablanketfilterbarriercould be created
by the placement of natural sediments having high cation-exchange capacity (e.g., glauconi-
tic greensand) in a vertical trench or as a blanket, respectively. Glauconitic greensands are
sediments with a high capacity for adsorbing cations (e.g., lead, mercury) from liquid solu-
tions.
Evaluation.Bench-scaleexperimentshavedemonstratedthatgreensanddepositsfrom
the Delaware Coastal Plain can remove heavy metals from spiked water samples and landfill
leachates. Greensands havebeen shown to retain more mercury from basic (high pH) solutions
than from acidic (low pH) solutions.To date, the effectivenessof natural greensand filter bar-
riers has not been proven in field applications, and a pilot field study wouldbe required prior
to full-scale implementation.
Data Requirements. Data needs include sources of greensand or other media with high
cation exchange capacity; extent of groundwater degradation, if any; extent of wetlands; depth
to water table; groundwater flow rates and direction; hydraulic gradient; aquifer profile; dis-
charge to surface water; and surface water flow rates. Bench-scale testing would be required to
evaluate this technology on a site-specific basis.
Subsurface Drains
Description. A subsurface drain or drains could be constructed hydraulically upgradient
of any disposal facility impacting groundwater to lower the groundwater table to a level below
the bottomof the impoundment(s). This technology is considered a containment action because
it physically isolates the waste from the underlying groundwater and reduces the potential for
leachateproductionand/orleachatemigration.Groundwatercollectedintheupgradient
drain(s) could be discharged to a nearby stream or storm water drainage system. Subsurface
drains can also be used to collect groundwater affected by site constituents. This technology is
further discussed in Section D under groundwater removal.
Evaluation. If the groundwater table is periodically above the bottom of a landfill or dis-
posal impoundment, this technology couldbe effective for reducing the potential migration of
constituents into groundwater.
Data Requirements. Data requirements include depth to groundwater table, groundwater
flow rates, depth of impoundment bottoms, soil and waste hydraulic conductivities or trans-
missivities, groundwater gradient, and aquifer profile.
70 et Wilson al.
D. Removal
Removal technologies focus on the physical removal
of affected media from the site, usually to
facilitate treatment and/or disposal.
Solid Waste, Soil,andlor Sediment Removal
Excavation
Description. Excavation is applicable for the removal of solid wastes and affected soils
and sediments. If materials must be removed, they can typically be excavated using standard
methods andpractices, although the volume of material to be removed could necessitate staged
excavation or other special handling requirements.
Evaluation. Although excavation alone is not a remedial technology, it may be required
in conjunction with other treatment and/or disposal actions. Fugitivedust and volatilization of
constituents into theair during excavation could pose short-term risks to human health and the
environment.
Data Requirements. Data requirements include extent, depth, and volume of waste and/or
affected soils and sediments; soil physical properties; and constituent concentrations.
Dredging
Description. Dredging is the removal of sediments from under water, which may be ac-
complished using hydraulic systems, clamshells, or other means of excavation.
Evaluation.Dredgingcaneffectively remove affectedsedimentsfromsurfacewater
courses. However, dredging operations can disturb aquatic life and potentially result in in-
creased mobilization of constituents downstream.
DataRequirements.Datarequirementsincludestreamflow rates, stream profile,and
sediment characteristics (extent, depth, and volume of affected sediments).
GroundwaterRemoval
Recovery Wells
Description. Affected groundwater can be collected with pumping wells located in the
affected aquifer, hydraulically downgradient of the constituent source area(s). By intercepting
groundwater, the migration of constituents from the source areas can be restricted. Collected
groundwater would probably require some type of treatment prior to discharge.
Evaluation. Recovery wells can be effected for long-term groundwatercollection in cer-
tain aquifers, although this technology may not be appropriate under all site conditions. Re-
covery well systems are most effective when measures are taken to remediate the source(s) of
constituents migration.
DataRequirements. Data requirementsincludedepth to water table, groundwater
flow rates and direction, hydraulic gradient, aquifer characteristics, and extent of affected
groundwater.
interceptor Trench
Description. An interceptor trench is typically constructedby excavating a narrow trench
into a stratum of concern, placing a perforated drainpipe alongthe bottom of the trench, and
backfilling the trench with some type of drainage aggregate. The drainpipe conveys waterby
gravity to a collection sump, and the water collectedin the sump is pumped out for treatment
and/or discharge to surface water.
Evaluation. Interceptor trenches havebeenfound to be effective for the collection of
shallow groundwater in unconsolidated aquifers, but they are not appropriate for all site con-
ditions. At shallow depths(10-20 ft), interceptor trenchesare typically more cost-effective and
perform better than recovery wells in unconsolidated aquifers.
Evaluation
Engineering for
Sites
Contaminated 71
Data Requirements. Data requirements include depth to water table, groundwater flow
rates and direction, hydraulic gradient, and aquifer characteristics.
Vapor Extraction
Description. A vacuum extraction system consists of a network of vapor withdrawal (or
vacuum) wells installed in the vadose (unsaturated) zone to remove volatile organic compounds
(VOCs). A vacuum is applied to promote movement of air and VOCs to the extraction well
points. An in-line water removal system can be provided to remove condensate and limited
quantities of recovered groundwater. Recovered vapors are treated in an in-line vapor-phase
carbon adsorption system (forVOC capture) or an exhaust fume incineration system (forVOC
destruction). Steam can be injected through injection wells to enhance the vacuum extrac-
tion process. Vacuum extraction is considered for the removal of VOCs from wastes and af-
fected soils.
Evaluation. Vacuum extraction has been provento be effective for the removal ofVOCs
from the vadose zone. This technology can be used to remediate soils in place, thereby mini-
mizing disturbanceto waste facilities that result from excavation and removal operations. This
technology is only effective for removal of volatile constraints.
Data Requirements. Data requirements include depth to groundwater, physical and chem-
ical properties of soils and wastes, soil and groundwater quality, and extent of affected soil
and waste.
E. Treatment
Treatment technologies reducethe toxicity, mobility, or volume of affected media or wastes,
thus reducing the potential for constituent exposure
to human health and the environment. Re-
moval and disposal technologies may be required in conjunction with treatment alternatives,
although some treatment technologies can be implementedin situ.
Solid Waste, Soil, andlor Sediment Treatment
Air Stripping
Description. Air stripping of volatile organic compounds (VOCs) in soils can be accom-
plished by a process of mechanical screening that involves the passage of excavated soils
through oneor more vibrating screens commonly used in construction projects. In this process,
the rate of volatilization is maximizedby soil disaggregation and the resulting increase of ef-
fective soil particle surface area.
Evaluation. The removal of VOCs from wastes and/or affected soils can reduce the po-
tential for migrationof VOCs into groundwater. The equipment, materials, and labor required
to perform VOC stripping of soils are readily available. Excavation of materials is required
prior to implementation of this technology, which would disturb the site and potentially result
in short-term exposure. Air emission and erosion and sedimentation controls and permits would
likely be required.
DataRequirements.Datarequirementsincludewastevolume,chemicalandphysical
characteristics of constituents, and soil physical properties.
Biological Treatment
Description.Biologicaltreatment,sometimesreferred to as bioremediation,generally
refers to the breakdown of organic constituents by microorganisms. The most common pro-
cesses are based on aerobicor anaerobic bacteria, suchas those processes used in the treatment
of muncipal wastewaters. In situ, pump-and-treat, solid-phase, slurry phase, and soil heaping
biological treatment techniques have been used to remediate contaminated sludges.
72 Wilson et al.
Effectiveness. The effectiveness of biological treatment can be influenced by a number of

parameters, including pH, temperature, availability of nutrients, and the presence ofheavy
metals. Some biological treatment methods have been successful for the treatment of certain
organic solvents,but this technology is not effective for the removal of heavy metals from solid
waste or soils.
Data Requirements. Data requirements include physical chemical characteristics of soils
and physical and chemical properties of constituents.
Asphalt Batching
Description. Asphalt batching can be used as an alternative to landfillingor on-site treat-
ment of soil containing petroleum hydrocarbons to recycle it into useful products such as as-
phalt paving material. After testing for petroleum hydrocarbon content (and the presence of
hazardous substances), the soil is delivered to the batch plant, where it is crushed and sieved
through screens to remove wood, metal, or other undesirable debris. Next, the soil is passed
through a gas- or oil-fired rotary kiln, where it is heated to approximately 350°F, which evap-
orates all the water and burns the petroleum hydrocarbon components. Thereafter, the soil is
blended with other aggregates and asphalt and delivered to the paving location.
Evaluation. Recycling by asphalt batching removes the contaminants from the original
site, destroys undesirablematerials, and providesa valuable constructionmaterial. Reasonable
safety cautions during the initial haulingand storage and adequate quality testingare the only
major technical difficulties related to asphalt batching. Local regulatory agencies may have
administrative control and shouldbe contacted prior to using this process. This process is best
for sandy soils rather than clay soils, because a high percentage of clay is not desirable in as-
phalt paving materials.
Data Requirements. Data requirements include chemical types and concentrations, phys-
ical properties of the soil, particularly grain size analysis, and the extent of constituents.
Soil Flushing
Description. Soil flushing involves the in situ injection or percolation of large volumes
of flushing solution to an area of waste and/or soil requiring remediation and the subsequent
collection or recovery of the flushing solution. The solution is intended to dissolve or precip-
itate constituents as it passes through the affected media. Water is a common flushing solution,
although aqueous surfactant solutions and organic solvents have also been used. Well points,
subsurface drains, or anothertype of collectionsystemmustbe installed to collect the
constituent-laden solution. The recovered solution requires treatment.
Evaluation. Soil flushing has been proven to be effectivefor the removalof heavy metals
from solid wastes and soils. Soil flushingmay not be effective for all organic constituents,but
the recovered groundwater and flushing solution can typically be treated with an alternative
method for the removal of organics. Cloggingof soil pores can limit the flushing of the soils,
thereby reducing the effectiveness of the treatment and preventing recoveryof the flushing so-
lution. Unrecovered flushing solution can contribute to increased groundwater degradation.
Data Requirements. Data requirements include chemical and physical properties of soil,
aquifer characteristics, groundwater flowrate and direction, physical and chemicalproperties
of constituents, and the extent of constituents.
Stabilization
Description. Stabilization technologies have been used to immobilize organic and inor-
ganic compounds in wet or dry media, using reagents to produce a stable mass. Stabilization
methods include cement-based methods, silicate-based (pozzolanic) methods, thermoplastic
methods, organic polymer methods, and others. Waste materials and/or affected soils can be
mixed in place with shallow or deep soil mixing systems, or the affected materials can be ex-
Evaluation
Contaminated 73
cavated and consolidated into oneor more locations before mixing. 'I)lpically, this technology
does not destroy constituents but incorporates them into a dense, homogeneous, low-porosity
structure that reduces their mobility. Stabilization has been proven to be effective for immo-
bilizing inorganic constituents (e.g., metals) but hashad limited success for volatile organics.
Because a reagent must be added to the soil, the volumeof treated soilmay be greater than the
original soil volume by as much as 20-100%.
Evaluation. This technology can restrict the migration of constituents from the waste im-
poundments and reduce the potential for subsequent exposure. It can be implemented in place.
However, its applicability to heterogeneous wastesmay be limited, as the proper selectionof a
stabilizing reagent for amixed waste may be difficult.
DataRequirements.Datarequirementsincludebench-scale or pilot-scaletestresults,
leachability of unstabilizedandstabilizedmasses,physicalandchemicalcharacteristics of
waste, and the extent and volume of waste.
Incineration
Description. Incineration is a thermal treatment method that uses high-temperature ox-
idation under controlled conditions to degrade waste materials into by-products that include
carbon dioxide, water vapor, ash, nitrous oxide, sulfur dioxide, and hydrochloric acid gases.
Air pollution controlsare typically needed to ensure that air quality standards are not violated.
Residual incinerator ashmay require stabilization priorto disposal due to high concentrations
of metals. Typesof incinerators that are commonly used for the remediation of solid waste and
soils include rotary kiln, fluidized bed, and infrared incinerators. Excavated soils can trans-
be
ported off-site for incineration,or they can be treated with a mobile incinerator assembled on
site. Incineration is not effective for the destruction of metalsin solid media.
Evaluation. Incineration is a feasible and well-developed technology for the destruction
of organic constituents, although residual ash would require stabilization prior to disposal if
high metals concentrations are present. Due to cost considerations, off-site incineration is most
appropriate for smallto moderate volumes of materials; on-site incineration would only be ap-
propriate for the incineration of large volumes of material. Waste handling and stack emissions
could present risks to human health and the environment unless appropriate healthand safety
equipment and emission controls are employed. Limited availability and capacity of off-site in-
cinerators can result in lengthy remediation schedules if large volumes of waste are present.
Public oppositionand permitting requirements could hinder the sitinganofon-site incinerator.
Data Requirements. Data requirements include a treatability study (test burn); ash con-
tent, heat value, and halogen content; and physical and chemical characteristics of waste.
Liquid Treatment
The liquid treatment technologies presented here may be applicable to the treatment of affected
groundwater, surface water, or water generated or collected during solid waste treatment.
Off-Site Water Treatment
Description. Affected groundwater recovered from the siteor water resulting from some
type of on-site treatment process is treated at an off-site treatment facility. Water is pumped or
hauled via tank trucksto an off-site treatment facilityor discharged to a publicly owned treat-
ment works (FQTW) upon authorization by the POTW.
Evaluation. Off-site facilities have been used successfully for the treatment of water con-
taining various constituents.If a large volume of water requires treatment, hauling the to water
an off-site facility can be extremely expensive and impractical. If the water is hazardous, a
permit is required for off-site transportation.
Data Requirements. Data requirements include identification of a facility, pilot-scaletest,
ground and/or surface water chemistry, and physical and chemical properties of constituents.
74 Wilson et al.
Air Stripping
Description. Air stripping to remove organics from groundwateris most often performed
by passing the water through a countercurrent air-stripping column tofacilitate the transfer of
volatile organics fromthe liquid phase to the gas(air) phase. Off gas treatmentmay be required
for vapor-phase VOC removal. Other methods of air stripping are employed that do not entail
countercurrent air andliquidflow(diffused aeration andmechanical aeration); however,
packed tower stripping is most widely used.
Evaluation. Air stripping has been proven to be effective for the removal ofVOCs from
groundwater, although it is not effective for the removal of metals. Stripping efficiency is re-
lated to the air-to-water ratio, system temperature, tower packed depth, and volatility of the
constituents. An air discharge permit is required, and offgas treatment may be required. Air
stripping can be prone to fouling, depending on mineral and bacterial levels in the water.
Data Requirements. Data requirements include groundwater and/or surface water chem-
istry, physical and chemical properties of constituents, and effluent target levels.
Biological
Description. In situ biotreatment is the aerobic or anaerobic microbial degradationof or-
ganic constituents in groundwater. The complete biodegradation process converts organics to
carbon dioxide and water (aerobic) or carbon dioxide and methane (anaerobic). In biotreat-
ment, a microbial population (biomass)is maintained, by injection of nutrients and oxygenor
methane, to feed on the organic substances present in the water. The microbial populations
available for forming the biomass are numerous, and many alternative designs are available for
both aerobic and anaerobic systems.
Effectiveness. Biotreatment is well documented in attaining high organic removal effi-
cienciesmeasured as COD or BOD reduction. However,some organicsubstances do not
biodegrade but are stripped to the atmosphere as the water is treated. Biotreatment methods
are most effective for water that has high VOC concentrations. High levels of inorganic ca-
tions (specifically calcium, iron, and magnesium) can exert toxic effects on anaerobic treat-
ment processes.
istry, physical and chemical properties of constituents, and effluent target levels.
Chemical Precipitation
Description.Chemicalprecipitationprocesses are commonlyused to removemetals
from water. Chemical precipitation is pH dependent in that acid or base is added to a solution
to adjust the pH to a point where the constituents to be removed have their lowest solubility.
Frequently a bulking agent such as lime or a soluble salt that forms insoluble metalprecipitates
is employed as a precipitant. The precipitant (lime, caustic, or sulfide) is added to the metal-
containing water, and thenthe solution is mixed with a flocculating agent (polymer)to promote
solidsagglomeration andsettling.Someorganic or inorganicsubstances (e.g., chelants)
present in the water may inhibit precipitation.
Evaluation. This technology could be effective for the removal of metals from collected
groundwater and/or process streams from other treatment technologies. Sludge produced during
the process would have to be dewatered or treated before disposal.
Data Requirements. Data requirements include bench-scale (iar) test results (precipitant
doses, setting rates, and sludge production); groundwater and/or surface water chemistry; phys-
ical and chemical properties of constituents; and effluent target levels.
Granular Activated Carbon Adsorption
Description. Carbon adsorption involves contact of a waste stream with activated car-
bon, usually by downward flow througha series of packed bed reactors. Molecular adsorption
Evaluation
Contaminated 75
onto granular activated carbon (GAC) occurs through physical and/or chemical forces in which
molecules are held on the surface of the carbon particle. A compound’s affinity for carbon
depends on its molecular size and water solubility. Constituents with high molecular weights
and low water solubilities exhibit a high affinity for carbon.
Evaluation. Granular activated carbon adsorption is well suited forthe removal of VOCs,
with the exception of vinyl chloride and chloromethane compounds, and some inorganic con-
stituents such as mercury have also shown a limited potential for adsorption onto GAC. Al-
thoughGACadsorptiondoesnotproduceanyoff-gases, the spentcarbon would require
regeneration or treatment prior to disposal. Adsorption of metals onto GAC may limit the re-
generability of the carbon. GAC is also subject to bacterial fouling.
istry and physical and chemicalproperties of constituents. Also, a pilot test would be required
to determine the adsorption capacity of the carbon for the organics to be removed and to es-
timate the carbon bed life.
Ion Exchange
Description. GAC adsorption is commonlyused for the removal of toxic metal ions from
solutions when recoveryof the concentrated metal isfeasible and/or a relatively low proportion
of competing non-heavy metal ions are present. The design of an ion-exchange system must
consider the specific ionsto be exchanged, the controlof influent bacteria and suspended sol-
ids, and the treatment of spent regenerant solutions.
Evaluation. Ion exchange could be effective for the removal of metals from collected
groundwater and/or process waste streams. Highly concentrated waste streams can usually be
separated with more cost-effective technologies.
Data Requirements. Data requirements include pilot-scale test results, groundwater and/
or surface water chemistry, and physicaland chemical properties of constituents.
Oxidation-Reduction
Description. Chemical oxidation-reduction reactions are used to reduce toxicity or sol-
ubility or to transform a substance to one that is more easily handled. Chemical reduction is
primarily used for the treatment of wastes containing hexavalent chromium. Common reducing
agents include sulfurdioxide, sulfite salts, and ferrous sulfate. Chemical oxidationcan be used
for the treatment of oxidizable organics. Chlorine (hydrochloride), hydrogen peroxide, and
ozone are common oxidizing agents. Ultraviolet light is used as a catalyst to facilitate chemical
oxidation reactions.
Evaluation. Chemical reduction could be effective for the removal of reducible organics
from collected groundwater and/or process waste streams. Chemical oxidation may be appli-
cable to some organic constituents.
DataRequirements.Datarequirementsincludepilot-scaletest results, groundwater
and/or surface water chemistry, physical and chemical properties of constituents, and bench-
scale testing.
Steam Stripping
Description. Steam stripping consists of passing superheated steam countercurrent to a
preheated groundwater stream in a packed or tray tower to strip VOCs and other organics
into the vapor phase. The off-gases from the columnare routed to a condenser, which can be
cooled using groundwaterin a non-contact mode. From the condenser, the condensate flows to
a decanter, where the organic layer is drawn off and the bottoms are routed to the stripping
tower influent. Effluent from the stripping tower can be routed to a polishing treatment or
discharged. The efficiency of stream stripping can be increased by operating the column at a
negative pressure.
76 Wilson et al.
Evaluation. Steam stripping will treat less volatile and more soluble wastes than air strip
ping andis more cost-effectivefor high VOC concentrations. Steam stripping could be effective
for the treatment of collected groundwater and/or process water containing highoflevels VOCs.
Stripped effluent may require treatment prior to discharge, and air pollution controls would
likely be required to reduce toxic emissions.
DataRequirements.Datarequirementsincludepilot-scale test results, groundwater
and/or surface water chemistry, physical and chemical properties of constituents, and bench-
scale testing.
Filtration
Description. Filtration is a process of separating and removing suspended solids from a
liquid by passing the liquid througha porous medium. Filtrationis a proven technology for the
removal oflow levels of suspended solids from liquid waste streams. In particular, granular
media filters have been demonstratedto be effective as partof mobile treatment systems as well
as on-site systems for hazardous wastewater treatment. filter The backwash would require treat-
ment prior to disposal due to high solids levels.
Evaluation. This technology could be effective for the treatment of collected ground-
water and/or process waters that have constituents, such as metals, in the form of suspended
solids. Filtration canbe an effective pretreatment process for technologies suchas ion exchange
and carbon adsorption.
istry and physical and chemical properties of constituents.
Neutralization
Description.Neutralization is used to treat wasteacids and wastealkalies(bases) to
eliminate or reduce their corrosiveness. More frequently, neutralization is used as a pretreat-
ment step prior to other liquid waste treatment processes. Care should be taken to avoid the
formation of hazardous compounds.
Evaluation. Neutralization may be required prior to the treatment or disposal of collected
groundwater and/or process waste streams.
Data Requirements. Data requirements include pilot-scale test results, groundwater and/
or surface water chemistry, and physical and chemical properties of constituents.
F. Disposal
Disposal technologies provide secure, permanent containment of affected media or wastes,
thus reducingthe potential for exposure to or migration of constituents. A removal action would
be required prior to the implementation of any disposal action.
Disposal of Solids
On-Site Landfills
Description. On-site landfilling is the placement of treated or untreated wastes in a dis-
posal unit (such as a landfill, surface impoundment, or vault) constructed on site to meet the
relevant standardsof RCRA and anyother applicable federal and state requirements. An on-site
landfill would provide containment and secure storageof affected solid media. Therisk of ex-
posure to constituents would be reduced by minimizing the mobility of the waste.
Evaluation. The construction of a new, approved, on-site landfillmay be impractical due
to the required disturbance of the waste, limited site area, and shallow groundwatertable. The
construction of an on-site landfill would involve high capital costs and long-term maintenance.
Data Requirements. Data requirements include site characteristics, permit requirements,
and physical and chemical properties of the waste.
Evaluation
Engineering for
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Contaminated 77
Off-Site Landfill
Description. Off-site landfilling is the transportation and disposal of untreated wastes or
treatment residues at an approved off-site landfill. An off-site landfill could provide for the
secure containmentof affected mediaor wastes. Wastesor treatment residues (e.g., incinerator
ash) would have to meet certain analytical parameters (e.g., TCLP) before off-site disposal
would be permitted. The risk of exposure to site constituents would be eliminated by removing
the affected mediaor wastes from the site. Excavationwould be required prior to the disposal
of the waste.
Evaluation. This technology could be a component of remediation for alternative cor-
rective measures that generate wastes or treatment residues that cannot be contained on site.
However, off-site disposalof waste would be relatively expensive, and existing landfill capacity
is limited. Permits would be required for transportation of wastesto a permitted facility.
Data Requirements. Data requirements include identification of a facility, permit require-
ments, and physical and chemical properties of the waste.
Disposal of Liquids
Surface Water Discharge
Description. Surface water discharge is the discharge of treated water to an existing body
of surface water. Priorto discharge, the water would have to meet all applicable environmental
standards including Surface Water Quality Criteria (SWQC) and National Pollution Discharge
Elimination System (NPDES) standards.
Evaluation. Discharge to surface water is a proven means of disposing of treated water.
Because discharged water would have to meet all applicable environmental standards, there
would be no adverse impacts on human health or the environment. The equipment, materials,
and labor requiredto construct a surface water discharge line are readily available. An NPDES
permit and other permitsmay be required prior to discharge, or a current NPDES permit may
require modification to include the new discharge. Periodic water quality sampling and main-
tenance of the discharge line would be required.
Data Requirements. Data requirements include surface water characteristics and effluent
limitations.
Reinjection
Description. Reinjection refers to the pumping or gravity flow of treated groundwater
back into the ground through injection wells or infiltration galleries. Reinjection could be used
for the disposalof treated waterif surface water discharge is not possible. Treated water would
have to meet all applicable environmental standards before reinjection. Reinjection can also be
used to provide more control during groundwater collection.
Evaluation. Reinjection has been used successfully at a number of sites for the disposal
of treated groundwater. Clogging of reinjection wells from silting, mineralization, and/or bio-
logical growth can reduce the effectiveness of reinjection. Reinjection of water into aquifers
with low permeabilities may not be practical. Groundwater modeling couldbe required to de-
termine the implementability of reinjection and to determine which reinjection method (injec-
tion wells or infiltration galleries) would be the most appropriate.
Data Requirements. Data requirements include aquifer and groundwater flow character-
istics and effluent limitations.
V. DEVELOPMENT AND EVALUATION OF REMEDIAL ALTERNATIVES

This section is intended to serve as a primer on the process of remedy selection. It focuses on
the identification, development, evaluation, and selection of appropriate remedial measures,
78 Wilson et al.
technologies, techniques, and procedures. The term “remedy selection” is used in the broad
sense of referring to the series of evaluations and assessments that take place inthe practice of
determining the most appropriate remedial action fora contaminated site. The reader can and
should read the various guidance documents issued by the USEPA and other regulatory agen-
cies that outline in detail the proper procedures for evaluating remedial technologies and al-
ternatives.Thesedocumentseffectivelypresent the agencies’requirements.This chapter
attempts to present, froma practitioners’ point of view, how the process really worksor some-
times doesn’t work.
In this section we review the basics of the remedy evaluation and selection process from
an engineeringperspective. The properengineeringperspectiveis essential tomaintain a
solution-oriented focus, as it is easy for the practitioner to become overwhelmed and side-
tracked in the regulatory procedural requirements of remedy selection and losethe focus of the
real goal-identification and selection of a balanced, protective, and cost-effective approach to
remediation of a given site. Obviously, this must be achieved in a manner that satisfies the
regulatory requirements, but it remains essential to keep the proper technical perspective.
It is important for the engineering practitioner to understand that remedy selection, like
many technical endeavors, is an art as well as a science. We firmly believe that in most cases
there is not just one “technically correct” remedy for a site or that a singular correct remedy
will be identified by any qualified engineer if one follows the specified procedures as defined
in various guidance documents prepared by state and federal regulatoryauthorities. Rather, the
appropriate remedy for a site is a balance of several factors that include technical, business, and
financial considerations as well as environmental protectiveness, compliance with standards,
and effectivenessand other criteria prescribed by the USEPA in the National Contingency Plan
(which serves as the main regulatory document outliningthe requirements for proper remedy
selection under the federal Superfund program andwill be addressed later).
A. Setting Remedial Objectives

The fmt step in selecting an appropriate remedyfor a site is to set realistic objectives. Reme-
diation objectives should be focused on ensuring a suitable level of protectiveness of human
health and the environment. Political, regulatory, and financial considerations should come
into play when assessing how to achieve the objectives, not in setting them. Some of the key
factors that must be integrated into setting the objectives are as follows:
1. Real environmental and human health risk (based on realistic exposure scenarios)
2. Current andplanned site use
3. Useof surroundingproperty
4. Impact of site on surrounding areas
5. Assessment of active versus historical contaminant migration
6. Public opinion/support/opposition
7. Technicalfeasibility of achieving objectives
With these factors in mind, there is one overriding questionthat frames the core of any set of
objectives regarding remedy selection: What remedy should be implemented?
This may seem like an obvious question, but very often the remedy selection process fo-
cuses on Whatremedy can be implemented? Whenthe focus is on what is possible rather than
what is necessary, appropriate, feasible,and cost-effective,an unnecessarily expensive remedy
will almost certainly be selected. The possible remedy, which often attempts to remediate to
background or preexisting conditions, often imparts little or no added risk reduction but costs
substantially more andimparts an increase in short-term risk duringthe implementation period
Evaluation
Engineering Sites
for Contaminated 79
due to the inevitable site disruption, which is typically proportional to the aggressiveness of
remediation. Therefore, like most endeavors, there is a point of diminishing returns beyond
which additional beneficial effectsare not obtained and in fact negative effects are probable.
The assessment of should versus can goes to the most basic, yet controversial issues dom-
inating site remediation projects after nearly 12 years of implementing Superfund and other
remediation programs: How clean is clean?
The answer to this fundamental question is different if you assess it from a technical or
scientific perspective than from a political, cost-benefit, regulatory, or financial perspective.
Therefore, by definition, the final answer is site-specific and must properly integrate and baf-
ance the many factors that drive the remedy selection process at each site.
A negotiation process must therefore take place between the parties that have genuine in-
terests at each site. Federal and state environmental regulatory agencies usually allow and even
facilitate this negotiationprocess by offeringtothe parties having a financialliability
and responsibility to remediate the site the privilegeof taking the lead technicalrole in defining
and evaluating alternative remedies. The financially liable parties may include the current
owner/operator, all past owners/operators, or a party that sent any waste to the site (e.g., a
company that formerly used a permitted landfill); these are known as potentially responsible
parties (PRPs).
B. RemedySelectionCriteria
The National Contingency Plan (NCP),as revised in March 1990, sets forth the selection cri-
teria to be used in the evaluation of remediation alternatives. Remedies are evaluated in three
steps in accordance with the NCP and USEPA guidance documents:
1. Identification and evaluation of remedial technologies-usually targeted at one or more
specific site problems
2. Combining of suitable technologiesintoremedialalternatives-usuallyintendedtoad-
dress the entire site
3. Detailed analysis of alternatives-intended to support subsequent remedy selection
The first two steps are initially evaluated according to three criteria: effectiveness, imple-
mentability, and cost. Upon review of the definitions of these three criteria, as stated in the
NCP, the reader will see that they are essentially a repackaging of the expanded set of nine
criteria prescribed for the third step. Therefore, in this text, the focus is on the nine criteria for
three reasons: ( l ) The step-by-step procedureis already described in the NCP; (2) the focus of
this section is on the overall concept and thought process of remedy selection, not on strict
procedures; and (3) the practitioner is well served to keep all nine criteria in mind from the
beginning.
The nine criteria are listed below in the prioritized order the NCP has assigned to them.
Each listing includes an explanationof what the criterion means, or should mean, in practical
application.
Threshold Criteria
These two criteria must be met.
Protectiveness of Human Health andtheEnvironment. Attaining an acceptableresidual
risk presented by the site. The target residual risk must be within the range of one addi-
tionalcancerriskper 10,OOO population (1 X to oneadditionalriskper1 O , OOO
, OO
(1 X Thesecalculatedrisklevelsareverysensitiveto the set of exposure as-
sumptions made and the toxicological parameters and factors applied. These factors are
Wilson et al.
continuously being updated; however, itoften takes years for new information to be
accepted in practice, especially if it shows less risk than previously assumed.
Compliance with Applicable or Relevant and Appropriate Requirements (ARARs). Compli-
ance with promulgated laws and standards. Often, proposed standards, guidelines, and
agency policiesare incorrectly “applied” as if they were promulgated standards. This cri-
terion is often the focus of controversy between the agency and the owner or PR€! In ad-
dition, there are waiver provisions in the NCP that are sometimes granted when ARARs
are particularly burdensome or expensive or when compliance actually increases site risk
(usually short-term risk).
Balancing Criteria
These five criteria should optimize the remedy. The first three are relatively more important:
Long-Term Effectiveness and Permanence. The ability of the remedy to achieve and main-
tain the target protectiveness on a long-term and permanent basis.It is important to note
thatoftentheconcept of permanence is incorrectlyinterpretedtomean “destruc-
tion.” Treatment and containment remedies can also be permanent with proper control and
maintenance.
Reduction in Toxicity, Mobility, or Volume. The degree to which the contaminantsare altered
or recycled to render them less toxic or less likely to migrate or reduce their volume.
Zmplementability. An assessment of whether the remedy can be constructed and executed in
a technicallyfeasiblemanner to achievetheremediationobjectives.Availabilityand
proven performance are addressed under this criterion.
The other two balancing criteria are considered to be relatively less important:
Short-Term Effectiveness. The risk and impacts imparted by the implementation of the rem-
edy,such as risk to remediation workers and local residents, including transportation-
related risks for off-site remedies.
Cost. The capital and operations and maintenance costsof implementing the remedy and the
net present value ofthe remedy. It is interesting to note that for government-led Superfund
(lead-fund) cleanups, the cost criterion often becomes relatively more important than if an
owner or PRP is the funding entity.
Modifying Criteria
State Acceptance. The special concerns requiredor requested by the state agency in the case
of a federally led Superfund project.
Community Acceptance. The special concerns required or requested by the local community
or local agency in the case of a federally led or state-led Superfund project.
These criteria are used to evaluate remedial alternatives prior to actual remedy selection.
This evaluation effort may be completed by either the regulatory agencyor the owner/operator
or a PR€? Only the agency can select the remedy. However, when an owner has accepted the
responsibility to conduct the evaluation, it should also anticipate remedy selection and in fact
go thmugh the process of “selecting” the remedy to facilitate effective interchange with the
regulatory agency.
We propose that the following additionalconsiderations be integrated withthe nine selec-
tion criteria stated above:
1. Efficacy of the remedy. Does it achieve the objectives? It is not a success to efficiently
solve the wrong problem.
Evaluation
Engineering for
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Contaminated 81
2. Availability of target remedy. Is the technology commercially available or just in the lab-
oratory development phase? This consideration is often sidestepped, even though it is
included in the implementability criterion, in the name of promoting innovative technol-
ogies. We support the development and useof innovative technology. However,this must
\ be balanced with the needs of the specific site.
3. Necessary pre-or post-treatment or other treatmenthandling requirements. These require-
ments add cost and often add time to the remediation schedule.Too often the focus is only
on the core technology, when in reality the sum of supplemental unit processesmay cost
more or impart higher short-term risk than the core process.
4. Total cost of the remedy overthe life of the remedy (capital, operation and maintenance,
and monitoring).
5. Use of innovative technology. Should be selected only when conventional technology
cannot achieveobjectives, or innovative technology can achieve equal or superior results
at a lower cost, or innovative technologycan achieve equalor superior resultsat the same
cost but in less time or with less site disruption.
6. Cash flow demand-the rate at which the remedy must be funded. This is critical in de-
termining affordability.
7. Technical and regulatory precedent. Has the remedy been implemented previously?
8. Degree of uncertainty in problem definition, especially in terms of the volume or area
requiring remediation. Unfortunately, many projects advance to the remedy selection
stage before the “problem” has been adequately defined.
9. Agency objectives, predispositions, and national or logical policies.
10. Legal situation. The negotiate/remediate/litigatedilemma.
11. Corporate commitment of owner or PRF!
These additional considerations are consistent with the concept, as proposed in this section, of
targeting a remedy that is necessary rather than one that is merely possible.
It is important to note that the “cost-benefit” concept is not often adopted by the regu-
latory agencies in the remedy selection process in any formal manner (except in the case of a
fund-led cleanup). Cost is delegated to a low-priority criterion, which often is used only to
select from among remedies that are essentially equal in all other criteria. This can lead to a
circumstance whereany marginal reduction in residual riskis considered appropriate regardless
of the incremental cost increase. This text proposes that properly balanced remediation can be
achieved only through a concept of risk-based remedy selection.
C. ”Selecting”theRemedy
A formal three-phase procedure for identification and evaluation of remedies is presented in
“Guidance for Conducting Remedial Investigationsand Feasibility Studies Under CERCLA”
issued by the USEPA in October 1988. This procedure can be overly prescriptive and rigid if
misinterpreted; however, it does facilitate the development of appropriate remedial alternatives
for a given site. Unfortunately, in the absence of the proper context, criteria, and objectives, it
is easy to follow this procedure throughthe development and selection of extremely expensive
and unnecessarily complex and burdensome remedies.
The first step in the remedy selection process is a basic understandingof the problem-the
nature and extentof contamination. It is not necessary to have completed the problem defini-
tion phase, known as the Remedial Investigation (RI), to begin to develop and evaluate solu-
tions, that is, remedies. In fact, it is beneficial to beginto focus onthe remedy as soon as there
is a basic understanding of the site contamination and remedial objectives. This “early fo-
cus on the remedy” allows the problem to be defined in the context of the possibldprobable
82 Wilson et al.
solutions. This serves to streamline the RI and ensure that those conducting it obtainthe site
and contaminant information necessaryto properly assess and select an appropriate remedy.
The initial information should definethe media affectedby contamination-groundwater,
soil, sludges; the basic geologyand hydrogeology of the site, and the type of contaminants-
volatiles, semivolatiles, pesticides/PCBs,and inorganics. A preliminary assessmentof whether .
or not there are active source areas of ongoing contaminant migrationis very important at this
early stage, as it will be one of the main factors to consider in the remedy evaluation process.
In addition, one will need a preliminary assessment of the real risk imposed by the site con-
taminants. This will form the beginning steps of what is known as a “baseline” risk assess-
ment, which will prove essential in proper and informed remedy selection.
Evaluating Remedial Technologies
Once you know these factors, you can begin to target the types of remedial technologies that
will abate specific unacceptable conditions and satisfy remedial objectives. Each typeof prob-
lem can be addressed by a technology or linked technologies. Itis vitally important to buildan
array of remedial technologies beginning with one that ensures satisfaction of the protective-
ness criterion for the targeted problem. This is often the least controversial criterion, as all
parties in a remediation project are interestedin ensuring protection of human health and the
environment. Assumptions madein calculating risk to assess protectivenessare sometimes the
subject of disagreement between the agencies and the owner, but the concept of protectiveness
is rarely in dispute. Many of the other evaluation criteria are the subject of greater disagree-
ment. Therefore, it is a good practice to identify a limited set of technologies that arguably
achieve the protectiveness goal.
The potential remedies may fall into one or more of the following categories of remedial
technologies presented in Section I V no action, institutional actions, containment, removal,
treatment, and disposal. Initially, one or more of the remedial technologies from these cate-
gories should be considered. At the early stages of the remedial investigation, one can afford
to be somewhat broadbased in assessing which remedies show real promise in achieving the
remedial objectives, including cost.However, it is a good idea to streamline the target remedies
as soon as possible. Concurrent progress onthe RI effort will help inthe streamlining process.
Once a focused set of technologies and remedies have been tentatively identified that
satisfy the protectiveness criterion, they must be compared to the additional criteria to see if
the remedies are still in compliance. If the remedies do not comply with successive criteria,
they must be modified or additional remedies developedas necessary to ensuresatisfaction of
the criteria.
After a targeted subset of remediation categories are identified, the next step is to define
the basic method,or subcategory, within that category. That is to say, if treatment is one of the
targeted categories, one must then identify whether that is best achieved through physicall
chemical, chemical, biological, or thermal treatment technologies.
The next step is to define the particular technology or process within the subcategoryjust
defined. For example, within the physicakhemical subcategory for treating groundwater, there
are several choices: air stripping, steam stripping, vacuum-enhanced stripping, carbon adsorp-
tion, resin adsorption, or other. For soil remediation within the physical containment subcat-
egory, choices include clay cap, RCRA (layered) cap, soil cover with synthetic membrane,
simple soil cover, and others.
Some practitioners will take the position that refinement of the remedy to the level dis-
played above should be deferred untilthe remedial design (RD) stage. However, the RD stage
comes after the remedy is selected. At that point the flexibilityto refine or modify the remedy
is minimal and is burdened by regulatory procedural limitations. Therefore, it is advantageous
Evaluation
Engineering for
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Contaminated 83
to evaluate remedies down to the specific technology stage prior to remedy selection. This will
sometimes require that treatability studies be conducted. This effort should also precede rem-
edy selection.
It is more difficult and requires more skill and knowledge to evaluate specific technologies
in the feasibility study (FS) stage and still maintain a focused and limited set of alternative
technologies; however, that is the best way to lead to the selection of the optimal remedy; one
that meetsthe remedial objectives including cost-effectiveness. It is oftentrue that a wide array
of technologies can be “made to work” at many sites. This reflects the concept of possible
versus necessary. The goal of the technology evaluation and selection process is not just to
identify any workable technology but to define the most balanced remedy.
Evaluating Remedial Alternatives

A remedial alternative is the combination of remedial technologies that have been targeted to
address the sum of the individual problems at a site. Many times, it is appropriate to modify
one or more component remedial technologies or partial remedies becauseof beneficial or neg-
ative “side effects” resulting from the combination of component remedies. For example,s u p
pose there are two types of sludges on a site and the optimal technology for each is different
when viewed separately. However, the volume of sludge A is five times that of sludge B. If
sludge B is amenable to treatment via the targeted technology for sludge A, it may be more
cost-effective overall to combine sludges A and B and treat them bythe sludgeA method, even
though there is a more efficient technology available for sludgeB. Overall, the elimination of
the sludge B technology is likely to more than pay for the increased volume to be handled by
the sludge A technology.
To put remedy selection in a logical context, it is useful to array the remedial alterna-
tives as a function of residual site risk versus total cost. Thisis shown graphically in Figure 1.
This “cost-risk” curve, when calibrated to an actual site, is a powerful tool that clearly shows
the choices available and their implications. If implementation of alternative A yields an ac-
ceptable residual site risk, then it should be chosen unless there are compelling and rational
reasons to implementone of the other alternatives. Thegraph clearly demonstratesthat
the residual risk curve approaches an asymptote at some point while total cost continues to
increase dramatically with respect to risk. This is the point of diminishing returns concept pre-
viously mentioned.
After protectiveness is ensured, there are two of the remaining eight criteria that tend to
move the “acceptable” remedy from left to right on Figure 1: compliance with ARARs and
long-term effectiveness andpermanence.
An oftenquoted rule of thumb is that if it costs X dollars to achieve protectiveness, it
will cost 3 X 5X dollars to achieve compliance with ARARs and 10-15X dollars to achieve
“permanence” (when is viewed as “destruction” of contaminants). This is why it is essen-
tial to begin by developing remedies that achieve the initial threshold criterion, protective-
ness. Then expand or modify the remedy, only as necessary, to progressively comply with the
additional criteria. This “bottom-up” approach is the best way to ensure compliance in the
most cost-effective manner achievable. Unfortunately, many remedies are selected onthe basis
of a “top-down” approach, which tendstoresult in unnecessarilyexpensiveremedies.If
you define a 15-20X remedy first, nearly all other remedies could be viewed as relatively
cost-effective.
One of the fundamental areas of controversy in remediation projects between owners or
PRPs and regulatory agencies is this cost escalationafter protectiveness hasbeen ensured. The
disagreements essentiallycenter around the argument that what is protective today may not be
so in the future, especially if proper controls are not maintained.
84 Wilson et al.
Predominant Remedial Action Predominant Remedial Action
Containment Excavatioflreatment
Degree of Cost Uncertainiy

/
Al. 1
0 5 10 15 20 25 30
Estimated RemediationCosts, Millions of Dollars
Figure 1 Representativecost-residualriskrelationship.
D. Typical Problems with Remedy Evaluation and Selection

The most pervasive problem regardingremedy selection in the years since the Superfund pro-
gram began is the dominance of a “define the problem” mentality instead of a “define the
solution” focus. By farthe greatest amountof effort, dollars, and timeat remediation sites has,
to date, been spent in the investigation of contamination, with RIs often taking years and the
feasibility study effort being limited to a few months. Unfortunately, this has led to situations
where the selected remedy was unable to achieve the objectives, was extremely and unneces-
sarily expensive, or was commercially unavailable,or to combinations of these andother fac-
tors. Obviously, this has been partly responsible for the poor reputation and extensive criticism
that plagues the Superfund program as well as other remediation programs.
This situation is gradually changing. Public demand and frustrated agencies and corpora-
tions are bringing pressures, sometimes opposing pressures, on the process. In the last few
years, the remedy selection process has gone from being very sequentialto showing some in-
creased degreeof integration regarding the definitionof the problem and the definition of the
solution. Additional necessary changesare expected.
Although overstudyingthe problem (the “Study it to death” mentality) is a real shortfall,
it is also possible and equally disadvantageous to “under-define” the contaminant situation
and prematurely proceed tothe remedial design and remedial action(RDRA) stage. Often pub-
lic or political pressures forcethe RUFS effort to be unrealistically acceleratedto the point that
the engineers who facethe task of identifying and evaluating remedies find that the problem is
Evaluation
Contaminated 85
not well defined. This inevitablyleads to a situation where allor most of the site-specific think-
ing is deferred to the subsequent remedial design phase. This may lead to the implementation
of a remedy that is substantially less than optimal. Premature remedy selection can lead not
only to a waste of funds but also to a situation where thewrong problem is “solved,” leaving
the real problem unremediated. Sometimes the problem that remains unsolved is due to the
contaminants that pose the “principal threats” at the site. In such a case (and unfortunately,
there are several), the contaminants that causethe lesser concernmay have been “efficiently”
abated, giving the illusion of remediation and protectiveness while the true site risk is mini-
mally affected.
One of the main deficiencies arising from a poor understanding of the site problems is a
high degree of uncertainty regarding the volume or area of contaminated media requiring re-
mediation. This is a major burden in the effort to define a protective, balanced, and cost-
effective remedy because remedy selection is not a linear process. The optimal remedy for
40,000 cubic yardsof soil contaminated with volatile and semivolatile organics may not be the
optimal remedy for 4OOO cubic yards of soil with the same level of the same contaminants.
Many factors prevent the simple adoption of a remedy for a similar application but a site of
substantially different magnitude.
VI. SUMMARY
This chapter has presented some of the issues that face the site remediation engineer in pro-
fessional practice andhas suggested someof the techniques applicablein the endeavorto clean
up the nation’s hazardous waste sites with a knowledge-based, cost-effective, and systematic
but integrated approach. The key concept presented in this chapter is oneof balance. There are
no perfect remedies;they all have disadvantages and limitations. Each site presents a unique set
of trade-offs. The challenge is to balance the pros and cons in a manner that satisfies the es-
sential objectives, is implementable, and is affordable to the funding entity. Without this bal-
ance, a strategy of either stall or litigate will likely result instead of a remediation strategy.
The business ofremedy evaluation and selection is extremely complex and requires a
working knowledgeof environmental regulation, environmental law, process engineering, cost
estimating, and construction engineering.No single chapter,or even a full volume, can attempt
to convey more than the very basics of this profession. To compound the situation, it is very
dynamic and changes continuously,so what was optimal in the past may not be acceptable in
the future. This makes the practice very challenging, but also very exciting.
Innovative Approaches to Cleanup
Level Development
Ronald J. Kotun, Richard F. Hoff, Robert J.Jupin,

Diane McCausland, and Patrick B. Moroney
Chester Environmental
Monroeville, Pennsylvania
1. INTRODUCTION
Recently proposed regulations on the federal and state levels establish uniform cleanup stan-
dards to provide objectives for remediating contaminated sites. The purpose of these standards
is to restore contaminated sites to levels that ensure protectionof human health and the envi-
ronment. These regulations may result in consistent cleanup decisions and may expedite the
remediation of contaminated sites by eliminatinglengthynegotiationsovertheextent of
cleanup. However, this “consistency” may result in overconservative remediations and exces-
sive expense or, more important, inadequate remediation.
As part of a remedial investigation, a baseline risk assessment is conducted to determine
if there is any potential for adverse health effects due to hazardous substances released froma
site in the absence of controls. The risk assessment identifies constituents of interest (COIs)
exposure scenarios, and likely receptors (residents, construction workers, etc.) and quantifies
the amount of chemical intakeby a receptor at the site. The amount of intake can be translated
into a risk value that indicates the extent to which public health may be affected. The results
of the baseline risk assessment document the magnitude of risk and identify its primary cause.
The results also provide a basis for a decision as to whether remedial action is necessary.
The U.S.Environmental Protection Agency (EPA) has established guidelinesthat provide
a consistent process for evaluating and documenting threats to the public health and the envi-
ronment. Consequently, risk assessment provides a means to determine site-specific cleanup
goals that are adequately protective of human health. Other scenarios consider the environ-
mental fate and transport of chemicals to determine whether chemicalsin one medium might
have an impact on another medium. These approaches consider factors suchas the spatial dis-
tribution of chemicals, interim measures currentlyin place to control chemicaltransport, plau-
sible exposure scenarios, likely receptors to chemical exposure,and the physical and chemical
properties of the chemicals. Therefore, the results generated from these approachesmay span
several orders of magnitude yet still resultin protection of human health and the environment.
More important, these approaches derive levels that are technologically and economically fea-
sible to attain.
87
88 Kotun et al.
In this chapter we present four case studies that consider the factors previously discussed
to establish cleanup levels. These cases illustrate various means to derive a cleanup level that
is technically defensible. However, these levels may not necessarily be the optimum for site
remediation. Usually, more than one approach should be explored to establish the optimum
cleanup level.
Case I explores an innovative approachto the derivation of risk-based cleanup levels for
carcinogenic polycyclic aromatic hydrocarbons (cPAHs). Using relative potency factors and
specific exposure scenarios and considering apparent remedial strategies, a cleanup level for
cPAHs in pond sediments was determined. The target cleanup level was developed by estab-
lishing a correlation between the cPAH concentration in a pond sediment sample and the cor-
responding risk. Plotting thesedata to generatea regression equation andselecting a target risk
level allows one to identify a cleanup level.
Case I1 employs a similar statistical and graphical approachto deriving cleanup levels for
cPAHs, but the approach is more complex because cleanup levels are also being derived for
pentachlorophenol (PCP) and arsenic. Risk-based cleanup levels can be derived for exposures
to single constituents by back-calculating a soil constituent concentration corresponding to a
target risk level using risk assessment methodology. However, when the risks result from ex-
posure to more than one constituent, the target risk level should be apportioned among the
individual constituents. The availablesite data were evaluated to determine the relative distri-
bution of the chemicals across the site. Target risk levels were then apportioned among the
individual chemicals according tothese relative distributions.
Case I11 uses EPA's recently developed Multimedia Exposure AssessmentModel (Multi-
med) to derive soil cleanup levels for a source area of chemical release that would be protective
of groundwater at a designated downgradient receptor location. In this study, Multimed was
used to model the unsaturated and saturated zone fate and transport of PAHs. Groundwater
investigations revealed that the PAHs may leach from source soils and migrate horizontally
through an underlying aquifer toa downgradient well location and an adjacentestuarine river.
The cleanup levelswere developed to be protective of humans consuming waterat the receptor
well location, organisms inhabiting the river, and humans consuming organisms from the river.
Soil cleanup levels were calculated byusing the dilution-attenuation factors derived by the
model in combination with partition coefficients to meet applicable and appropriate perfor-
mance standards in the water.
Finally,Case IV employs other environmental fate and transportmodels,specifically
EPA's Organic Leachate Model (OLM) and Vertical and Horizontal Spreading (VHS)model,
to determine a soil cleanup goal for carcinogenic PAHs that is protectiveof underlying ground-
water quality. These two models account for the leaching of cPAHs into groundwater and their
dilution in the shallow saturated zone affordedby dispersion. Use of these analytical solutions
to derive a soil cleanup level providesa timely, cost-effectivealternative to complex numerical
modeling. Furthermore, the conservatism of the results may account for some of the temporal
and spatial variations inherent in even the simplest groundwater flow domainsnot accounted
for in complex models.
II. CASE STUDY I: REGRESSION ANALYSIS AND APPARENT

REMEDIAL STRATEGIES TO DERIVE CLEANUP LEVELSFOR
CARCINOGENIC PAHs
A. Introduction
The Comprehensive Environmental Response, Compensation, and Liability Actof 1980, as
amended (Superfund),is a national program that establishesa means to respond to releases of
Cleanup 89
hazardous substances.The National Oil and Hazardous Substance Pollution Contingency Plan
(NCP) is theregulationthatimplementsSuperfund and establishesthegeneralapproach
for remediation of hazardous waste sites. The objective of the program is to protect human
health and the environment fromthe potential harm posed by the constituents presentat these
sites.
The U.S. Environmental Protection Agency (EPA), administrator of Superfund, has es-
tablished a framework for assessing risks to human health that ultimately determines whether
remedial action is necessary at a site. The risk assessment process, as set forth in EPA's Risk
Assessment Guidancefor Superfund, Volume I, Human Health Evaluation Manual(Part A) [l],
provides an analysis of baseline risks, determines theneed for remedial action, and establishes
a basis for calculating cleanup levels. This process provides an alternative to meeting regula-
tory cleanup criteria and allows for the use of site-specific information to establish practical
remedial alternatives.
Cleanup levelsare being established for a pond that is adjacent to a former wood-treating
facility that operatedfor 18 years. The facility used creosote asthe preserving chemical.Of the
27 shallow sediment samples collected from the pond, cPAHs were detected in all samples with
total concentrations ranging from 0.807 to 144.82 mgkg (Table 1). In many cases, the high
degree of contamination is limited to a small area and is notcharacteristic of the entire site. A
frequency distribution of the cPAHs in the shallow pond sediments indicates that only fourof
the 27 samples had total cPAHs exceeding 30 mg/kg and seven had total cPAHs exceeding
10 mgkg (Table 2).
A risk assessment was prepared in accordance with Superfund for this pond to establish
baseline risks for all potential receptors and exposure scenarios. Based on the data, children
wading in the pond and coming into direct contact with the cPAH-impacted sedimentsare those
at the greatest potential risk. Therefore, development of cleanup levels for pond sediments is
based on this most sensitive receptor.
The primary objective of establishing cleanup levelsat this site is to be protective of hu-
man health, specifically the health of children wading in the pond. These children may come
in contact with the cPAHs in the sediments through dermal contact and incidental ingestion.
Baseline risks associated with exposure to the cPAH-contaminated sediments are based on the
application of Chu andChen's relative potency factor approach [2]. Using the site-specific data
and the relative potency factors,a cleanup level canbe calculated. Sediments withcPAH con-
centrations above a certain concentration would be removed, thus resulting in a reduced av-
erage concentration of cPAHs and a concomitant reduction in risk.
B. Chu and Chen's Relative Potency Factor Approach

Originally, risks attributed to exposure to cPAHs were derivedby assuming that all cPAHsare
equipotent to benzo[a]pyrene. Realizing that there is much scientific evidence that demon-
strates that benzojalpyrene is regardedas one of the most potent cPAHs and that all cPAHs are
not equipotent [2], alternative methods have been developed that assess risks more fairly. A
study conducted by Margaret Chu and Chao Chen of EPA's Carcinogenic Assessment Group
provides evidence to support these contentionsand also provides relative potency factorsthat
. allow for a more appropriate evaluation of risks associated with these less potent cPAHs.
Relative potency factors (RPFs) for six cPAHs are presented in Table3. These cancer slope
factors are derived by multiplying benzo[a]pyrene'soral cancer slope factorof 11S 3 [mg/(kg/
day)]" [3] by the RPF. Ultimately, potential risks are calculated by summing the products of
the cPAH concentrations and the corresponding cancer slope factors[l].
The total risk can be defined by the equation
Kotun et al.
2
l l l l $ l l l l
0
Cleanup Level Development 91
Table 2 Frequency Distribution of Total cPAHs in Pond Sediments"

Concentration
range (mag) Number of samples
BCLDL 0
DL5 9
5- 10 8
10-20 4
20-30 2
30-40 1
40-50 0
50-60 0
60-70 0
70-80 0
80-90 2
90- 100 0
100-1 10 0
110-120 0
120-130 0
130-140 0
140-150 1
>150 0
"BDL = below detection limits; DL = detection limit.
RL = x n
i= 1
-
(CSi CSFi EXP)
where RL is the risk level from exposure to cPAHs, CS, is the concentration of cPAH,, CSF,
is the cancer slope factor for PAH,, and EXP is the product of intake parameters to establish
long-term daily intakeof cPAH,.
EXP is defined as
CR EF ED
EXP =
BW-AT
where CR is the contact rate (ingestion rate or surface contact), EF the exposure frequency, ED
the exposure duration, BW the average body weight, and AT is the averaging time.
For children, an exposed skin surface area of 3768 cm2 was assumed to account for 50%
of the total body surfacearea. The exposed surface areais limited to 50% because itis unlikely
that the total surfacearea would be covered with sediment [4]. Absorption factorswere used to
reflect the desorption ofchemicalfrom the sedimentand the absorption of thechemical
through the skin to the bloodstream. A value of 5% was used for cPAHs[4]. Adherence to skin
was estimated at 1.45 mg/cm2 [4]. An exposure frequency of24 days per year(2 days per week
during the summer) for an exposure duration of 13 years was used. The average body weight
was 41.5 kg [5]. The averaging time was 70 years [l].
There are no recommended values for the amount of sediment a child may incidentally
ingest; therefore,the recommended incidental ingestion rate of 100 mg/day was used [6], with
only 50% of the sediment coming from the site. The exposure frequency, exposure duration,
body weight, and averaging timeare the same parameters thatwere used to assess risks due to
dermal exposure.
92 Kotun et al.
Table 3 Chu and Chen Relative Potency Factors for cPAH

factorpotency
Relative
Compound
Benzo[a]pyrene 1 .o
anthracene
Dibenzo[a,h] 0.69
fluoranthene
Benzo[b] 0.08
Chrysene 0.00122
Indeno[ 1,2,3-cd]pyrene 0.0171
anthracene Benzo[a] 0.0134
pyrene Benzo[k] 0.00444
Source: Chu and Chen [2].
With no remedial action taking place, the average cPAH concentration in the pond sedi-
ment is 20 mgkg. The risk to children exposedto these sediments through dermal contact and
incidental ingestion using the previously stated assumptions is 7.3 X
C. Site-Specific Development of Risk-Based Cleanup Levels

Each sediment sample consists of a different compositionof cPAHs that results in
a correspond-
ingly different probability of risk. For example, two sediment samples may have equivalent
total cPAH concentrations. However, the one sample that has a greater percentage of ben-
zo[a]pyrene, one of the most potent cPAHs, will pose the greater probability of risk. To illus-
trate this relationship among the sediment samples, a log-log plot of the probability of risk
versus the total cPAH concentration was developed (Figure 1). Cleanup levels correspondingto
1E44
1E47
0.1 1 10 100
Total Carcinogenic PAHs (rngwg)
Figure 1 Risks to children associated with total cPAHs resulting from exposure to pond sediments.
Table 4 Total cPAHConcentrations and Their

Corresponding Target Risk Levels
Total cPAH concentration
Risk (mgncg)
10~-4 280
IOE-~ 28
10E-6
target risk levels can be determined by simply locating them on the regression line. For ex-
ample, a target risk level of lo-’ corresponds to an average total cPAH concentration of 28
mg/kg (Table 4).
This pond has only fourof its 27 samples with totalcPAH concentrations exceeding a con-
centration of 30 mgkg (approximately the target risk of lo-’)). Remediating areas with ele-
vated levels of total cPAH to this concentration or “pickup level” would reduce the average
total cPAH concentration, or cleanup level,in the pond and consequently reduce the associated
risk. Table 5 presents various pickup levels and the risks that correspondto the cleanup levels
for children who wade in the pond. A pickup level of 30 mgkg results in a reduction of the
cleanup level for total cPAH concentration from 20 mgkg to 12 mgkg with a corresponding
reductioninriskfrom 7.3 X loF6to 4.3 X This approachresultsinlimitingthereme-
diation to the heavily impacted areas and minimizing unnecessary cleanup.
D. Conclusion
Risk assessment provides a means to determine whether chemicals present on a site exist in
concentrations that pose a potential threat to public health or the environment. The risk as-
sessment performed for this pond indicated that exposure to sediments from thepond presented
a significantrisk, with children wading in thepond being the most sensitive receptor. There are
be impractical
isolated areas in the pond that obviously require remediation; it would certainly
to remediate the entire pond to pristine conditions. Using risk assessment principles, acPAH
level can be estimated to which one can be exposed and still have a negligible probability of
developing cancer.
Our assessment of the site indicated that remediation to an average concentration of 30
mgikg would result in a risk level of l X lo-’. Without any remedial action, exposure to the
averagecPAHconcentrationthroughoutthesiteresultsinarisk of 7.3 X Remediating
areas in excess of 30 mgkg, the so-called pickup level, will lower the site average concentra-
Table 5 Pickup Levels, ResultingCleanupLevels,andTheir

Corresponding Risks to Children Wading in the Pond and Exposed
to Impacted Sediments
Pickup level (mg/kg) Site cleanup level ( m a g ) Risk level
7.3E-06
No action 20
90 18 6.68-06
70
6.OE-06 16
5.2E-06
50 14
30
4.3E-06 12
3.7E-06
20 10
2.6E-06
10 7
94 Kotun et al.
tion to a cleanup level of 12 mgkg and concomitantly reduce the risk by 41%. In essence,
determination of a site pickup level for cPAHs through regression analysis to meet a target risk
level can result in a practical remediation that is protective of public health, minimizes the
volume of sediments to be removed, and is most likely cost-effective.
111. CASE STUDY II: STATISTICAL METHODS TO DERIVE CLEANUP

GOALS FOR A SITE IMPACTED BY MORE THAN ONE CHEMICAL
A. Introduction
Cleanup levelsare being established to address contaminated surface and subsurfacesoils at a
wood-treating site that operated for approximately 65 years. The facility used creosote and pen-
tachlorophenol as wood-preserving chemicals.In general, polynuclear aromatic hydrocarbons
(PAHs) and pentachlorophenol were detected in nine areas of the site, ranging in concentration
from 1 to 10,800 mgkg and from 0.1 to 240 mgkg, respectively, The areas showingthe high-
est concentrationsof PAHs or pentachlorophenol were located or inadjacent to the treating area
and in a former disposal area. Although wood was never treated with chromated copper ar-
senate (CCA) at this site, arsenic and copper were detected above background levels in the
wood storage yard, at concentrations ranging from 24 to 369 mgkg and from 0.005 to 1.13
mg/kg, respectively.
A risk assessment was prepared .in accordance with Superfund for this site to establish
baseline risks for all potential receptors and exposure scenarios. Based on the data, on-site
workers and construction workers coming into direct contact with the impacted surface and
subsurface soilswould be at the greatest potentialrisk. Therefore, development ofcleanup lev-
els for surface and subsurface soilsis based on these most sensitive receptors.
The primary objective of establishing cleanup levels at thissite is to be protective of hu-
man health, specifically the health of on-site workers and construction workers. These indi-
viduals may come into contact with the constituents in the surfaceand subsurface soils through
dermal contact, incidental ingestion, and inhalation. Using site-specific
the data and targetrisk
levels, a cleanup level can be calculated.
Constituents detected at the site exhibit both carcinogenic and noncarcinogenic adverse
health effects. Potential adverse health effects due to carcinogenic substances are derived dif-
ferently from those due to noncarcinogenic substances. Therefore, cleanup levels have to be
developed to address both carcinogenic and noncarcinogenic adverse health effects. Theseare
dealt with in turn in the following sections.
B. Cleanup Levels for Potentially Carcinogenic Constituents

Results of the risk assessment indicated that potential risks for exposureof on-site workers and
construction workers to surface and subsurface soils were above the U.S. EPA's target risk
range of 10-4-10"j [7];therefore, risk-based levels were derived for these potential human
receptor groups. Constituents evaluatedin the risk assessment included PAHs, pentachlorophe-
nol, volatile organic compounds (VOCs), and metals. Cleanup levels can be developed for all
of the evaluated constituents of interest (COIs), but this is not necessary if the potential risks
from the individual COIs are insignificant. Following EPA Region 111 guidelines, cleanup lev-
els were developedfor only those constituents that contribute to 99% of the total potentialrisk.
Tables 6 and 7 present a summary of the potential risks and the percent contribution of the
individual constituentsto the total risk for the evaluated human receptor groups. As can be seen
from these tables, PAHs, pentachlorophenol, and arsenic were the COIs responsiblefor 99% of
Table 6 Summary of Potential Risks of Surface Soils to On-Site Workers

B Area Constituent
A Area D E Area
Potential risk
PAHs 4.7E-04 4.4E-03 1.7E-03 7.8E-05 15e-03
Pentachlorophenol 8.6E-06 1.4E-06 1.4E-04 8.8E-06 1.5E-06
Benzene O.OE+OO 1.5E-10 2.3E-09 4.6E-09 O.OE+OO
Styrene O.OE+OO 7.3E-11 5.5E-10 8.9E-10 O.OE+OO
Arsenic 2.8E-05 1.OE-04 O.OE+OO 5.8E-05 1.1E-05
Chromium O.OE+OO O.OE+OO O.OE+OO 3.1E-07 3.5E-07
Total potential risk 5.1E-04 4.5E-03 1.9E-03 8.5E-04 1.6E-03
Percent contribution to total potential risk
~~~
99.14%
PAHs 92.04%
92.66%
97.73%
92.75%
%7.34%0.03%
Pentachlorophenol
1.69% . 0.10%
.00% Benzene
00% Styrene
0.00% Chromium 0.04% 0.02%
56% Arsenic
Table 7 Summary of Potential Risks of Surface and Subsurface Soils to Future

Construction Workers
B Area Constituent
A Area D E Area
Potential risk
PAHs 2.8E-05 4.6E-04 2.3E-05 1.8E-05 6.2E-05
Pentachlorophenol l .4E-07 1.8E-08 1.7E-06 1.6E-07 1.OE-07
Benzene O.OE+OO 7.9E- 12 3.8E- 11 4.7E- 11 2.2E- 10
Styrene 4.6E- 13 1.6E- 12 1.4E-09 9.3E- 12 1.9E- 11
Arsenic 7.OE-07 2.8E-06 O.OE+OO 1.6E-06 3.8E-06
Chromium 4.2E-08 4.2E-07 O.OE+OO 5.OE-08 8.OE-08
Total potential risk 2.9E-05 4.6E-04 2.5E-05 1.9E-05 6.6E-05
Percent contribution to total potential risk
PAHs 96.99% 99.30% 93.25% 90.48% 93.98%
Pentachlorophenol 0.47% 0.00% 6.74% 0.85% 0.16%
Benzene 0.00% 0.00% 0.00% 0.00% 0.00%
Styrene 0.00% 0.00% 0.01% 0.00% 0.00%
Arsenic 2.40% 0.61% 0.00% 8.42% 5.75%
Chromium 0.14% 0.09% 0.00% 0.26% 0.12%
100.00%
100.00% 100.00% 100.00% 100.00%
the potential risk to on-site workers and construction workers; thus cleanup levels were derived
only for these COIs.
Potential risks were estimated in the risk assessment by evaluating exposuresto site surface
and subsurface soils via dermal contact, incidental ingestion, and inhalation exposure path-
ways. Applying the 99% contribution criteria mentioned aboveto each exposure pathway in-
dicated that cleanup levels shouldbe derived using eachof the evaluated exposure pathways.
96 Kotun er aZ.
Risk-based cleanup levels were derived using the procedures and exposures assumptions
presented in the risk assessment forestimating potential risk. Instead of using the sampled CO1
concentration in soil and solving the risk equations for potential risk, a target risk level was
assumed and the risk equations were solved for the concentration of the CO1 in soil.
The following equation was used in the risk assessment to estimate potential risk (PR):
PR = C, CSF EXP -
where C, is concentrationof COI, CSFis cancer slope factor, andEXP is the product of intake
parameters used to establish long-term daily intakeof COI.
EXP is defined as
EXP = (CR EF ED)/(BW AT)
where CR is contact rate, EF is exposure frequency, ED is exposure duration, BW is average

body weight, and AT is averaging time.
Solving Equation (3) to yield a soil concentration results in
C, = PR/(CSF EXP) (4)
Soil
cleanuplevels were
derived
for
target
risk
levels and
of as required by
the U.S. EPA.
Using the above method and the same intake assumptionsas were used in the risk assess-
ment,
cleanup
levels
corresponding to were
and calculated
pentachlo-
for
rophenol and arsenic and are presented in Table 8.
A different methodwas used for deriving cleanup levels for PAHs. PAHs comprise several
constituents, and itis more desirable to express a cleanup level for PAHs as total PAHs than to
derive cleanup levels for each individual constituent. First, the potential risk resulting from
exposure to only PAHs for on-site workers and construction workers was calculated at each
soil-sampling location. Second, the concentrationsof total PAHs were plotted against the cor-
responding potential risks as shown in Figures 2 and 3. Having statistically significant corre-
lations (R2), the cleanup goalscorresponding to lov5,and risklevels were located
on the plot and are presented in Table8. The cleanup levels presented in Table8 are appropriate
for those areas of the site that contain only PAHs, pentachlorophenol, or arsenic and not a
combination of the three COIs.
Table 8 CleanupLRvels (mgkg)with No

Apportioning of Target Risk Levels
Target risk level
Constituent 10-6
10-~ 10-5
On-site workers
Pentachlorophenol 700 70 7
Arsenic 314 31 3
Total PAHs 229 16 1
Construction workers
Pentachlorophenol 30,500 3050 305
Arsenic 6,620 662 66
Total PAHs 20,000 1300 85
Cleanup 97
Total PAHs (mg/Kg)

Figure 2 Potentialrisk vs. total PAHs-on-site workers.
1.
o Ea
Y
.v, 1.oE-05
a
l.OE-07
1.
o Ea
Figure 3 Potentialrisk vs. total PAHs-construction workers.

98 Kotun et al.
Table 9 Distribution of Risk to On-site Workers from Exposure to Surface Soils

Arithmetic
Standard
Minimum
mumdeviation mean
Constituent
Potential risk
PAHs 4.7E-04 1.2E-03 2.OE-06 6.3E-03 7.8E-05
Pentachlorophenol 3.8E-06 8.9E-06 O.OE+00 4.1E-05 8.2E-07
Arsenic 3.7E-05 3.5E-05 1.2E-06 1.5E-04 2.6E-05
Total 5.1E-04 1.2E-03 8.OE-06 6.5E-03 1.1E-04
Percent contribution
PAHs 64.88% 30.31% 4.51% 99.09% 71.16%
Arsenic 33.37% 30.04% 0.37% 95.28% 25.51%
Since the total potential riskfor most areas of the site is the result of exposure to several
COIs, the target risk levels must be apportioned among the COIs. The target risk level was
apportioned basedon the contributions of the risk levelsof the individualCOIs. For example,
if the site average potential risk level is 1 X and the site average potential risk from PAHs
is 7.5 X itwould be assumedthat (7.5 X 10-5)/(1 X or 75%, of thetargetrisk
level would be apportioned amongthe PAHs. This is the preferred method for apportioning the
target risk level among the COIs of the site, since potential risk is based on both the toxicity
and the concentration of the COI.
Polycyclic aromatic hydrocarbons, pentachlorophenol, and arsenic were identified above
as the major contributors tothe potential risk at the site. Eighty-seven surface samples and65
subsurface samples were collected at the site and analyzed for PAHs and pentachlorophenol,
but only 32 of the surface soil samples and 27 of the subsurface samples were analyzed for
arsenic. Only those soil samples analyzed for all three COIs were used in determining the ap-
portionment of the risk levels.
The potential risk of exposure to PAHs, pentachlorophenol, and arsenic for on-site workers
and construction workers was calculated for each of the selected soil samples. The average
contribution of each CO1 to the total risk for on-site workers is presented in Table 9. Table 9
illustrates that 65% of the total risk for on-site workers is due PAHs,
to 33%is due to arsenic,
and 2% is due to pentachlorophenol. Table 10 shows that 75% of the potential risk for con-
struction workers is due to PAHs, 23% is dueto arsenic, and 1.4%is due to pentachlorophenol.
The target risk levels were apportioned according to these distributions. As an example, as-
suming a targetrisklevel of 1 X for on-siteworkers,cleanuplevelswouldbederived
for PAHs corresponding to 65% of the 1 X or a 6.5 X lo-’ targetrisklevel. A
3.3 X lo-’ target risk level would be used for arsenic,and a 2 X targetrisklevelfor
pentachlorophenol.
Cleanup levels for on-site workers and construction workers based on the apportioning
method described above are presented in Table 11.As can be seen from thetable, cleanup goals
for on-site workers are lower than the corresponding goals for construction workers.
C. Cleanup Levels For Noncarcinogenic Constituents

Results of the risk assessment indicated that total hazard indices for on-site workers
and con-
struction workers were above the “acceptable” level of 1.O for some areas of the site. Tables
12 and 13 present a summary of the hazard indices and the percent contribution of the indi-
Table 10 Distribution of Risk to Construction Workers from Exposure to Surface and

Subsurface Soils
Arithmetic
Standard
tion mean
Constituent Minimum Maximum Median
Potential risk
~~
PAHs 2.6E-02 l.lE-01 3.6E-05 8.2E-01 1.1E-03

Arsenic 9.6E-04 1.6E-03 2.OE-08 7.5E-03 1.4E-04
Pentachlorophenol 1 .OE-04 3.OE-04 1.9E-07 1.9E-03 1.2E-05
Total 2.7E-02 l.lE-01 3.7E-05 8.2E-01 2.2E-03
Percent contribution
PAHs 75.64% 31.77% 2.49% 99.%% 94.36%
Arsenic 22.94% 31.78% 0.00% 97.43% 1.78%
Table 11 CleanupLevels ( m a g ) with Apportion

Apportionment of Target Risk Levels
Target risk level
Constituent 10-4 10-5 10-6
On-site workers
Pentachlorophenol 14 1.4 0.14
Arsenic 104 10 1 .o
Total PAHs 140 10 0.7
Construction workers
Pentachlorophenol 427 43 4
15 Arsenic 152 1515
PAHs Total 5350 445 35
vidual constituents to the total hazard index for the evaluated human receptor groups. As can
be seen from these tables, PAHs, pentachlorophenol, arsenic, copper, chromium, and zinc are
the COIs thatare responsible for 99%of the hazard index for on-site workers and construction
workers.
When the total hazard index exceeds 1.0, EPA guidelines [l] recommend that COIs be
segregated by target organ effects and mechanism of action to derive separate hazard indices
for each group. The COIs were segregated by effect and mechanismof action, and the resulting
hazard index still exceeded unity, indicating that the cleanup levels would also have to be de-
rived for noncarcinogenic COIs.
Past experience has shown that when cleanup levels are developed for constituents thatr
exhibit both carcinogenic and noncarcinogenic effects, those developed to address the carci-
nogenic effects are always lower than those developed to address the noncarcinogenic effects.
If the cleanup levels developed for the carcinogenic effects are also protective of the noncar-
cinogenic effects, then cleanup levels to address the noncarcinogenic effectsneed not be sep-
arately developed. Plots of the total hazard indices (for exposures to allCOIs, not just PAHs)
versus total PAHconcentrations are shown in Figures4 and 5. The targetcleanup level fortotal
PAHs corresponding to the target risk range presented in Table 8 is 140 mgikg for on-site
workers and 5350 mgikg for construction workers. The loF4cleanup level of 140 mgkg for
100 Kotun et al.
Table 12 Summary of Hazard Indices-Surface Soils and On-site Workers

Area A
Constituent
Area BArea C Area D Area E
Hazard Index
PAHs 2.3E-02 2.6E-01 1.1E+00 1.7E-01 3.7E-01
Pentachlorophenol 6.7E-03 1. IE-03 l.lE-01 6.88-03 1.2E-03
Phenol O.OE+OO 3.9E-05 2.6E-06 1.OE-05 1.9E-06
Toluene O.OE+OO 2.2E-07 4.5E-06 7.1E-06 O.OE+OO
Ethylbenzene O.OE+OO 2.9E-07 1.4E-05 1.2E-05 O.OE+OO
Styrene O.OE+OO 5.1E-07 3.8E-06 6.2E-06 O.OE+OO
Xylenes (total) O.OE+OO l.lE-07 1 .OE-04 4.8E-06 O.OE+OO
Arsenic 4.5E-02 1.6E-01 O.OE+OO 9.OE-02 1.8E-02
Chromium 3.5E-03 3.3E-02 O.OE+OO 6.6E-03 7.6E-03
Copper 4.1E-03 8.lE-02 O.OE+OO 7.OE-03 2.4E-03
Zinc 2.3E-03 3.1E-02 1.4E-03 1.9E-03 l.lE-03
Hazard index0.29 1.22
0.09 0.57 0.40
Percent contribution to total hazard index
92.54%
PAHs 60.70% 91.08%45.87%26.90%
0.29% 2.39% 8.79% 0.20% 7.89%
Pentachlorophenol
Phenol 0.00% 0.01% 0.00% 0.00% 0.00%
Toluene 0.00%0.00% 0.00%
0.00% 0.00%
Ethylbenzene 0.00% 0.00% 0.00% 0.00% 0.00%
Styrene 0.00% 0.00% 0.00%0.00% 0.00%
Xylenes0.01%
(total) 0.00% 0.00% 0.00% 0.00%
4.40%Arsenic
31.46% 0.00% 28.37%53.48%
1.89% 2.32% 0.00% 5.78% 4.14%
Chromium
Copper 14.35% 4.86% 0.00%0.61% 2.45%
0.28% 0.67% Zinc 0.12% 5.43% 2.72%
on-site workers corresponds to a total hazard index of 0.01 on Figure 4. The cleanup level
of 5350 mgkg for construction workers corresponds to a total hazard index of 1.O on Figure5 .
Remediating the site to the cleanup levels based on potential risk will lower the total hazard
indices for all the Cols to 1.O or lower; therefore, separate cleanup levelswere not derived for
noncarcinogenic compounds.
D. Conclusion
Risk assessment provides a means to determine whether constituents presentat a site exist in
concentrations that pose a potential threat to public health or the environment. The risk as-
sessment performed as part of the remedial investigation study for the site indicated that ex-
posuretosurfaceandsubsurfacesoilspresented a significant risk to on-site workersand
construction workers. Risk assessment methodology along withstatistical and graphical meth-
ods were used to derive cleanup levels for the site.
For areas that contain all COIs, the risk-based cleanup goals at the risk level were 140
mg/kg for total PAHs, 104 mgkg for arsenic, and 14 mgkg for pentachlorophenol. For areas
of the site that contained only a single constituent, the risk-based cleanup goals at the
risk levelwere 230 mg/kg for totalPAHs, 314 mgkg for arsenic,and 700 mg/kg for pentachlo-
rophenol.
Cleanup 101
Table 13 Summary of Hazard Indices4urface and Subsurface Soils, Future Construction Workers
ea A Constituent
Area E Area D Area
B C Area
Hazard Index
PAHs 9.5E-01 1.3E+00 7.OE-01 1.2E-01 1.6E+00
Pentachlorophenol 5.3E-03 7.OE-04 6.5E-02 6.4E-03 4.1E-03
Phenol 2.OE-06 1 SE-05 61.E-06 3.7E-06 1.9E-05
Tolulene 7.6E-08 6.8E-07 4.7E-06 3.8E-06 7.7E-06
Ethylbenzene 2.5E-07 4.6E-07 1.1E-05 6.1E-06 1.8E-05
Styrene 1.6E-07 5.7E-07 2.1E-06 3.2E-06 6.6E-06
Xylenes (total) l.lE-07 1.4E-07 5.3E-05 2.5E-06 3.8E-06
Arsenic 4.68-02 1.8E-01 O.OE+OO l.lE-01 2.5E-01
Chromium 2.9E-02 2.8E-01 O.OE+OO 3.4E-02 5.4E-02
Copper 4.2E-03 9.8E-02 O.OE+OO 1.4E-02 1.2E-02
Zinc 5.9E-03 3.5E-02 1.9E-03 3.OE-03 3.3E-03
4-Methylphenol 1.3E-04 1.4E-05 9.9E-05 O.OE+OO 3.7E-04
2-Methylphenol 8.3E-05 O.E+00 9.9E-05 O.E+00 3.7E-04
2,4-Dimethylphenol 6.9E-04 2.4E-05 2.5E-04 O.OE+00 1.OE-03
1.88
Hazard Index 0.28 1.040.76 1.93
Percent contribution to total hazard index
PAHs 91.26% 68.85% 91.21% 41.61% 82.79%
Phenol 0.00% 0.00% 0.00% 0.00% 0.00%
Phenol 0.00% 0.00% 0.00% 0.00% 0.00%
Tolulene 0.00% 0.00% 0.00% 0.00% 0.00%
Ethylbenzene 0.00% 0.00% 0.00% 0.00% 0.00%
Styrene 0.00% 0.00% 0.00% 0.00% 0.00%
Xylenes (total) 0.00% 0.00% 0.01% 0.00% 0.00%
Arsenic 4.41% 9.50% 0.00% 37.97% 13.16%
Chromium 2.77% 14.71% 0.00% 12.06% 2.89%
Copper 0.40% 5.08% 0.00% 5.03% 0.66%
Zinc 0.57% 1.82% 0.25% 1.05% 0.17%
CMethylphenol 0.01% 0.00% 0.01% 0.00% 0.02%
2-Methylphenol 0.01% 0.00% 0.01% 0.00% 0.02%
2,CDimethylphenol 0.07% 0.00% 0.03% 0.00% 0.06%
IV. CASE STUDY 111: DERIVATION OF SOIL PAH CLEANUP GOALS

USING THE MULTIMED MODEL
A. Introduction
A remedialinvestigatiodfeasibilitystudy (RUFS) was conductedat a former wood-treating and
storage facility in Virginia that is currently included onEPA's National Priority List (NPL) of
Superfund sites. A finalRI report, which characterized the natureand extent of contamination
of surface and subsurface soils at the site as well as groundwater in the shallow, unconfined
Columbia Aquiferand the deep Yorktown Aquifer beneath the site, was submittedto the EPA
and VDWM and was subsequently approved. Analytical groundwater data acquired for the
shallow, unconfined aquifer during the RI revealed that detectable concentrationsof polycyclic
aromatic hydrocarbons (PAHs) were present in the groundwater. Analytical data acquired dur-
ing the RI also revealed the presenceof the samePAHs in the unsaturated zone soils above the
102 Kotun et al.
10
v 0.1
2
U
0.001
o.Ooo1
10 100 1
Total PAHs (mg/Kg)
Figure 4 Totalhazardindex vs. total PAHs-on-site workers.
100
10
0.1
0.01
0.001
1 10 100 1O
, oo
Total PAHs (mg/Kg)
Figure 5 Totalhazardindex vs. totalPAHs-constructionworkers.
Table 14 Summaryof Polycyclic Aromatic Hydrocarbons

(PAHs) Detected in Soil and Groundwater Samples During
Remedial Investigation
Potentially carcinogenic PAHs Noncarcinogenic PAHs
Benzo[u]anthracene Acenaphthene
Benzo[u]pyrene Acenaphthylene
Benzo[b]fluoranthene Anthracene
Benzo[k]fluoranthene Benzo[g,h,qperylene
Chrysene Fluoranthene
Dibenzo[a,h]anthracene Fluorene
Indeno[ 1,2,3-cdlpyrene Naphthalene
Phenanthrene
Pyrene
shallow aquifer. Both potentially carcinogenic and noncarcinogenic PAHs (cPAHs and nPAHs,
respectively) that are commonly associated with wood-treating and storage activities were
identified as contaminants in a public health and environmental assessment (PHEA) that was
performed as part of the final RI for the site (Table 14).
l h o areas, areas A and B, were delineated as potential source areas on the western and
eastern portions of the site, respectively (Figure 6). The presence of PAHs in the soil and
groundwater samples collected from these areas implies the possibility of downward vertical
movement of organic leachate from the unsaturated zoneto the groundwater of the Columbia
Aquifer. Once in the groundwater, the potential exists for the transport of PAHs from beneath
source areas A and Bto a receptor domestic welland an adjacent estuarine river, respectively.
Although the aquifer is not currently being used as a potable water supply, it could be used as
such in the future. Hypothetical off-site domestic wells in areas west of the site are therefore
considered to be potential receptors in a future scenario. The adjacent river is considered beto
a potential environmental receptor for those PAHs that have leached from the soil into the shal-
low aquifer at the site.
For the purpose of conducting a focused feasibility study, it became necessary to develop
soil cleanup goals for PAHs that were protective of (1) humans consuming groundwater at a
receptor well location impacted by area A, (2) organisms inhabiting the river, and(3) humans
consuming organisms from the river impacted by area B. It was suggested by EPA that this task
be performed by applying EPA's Multimedia Exposure AssessmentModel (Multimed) to des-
ignated source area(s) at the site [8]. The monitoring well designated MW-l02 (Figure6 ) , in-
stalled in the Columbia Aquifer in the southwestern portion of the site, was selected as the
receptor welllocationfor PAHs migrating fromareaA, sinceitissituateddowngradient
of source area Aand PAHs weredetected in groundwater samples collected from this location.
In addition, property west of the site is more likely to undergo residential development than
property at any other on-site or offsite location. The adjacent river, as stated previously, was
determined to be the potential environmental receptor for constituents migrating from source
area B.
The purpose of Multimed in the development of soil cleanup goals was the derivationof
dilution-attenuation factors (DAFs) that are used as multipliers for selected applicableand ap-
propriate performance standards at the receptor location of interest. This will be explained in
greater detail in a later discussion.
104 Kotun et al.
a
CI
I
d
W
B
- +-
B. Description of Multimed
Multimed is a recently developed user-friendly computer model that is capable of simulating
the release of chemicals in leachate form from a source (or designatedarea) at the site to soils
directly beneath the source. In addition, Multimed can be used to further simulate chemical
fate and transport in the unsaturated and saturated zones, followedby possible interceptionof
the subsurface plume by a specified receptor (e.g., a well or surface stream).
The fate and transport of a chemical released from a source is simulated by incorporating
the known responses of the chemical toa number of complexphysical, chemical,and biological
processes the chemical encounters as moves
it in the multimedia environment. These responses
are incorporated as chemical-specificvariable input data by the model user. Other variable in-
put data, such as source-specific and aquifer-specific data, must also be incorporated by the
user. For some of the variable input data, the model provides the user with an optionto either
manually specify values for the variable input data (constant input) or have the model mathe-
matically derive the variable input data from other constant inputs (derived input).
After all relevant input data have been defined and the type of output desired has been
specified, the multimedia transport of each contaminant is mathematically simulated by the
model. An output file is then generated showing final concentrations of specific constituents
and any other pertinent information(i.e., times of concentration Occurrences or statistical dis-
tributions resulting from multiple iterations). The final downgradient concentration(s) calcu-
lated by the model can be used to represent potential toxic exposureconcentration(s)to which
human and/or environmental receptors may be subjected.
For this site, deterministic and Monte Carlo simulations of steady-state unsaturated and
saturated zone flowand transport were performed using Multimed.A Gaussian boundary con-
dition was applied to the saturated zone transport of the contaminants away from the source,
with the maximum concentration occurring at the source.
Steady-state conditions in the model were used for the approximation of a system mass
balance in which water entering the flow systemis balanced by the water leaving the system.
There is no significant temporal variationin the system. Thus, the assumption of a steady-state
system basically simplifies the mathematical equations used in describing the flow and trans-
port processes and reduces the amount of input data, since no information on temporal vari-
ability is necessary.
The primary assumption of steady-state flow and transport is that the source is of a suf-
ficiently large chemical mass to ensure that the final downgradient contaminant concentration
in the groundwater is maintained at the receptor location. The source is assumed to be con-
tinuous and constant, without decay or any other temporal variation.
In the deterministic model of steady-state conditions, each inputvariable is of fixed value
and is assumed to havea fixed mathematical relationship with the other variables. Each run of
a deterministic model can result in either the output of one maximum concentration or time-
stepped concentrations occurring over a specified time interval. For this site, the output se-
lected was the maximum concentration that wouldOccur over an arbitrarily selected 500-year
period.
The deterministic mode of the Multimed model should only be applied to one or more
particular modeling situations in which all values for the input variables are known or can be
assumed with a high level of confidence. If there is uncertainty as to the values of input vari-
ables, then the simulation(s)may be performed within the MonteCarlo framework, wherethe
randomness and uncertaintiesof values inherent in the modeled system can be evaluated. Input
values in the deterministic model were either constant or derived values. Tables 15-17 present
106 Kotun et al.
Table 15 Summary of Multimed Input Parameters Used in Modeling PAH

Leachate Flow and Transport Through the Unsaturated Zone for Modeling to
MW-l02 and the River-Deterministic Model of Steady-State Conditions
its variable Input type
Unsaturated zone material variables

Depth of unsaturated zone m 1 Constant
Number of layers - 1 Constant
Saturated hydraulic conductivity 4.42" cmlhr Constant
Unsaturated zone porosity - 0.38b Constant
Unsaturated zone function variables
Alfa coefficient cm" 0.075' Constant
Residual water content - 0.065* Constant
Van Genuchten exponent - 1 .89' Constant
Unsaturated zone transport variables
Bulk density of soil for layer @cm3 1.4P Constant
Longitudinal dispersivity of layer
0.042' m Derived
Percent organic matter - 0.59 Constant
Thickness of layer m 1 Constant
"Literature value obtained from Mulrimed User's Manual, Table 6-2. for sandy loam.
bValue obtained from Mulrimed User's Manual, Table 6-3. Represents average porosity for sand
(fine and coarse), gravel (fine and coarse), silt, and clay.
'Literature value obtained from Mulrimed User's Manual, Table 6-5, for sandy loam.
dLiterature value obtained from Mulrimed User's Manual, Table 6 - 4 , for sandy loam.
=Literature obtainedfrom Mulfimed User's Manual, Table 6-8, for sandy loam.
'Value obtained from the calculation av = 0.02+ O.O22L, where UY is longitudinal dispersivity
(unsaturated flow in the vertical direction) and L is the depth of the unsaturated zone = Im.
Xiterature value obtained fromMultimed User's Manual. Table 6-7,for group B soils.
all values used in defining the unsaturated and saturated zone input variable parameters as-
sumed for the site in the deterministic model.
The Monte Carlo method provided a means of applyingthe known uncertainty associated
with an input variable to that variable. This uncertainty is expressed as a cumulative probability
distribution. For each uncertain inputvariable, a probability distribution must be specified that
best describes the frequenciesof Occurrence of measured valuesfor that variable.As the Monte
Carlo simulation is run overa large number of iterations (the number of iterations is specified
by the user), random values generated froma specified probability distribution are assigned to
the variable. For this site, 500 Monte Carlo simulations were performed by Multimed. The
probability distribution may be specified as uniform, log,, uniform, normal, log,, normal, ex-
ponential, empirical, or the Johnson system of distributions, Relating the input variableto any
one cumulative probabilitydistribution may be difficult. The difficulty arises from the fact that
the specification of a distribution for an input variable requires a large amount of site-specific
data that may not be available.
The types of values assigned to the Monte Carlo, steady-state input variables were either
constant, derived, or ranges of uniform distribution. For this site, a uniform distribution of
values was specified for each select input variable due to the lack of site-specific data for those
variables. All values used in defining the unsaturated and saturated zone inputvariable param-
eters assumed forthe site in the Monte Carlo steady-statemodel are presented in Tables 18-2 1.
Cleanup 107
Table 16 Summary of Multimed Input Parameters Used in Modeling PAH Leachate Flow and
Transport Through the Saturated Zoneof the Columbia Aquifer to Receptor Well Location MW-102-
Deterministic Model of Steady-State Conditions
Input
Chemical-specific variables
Acid-catalyzed hydrolysis 0" Constant
Base-catalyzed hydrolysis rate 0" Constant
Biodegradation coefficient (sat. zone) 0" Constant
Dissolved phase decay coefficient 0" Constant
Distribution coefficient, Kd - Derivedb
Neutral hydrolysis rate constant 0" Constant
Normalized distribution coefficient, Koc -a Constant
Overall chemical decay coefficient v Constant
Overall first-order decay coefficient 0" Derived
Reference temperature 25 Constanf
Solid-phase decay coefficient 0" Constant '
Source-specific variables
Area of western source 8260' Constant
Duration of pulse - Constant'
Infiltration rate 0.3178 Constant
Initial concentration of leachate l00h Constant
Length scale of source 90.88' Derived
Near-field dilution >lg Derived
Recharge rate 0.317g Constant
Source decay constant v Constant
Spread of contaminant source 15.1' Derived
Width scale of source 90.88' Derived
Aquifer-specific variables
Angle off centerline of plume 0 Constant'
Aquifer porosity 0.38' Constant
Aquifer thickness 5.34 Constant
Bulk density 1 .49k Constant
Distance to receptor,X, 183' Constant
Groundwater seepage velocity -m Derived
Hydraulic conductivity 442 Constant
Hydraulic gradient 0.006 Constant
Longitudinal dispersivity 18.3" Constant
Mixing zone depth -m Derived
Organic carbon content (fraction), f, 0.005" Constant
Particle diameter 0.03p Constant
Retardation Coefficient - Derived
Temperature of aquifer 18 Constant'
Transverse dispersivity 6.1" Constant
Vertical dispersivity 1.02" Constant
pH 6.5 Constant'
.Literature value obtained from Ref. 11.
bDistributioncoefficient (not presented by model output) was derived from the calculation K,, = K, f,, where K,
is the normalized distribution coefficient and f, is the organic carbon content (fraction).
'Conservative input value assumed.
dValue will be zero since it is derived from solid and dissolved phase coefficients, which themselves were assigned
a value of zero.
108 Kotun et al.
Table 16 Continued
Temporal factors are ignored under steady-state conditions.
'Area was designated as shown in Figure 7. Model assumed area is square, approximated area at 8260 mz with
length = width = 90.88 m.
%filtration and recharge rates selected for model represents minimum values derived from Hydrological
Evaluation of Landfill Performance (HELP) model.
hAssumedvalue.
'Spread of Gaussian contaminant source = (width of source)/6.
jValue represents mean of the mean porosity values for materials ranging from fine sand to clay-Table 6-3,
Multimed User's Manuul.
'Literature value obtained from Multimed User's Manual, Table 6.8. for sandy loam.
'Determined from Figure 7.
"'Modelderived value unknown to user.
"Longitudinal dispersivity,a, = 0. I X,;transverse dispersivity = aU3; vertical dispersivity = 0.056 d.
"No site-specificf, data available. Input value of0.005 is a model default value that falls within range off,
values derived fromfom values obtained fromMulrimed User's Manual, Table 6-7,for group B soils using the
equationf, = foJ172.4.
Wean particle diameter assumed from range givenfor medium sand in Table6-10 of Multimed User's Manual.
SActual modelderived R,, value unknown to user.
Transport Through the Saturated Zone of the Columbia Aquifer to the Adjacent River-Deterministic
Model of Steady-State Conditions
Variable Input type Input
Units Value
Acid-catalyzed hydrolysis rate 0" Constant
Basecatalyzed hydrolysis rate 0' Constant
Biodegradation coefficient (sat. zone) v Constant
Dissolved phase decay coefficient oe Constant
Distribution coefficient, Kd - Derivedb
Normalized distribution coefficient. K, -a Constant
Overall chemical decay coefficient 0' Constant
Overall first-order decay coefficient Od Derived
Reference temperature 25 Constant'
Solid-phase decay coefficient 0' Constant
rea of eastern sourcef 10,Ooo Constant
Duration of pulse - Constant'
Infiltration rate 0.317g Constant
Initial concentration of leachate 100h Constant
Length scale of sourcef 100 Derived
Near-field dilution >1g Derived
Recharge rate dy
r 0.317g Constant
Source decay constant yr-' 0' Constant
Spread of contaminant source m 16.7 Derived'
Width scale of sourcef m 100 Derived
Angle off centerline of plume 0 Constant'
Aquifer porosity 0.38' Constant
Cleanup 109
Table 17 Continued
Input
Aquifer m 5.34 Constant
Bulk 1.49k Constant
to Distance X, m 244' Constant
velocityseepage
Groundwater - Derived"'
ivity Hydraulic dy
r 820 Constant
Hydraulic - 0.006 Constant
rsivity Longitudinal 24.4 Constant"'
Mixing - Derived'"
fraction),
content
carbon
Organic f, - 0.005 Constanto
Particle 0.03 ConstantP
Retardation coefficient - - Derivedq
Temperature of aquifer ' "C 18 Constante
vity Transverse m 8.13 Constant"
Vertical 1.37 Constant"
PH - 6.5 Constant'
'Literature value obtained from Ref. 1 I .
bDistribution coefficient (not presented by model output) was derived from the calculation Kd = K,f,, where K,
is the normalized distribution coefficient andf, is the organic carbon content(fraction).
cConservative input value assumed.
dValue will zero since it is derived from solid and dissolved phase coefficients, which themselves W- assigned
a value of zero.
Temporal factors are ignored under steady-state conditions.
'Area was designated as shown in Figure 7. Model assumed area is square, approximated area at 10,ooO m* with
length = width = IOOm.
%filtration and recharge rates selected for model represents minimum value derived from Hydrological Evaluation
of Landfill Performance (HELP) model.
hAssumed value.
'Spread of Gaussian contaminant source = (width of sourceY6.
jValue represents mean of the mean porosity values for materials ranging from fine sand to clay-Table 6-3,
Mulrimed User's Manual.
'Literature value obtained from Uulrimed User's Manual, Table 6-8, for sandy loam.
'Determined from Figure 7 .
"Modelderived value unknown to user.
"Longitudinal dispersivity, aL = O . l X r ; transverse dispersivity = d 3 ; vertical dispersivity = 0.056oL.
"No site-specificf, data available. Input value of 0.005 is a model default value that falls within range off,
values derived fromf, values obtained fromUulrimed User's Manual, Table 6-7,for group B soils using the
equationf, = fJ172.4.
Wean particle diameter assumed from range given for medium sandin Table 6-10 of Multimed User's Manual.
qActual modelderived Rd value unknown to user.
C. Use of Output Data For Derivation of

Site-Specific Soil Cleanup Goals
As stated previously,the purpose of Multimed inthe development of site-specificcleanup goals
is the derivation of dilution-attenuation factors.These derived factors are then used as multi-
pliers for selected performance standardsat the receptor locations of interest. Rather than de-
veloping a soil cleanup level for each PAH compound individually, one soil cleanup goal
for total PAHs was calculated that will be protective of the groundwater at monitoring well
MW-102,marine organisms in the river, and humans consuming organisms from the river.
110 Kotun et al.
Table 18 Summary of Multimed Input Parameters Used in Modeling PAH Leachate Flow
and Transport Through the unsaturated Zone for Modeling to MW- 102-Monte Carlo Model
of Steady-State Conditions
variable Input
~ ~~~~~ ~

Depth of unsaturated zone 0.613-1.33 Uniform
Number of layers 1 Constant
Saturated hydraulic conductivity l .O-150 Uniform
Unsaturated zone porosity 0.250-0.500 Uniform
Alfa coefficient 0.005-0.145' Uniform
Residual
water
content ' 0.034-0. 100b Uniform
Van Genuchten exponent 1.09-2.68' Uniform
Bulk density of soil for layer @cm3 1.25-1.76' Uniform
Longitudinal dispersivity of layer m Derivedd
Percent organic matter - 0.180-1.30' Uniform
Thickness of layer m 0.500-2.00' Uniform
'Literature values obtained from Multimed User's Manual, Table 6-5, for sandy loam.
kiteramre values obtained from Multimed User's Manual, Table 6 - 4 , for sandy loam.
'Literature values obtained from Multimed User's Manual, Table 6-8, for sandy loam.
dDerived values obtainedfrom the calculation av = 0.02+0.022L, where av is the longitudinal dispersivity (unsat-
urated flow in the vertical direction) and L is the depth of the unsaturated zone = lm.
'Literature values obtained from Multimed User's Manual, Table 6-7, for group B soils.
Transport Through the Saturated Zone of the Columbia Aquifer to Receptor Well Location
MW-102-Monte Carlo Model of Steady-State Conditions
Input Value(s)
Acid-catalyzed
hydrolysis
rate (MY r r l 0" Constant
yr)"
Base-catalyzed
(Mhydrolysis
rate 0" Constant
Biodegradation coefficient
(sat.
zone) Yr- I 0' Constant
coefficient
Dissolved
decay
phase Yr" 0" Constant
coefficient,
Distribution
of K,, - - Derivedb
constant
hydrolysis
Neutral
rate Yr" 08 Constant
Normalizeddistribution
coefficient, K, &g 14.2-5,500,0008 Uniform
Overall
chemical
decay
coefficient
yr- I 0' Constant
Overall
first-order
decay
coefficient Yr- ' Od Derived
temperature Reference 25' Constant
coefficient
decay
Solid-phase Yr" 0" Constant
source'western of Area 8260 Constant
rate Infiltration dYr 0.317-0.587' Uniform
concentration
leachate
mg/L
Initial
of 100" Constant
ourcef of scale Length 90.88 Derived
dilution Near-field - l' Derived
te Recharge dYr 0.308-0.744 Uniform
constantdecaySource Yr- I OC Constant
Cleanup 111
Table 19 Continued
Input type
of Spread
ale Width
e off Angle v Constant
Aquifer -
Uniform 0.26-0.57j
Aquifer
Bulk
o Distance X, m 183' Constant
WYrvelocity
Groundwater
seepage - Derived
ctivity Hydraulic
Hydraulic gradient - Uniform
0.0011-0.0100
ersivity Longitudinal m Constant 18.3"'
ne Mixing - Derived
Organic carbon content (fraction),f, - Uniform
0.0010-0.0076"
Particle Uniform
Retardation coefficient - - Derived
Temperature16-25'
of aquifer "C Uniform
Transverse dispersivity m 6.1"' Constant
Vertical dispersivity m 1.02"' Constant
PH - Constant 6.00-9.00'
"Literature values obtained from Ref. 11.
bDistribution coefficient was derived from the equation Kd = K,f,, where K, is the normalized distribution co-
efficient andf, is the organic carbon content (fraction).
'Conservative input value assumed.
dValue will be zero since it is derived from solid and dissc!ved phase coefficients, which themselves were assigned
a value of zero.
'Assumed value(s).
' h a was designated as in Figure 7. Model assumed area is square, approximated area at 8260 m*, with
length = width = 90.88 m.
%filtration rates selected for model represent the minimum and maximum values derived from Hydrological
hAssumed value.
'Spread of Gaussian contaminant source = (width of source)/6.
@orosity values represent range fromfine sand to Clay-Mulrimed User's Manual, Table 6-3.
'Literature values obtained from Mulrimed User's Manual, Table 6-8. for sandy loam.
'Determined from Figure7.
"'Longitudinal dispersivity, OL. = O.lX,; transverse dispersivity = oU3; vertical dispersivity = 0.056aL.
"No site-specificf, data available. Input value range obtained fromMulrimed User's Manual, Table 6-7, for group
B soils using the equationf, = f0,,,/172.4.
OParticle diameter range assumed for particle types ranging from fine silt to coarse gravel, given in Table6-10 of
the Mulrimed User's Manual.
The groundwater performance standard assumed at well location MW-l02 for the deriva-
tion of a soil cleanup goal for total PAHs at area A was the proposed maximum contaminant
level (MCL) for benzo[a]anthracene,O.OOO1 mg/L [9]. Although there are various MCLs and
DWELs established for the individual PAH compounds, this MCL was selected for the total
PAHs since it represents the most health-conservative drinking water standard. The perfor-
mance standards assumed of soil cleanup goals for total
at the river for the derivation PAHs that
were protectiveof marine organisms and humans consuming organisms from the river impacted
by area B were 0.3 and O.oooO311 mg/L, respectively [lo].
112 Korun er al.
Table 20 Summary of Multimed Input Parameters Used in Modeling PAH Leachate Flow
and Transport Through the Unsaturated Zone for Modeling to the Adjacent River-Monte Carlo
variable Input type
~

Depth of unsaturated zone 0.500-2.00 Uniform
Number of layers 1 Constant
Saturated hydraulic conductivity 1.0-150 Uniform
Unsaturated zone porosity 0.250-0.500 Uniform
Alfa coefficient 0.005-0.145" Uniform
Residual water content 0.034-0.l00b Uniform
Van Genuchten exponent 1.09-2.68' Uniform
Bulk density of soil for layer @cm3 1.25-1.76' Uniform
Longitudinal dispersivity of layer m Derivedd
Percent organic matter 0.180-1 .30' Uniform
Thickness
layer
of . m 0.500-2.00" Uniform
'Literature values obtained from Mulrimed User's Manual, Table 6-5, for sandy loam.
bLiterature values obtained from Mulrimed User's Manual, Table 6-4, for sandy loam.
'Literature values obtained from Mulrimed User's Munual. Table 6-8, for sandy loam.
dDerived values obtained from calculation m = 0.02+0.022L, where av is longitudinal dispersivity (unsaturated
flow in the vertical direction) and L is depth of the UnSaNrated zone = 1 m.
'Literature values obtained from Mulrimed User's Manual, Table 6-7,for group B soils.
Transport Through the Saturated Zone of the Columbia Aquifer to the Adjacent River-Monte Carlo
~
Input Variable type Input Value(s) Units

Acidcatalyzed hydrolysis rate 0" Constant
Basecatalyzed hydrolysis rate 0" Constant
Biodegradation coefficient (sat. zone) 0" Constant
Dissolved phase decay coefficient 0" Constant
Distribution coefficient, K,, - Derivedb
Normalized distribution coefficient.K, 14.2-5,500,0008 Uniform
Overall chemical decay coefficient W Constant
Overall firstader decay coefficient Od Derived
Reference temperature 25" Constant
Solid-phase decay coefficient 0" Constant
k e a of eastern sourcef 10,Ooo Constant
Infiltration rate 0.317-0.587' Uniform
Initial concentration of leachate 100h Constant
Length scale of sourcef 100 Derived
Near-field dilution 'l Derived
Recharge rate 0.308-0.744 Uniform
Cleanup 113
Table 21 Continued
Input type
Source decay constant p-' 0' Constant
Spread of contaminant source m 16.7 Derived'
Width scale of sourcef m 100 Derived
off Angle v Constant
Aquifer - 0.26-0.57' Derived
Aquifer 4.57-6.10 Uniform
Bulk .76k 1.25-1 Uniform
o Distance X, m 244' Constant
velocity
Groundwater
seepage mm - Derived
uctivity Hydraulic dYr 142-3.780 Uniform
ent Hydraulic - 0.0059-0.0068 Uniform
ersivity Longitudinal 24.4" Constant
e Mixing - Derived
(fraction),
content
carbon
Organic f, - 0.0010-0.0076" Uniform
r Particle 0.0004-0.2000" Uniform
cient Retardation - - Derived
Temperature of aquifer "C 16-25" Uniform
Transverse dispersivity m 8. 13" Constant
Vertical dispersivity m 1.37" Constant
PH - 6.00-9.00' Constant
'Literature values obtained from Ref. 11.
bDistribution coefficient was derived from the equationKd = K, f,, where K, is the normalized distribution CO-
efficient andf, is the organic carbon content (fraction).
CConservative input value assumed.
''Value will be zero since it is derived from solid- and dissolved-phasecoefficients, which themselves were assigned
a value of zero.
'Assumed value(s).
fh was designated as in Figure 7. Model assumed m is square. approximated area at 1O.ooO m*, with
length = width = 100 m.
Infiltration rates selected for model represents the minimum and maximum values derived from the Hydrological
hAssumed value.
'Spread of Gaussian contaminant source = (width of sour~e)/6.
jPorosity values represent range from fine sand to clay-Table 6.3. Mulrimed User's Manual.
'Literature value obtained from Multimed User's Manual, Table 6-8, for sandy loam.
'Determined from Figure 7.
mLongitudinal dispersivity, al. = 0. I X,;transverse dispersivity = aLJ3; vertical dispersivity = 0.056aL.
"No site-specific f, data available. Input value range obtained fromMultimed User's Manual. Table 6-7,for group
B soils using the equation f, = fJ172.4.
OParticle diameter range assumed for particletypes ranging from fine silt to coarse gravel, given in Table 6-10 of
the Multimed User's Manual.
Prior to discussing the actual calculation process, Table 22 presents and defines the pa-
rameters that were used in the development of soil cleanup goals.
1. GroundwaterApproach
of groundwater at the designated
The calculations for developing soil cleanup goals protective
receptor well location MW-l02 are as follows.
114 Kotun et al.
Table 22 Parameters Used for Derivation of Soil Cleanup Goals

C,,,, Riverconcentrationofacontaminant,equaltotheappropriate AWQC
DAFDilution-attenuationfactorderivedfromMultimedastheratiobetweentheinitialleachate
concentration at the source and the modeled downgradient groundwater concentration at
the receptor
RM Rivermixing(dilution)factorforcontaminantsintheriver
Dd Soilwaterequilibriumpartitioningcoefficientusedforderivinginterimsoilcleanup'goals
from steady-state modeling
ci Initial
contaminantleachate
concentrationat
source
Cf Finaldowngradientgroundwaterconcentrationatreceptorlocation
CS, Contaminantconcentrationingroundwateratpointofdischargeintoriver,back-calculated
from river concentration,C,,,
C,, Contaminantconcentrationingroundwateratmonitoringwell MW-102,equaltotheappro-
priate groundwater performance standard
Cl Leachateconcentrationatsource,back-calculatedfromdowngradienttargetgroundwater
concentration (performance standard) at receptor location
CS Soilconcentrationcorrespondingtointerimsoilcleanupgoal
1. Initial PAH concentrations (Ci)are modeled from the designated source area through the
unsaturated and saturated zones to the receptor location at monitoring well MW-102. A
groundwater concentration at this location (C') is output by the model.
2. The following relationship is then used to calculate a dilution-attenuation factor:
DAF -*Ci/Cf
3. Assuming that the target PAH groundwater concentration at location MW-l02 is mul-
tiplying by the model-derivedDAF(derived in step 2) givesthe PAH leachatecon-
centration (C,) at the source, or
C/ = C,, * DAF
4. Finally, multiplication of C, by the distribution coefficient (Kd) results in a soil concen-

tration at the source corresponding to the soil cleanup goal. This partitioning is expressed
as
c, = C&
2. River Approach
The calculations for developing soil cleanup goals protective of the river are as follows.
1.Initialleachate PAH concentrations (Ci) are modeledfrom the designatedsourcearea

through the unsaturated and saturated zones to the point of groundwater discharge at the
river. A groundwater concentration at this location (C/>is output by the model.
2. The following relationship is then used to calculate a dilution-attenuation factor:
DAF = CiCf
3. Assuming that the target river concentration is Caw,, the targeted PAH concentration in
the groundwaterat the point of discharge intothe river (C,) can be calculated by multi-
plying with RM, or
C, = Cawv RM
Cleanup Level Development I15
4. Multiplying Cgwby the derived DAF from the model gives the leachate concentration at
the source (Cl):
Cl = c, * DAF
5 . Finally, multiplication of Cl by the distribution coefficient (Kd) results in a soil concen-

tration at the source correspondingto the soil cleanup goal. Thispartitioning is expressed
as
CS= c&
3. Soil Cleanup Goals for TotalPAHs
The calculation for developing soil cleanup goals for total PAHs that are protective of the
groundwater at monitoring well location MW-l02 and the river is as follows.
1. The leachate concentration of total PAHs (C,,TpAH) at each sourceis calculated in the same
manner as follows.
For protection of groundwater at MW-102,
C1,TPAH = c s td DAF
For protection of the river,
C~,~=
AHC,,,, RM
DAF
Since the MCLs and DWELs are different for each PAH, the lowest groundwater perfor-
mance standard (O.OOO1 mg/L - proposed MCL for benzo[a]anthracene) is being used for
totals PAHs as a conservative approach.
( C s , p A H ) must take into account
2. Since the calculationof a soil cleanup goal for total PAHs
the Kdof each PAH (Kd,pAH) as well as the percent distribution of each individual PAH
(%DpAH) across the area of interest, the following assumptions can be made regarding the
derivation of the soil cleanup goal.
For each PAH,
C1,PAH = Cs.PAH/Kd.PAH (5)
where
C~,PAH %DPAH
= C~.TPAH (6)
Substitution of Equation (6) into Equation ( 5 ) yields the relationship
c/,PAH = (Cs.TPAH %DPAH)/Kd,PAH (7)
For total PAHs, Equation (7) becomes
By moving Cs H,. outside the summation and rearranging, the following expression for
the calculation of a soil cleanup goal for total PAHs is obtained
Table 23 presents a summary of the mean percent distribution of each PAH in soil at the
site (%D),the distribution coefficient (Kd)of each PAH, and the adjusted distribution coeffi-
cient obtained for each PAH by dividing each Kd value by the corresponding %D.
116 Kotun et al.
Table 23 Summary of Diskibution Coefficients for Polycyclic Aromatic Hydrocarbons

~
Mean percent Distribution

Adjusted coefficient
distribution,"
Polycyclic
aromatic
hydrocarbon
(cm3/g)
%D Kd value,b K; (cm3/g)
Benzo[a]anthracene 6.33 6900 109,005
Benzo[a]pyrene 5.33 27500 515,947
Benzo[b]fluoranthene 10.0 2750 27,500
Benzo[k]fluoranthene 9.72 2750 28.292
Chrysene 7.66 loo0 13,055
Dibenzo[a,h]anthracene 1.S5 16500 1,064,516
Indeno[l,2,3-cdjpyrene 3.01 8OOO 265,78 1
Acenaphthene 2.96 23 777
Acenaphthylene 1.45 12.5 862
Anthracene 5.75 70 1,217
Benzo[g,h,i]perylene 2.97 8o00 269,360
Fluoranthene 15.6 190 1,218
Fluorene 3.23 36.5 1.130
Naphthalene 2.74 4.7 172
Phenanthrene 9.83 70 712
Pyrene 11.8 190 1,610
Sum K: = 2,301,155
'%D for each PAH = (mean PAH conc./total mean PAH conc.) 100%.
bKd = K,J(%D)/100].
D. Results
1. Dilution-Attenuation
Factors
Table 24 presents a summary of the dilution-attenuation factors (DAFs) that were derived
from the final downgradient groundwater concentrations estimated at two receptor locations
(MW-102 and the river) by the Multimed simulationsof steady-state flow and transport from
Table 24 Summary of Dilution-Attenuation Factors from Flow andTransport Models

Through Unsaturated and Saturated Zones-U.S. EPA Exposure Assessment Multimedia Model,
Steady-State Conditions
Modeled
groundwater
finalModeled
concentration dilution-
Assumed for total PAHs attenuation
initial leachate receptor
facto?
at for
concentration
location
(mg/Ll total PAHs
for total PAHs
Model type for steady-state
conditions
source"
at (mg/L) MW-IO2 River
MW-102
River
PAHs of Deterministic
models 11.71 0 011.9 8.52 8.38
9.8Carlo
models 45 10.2 2.23 100
Monte of PAHs'
~~~
'Initial leachate concentration at source location is in the unsaturated zone. 100 m& was assumed for modeling
presentation.
bDilution-attenuation factors (dimensionless)are used for calculations of interim soil cleanup levels.
'Values presented for Monte-Carlo simulations representthe 95th percentile.
Cleanup 117
Table 25 Summary of Interim Soil Cleanup Goals for PAHs Protective of Groundwater and the
Adjacent River
Protective of Protective of
humans consuming humans consuming Protective of
groundwater from aquatic organisms marine organisms
Well MW-102 (mgkg) from river (mgkg) in river (mgkg)
Deterministic Monte Carlo Deterministic Monte Carlo Deterministic Monte Carlo
model model" model model" model model"
10,355 2738 403,852,703
35,067 41,866 338,269,785
'Interim soil cleanup goals presented for the Monte Carlo model represent the 95th percentile.
the source areas of the site, through the saturatedand unsaturated zones. The table shows that
two DAFs were determined for each receptor location. One DAF was derived based on the
results of a deterministic model, the other based on the 95th percentile results
of a Monte Carlo
model of 500 iterative simulations.
The groundwater concentration of all PAHs estimated at receptor location MW-102by
the deterministic and Monte Carlo simulations of steady-state conditions were 8.38 and 2.23
mg/L, respectively. Sincethe original leachate concentration was arbitrarily assumed to be 100
mg/L (for ease of presentation), the corresponding DAFs derived from the results of the de-
terministic and Monte Carlo modeling efforts to receptor location MW-102 are l l.9 and 45,
respectively.
Thegroundwaterconcentrations of all PAHs estimated at thepoint of groundwater
discharge to the river by the deterministic and Monte Carlo simulations of steady-state con-
ditions were 8.52 and 10.2 mg/L, respectively. Since the original leachate concentration was
100 mg/L, the corresponding DAFs derived from the results of the deterministic and Monte
Carlo modeling efforts to the river are 11.7 and 9.8, respectively.
2.SoilCleanupGoals
The DAFs derived and summarizedin Table 24 were usedto calculate soil cleanup goals for the
site that are protective of (1) the groundwater at monitoring well MW-102, (2) humans con-
suming aquatic organisms from the river, and (3) marine organisms in the river. These soil
cleanup goals are presented in Table 25.
Table 25 shows that the soil cleanup goals for totalPAHs in area A, derived from the re-
sults of the deterministic and Monte Carlo simulations, for protection of humans consuming
groundwater at the receptor well location were 2738 and 10,355 mgkg, respectively. The soil
cleanup goals for total PAHs in area B,derived fromthe results of the deterministic and Monte
Carlo simulations, for protection of the humans consuming river organisms were 41,866 and
35,067 mgkg, respectively. The soil cleanup goals for total PAHs in area B, derived from the
results of the deterministic and MonteCarlo simulations, for protection of river organismswere
both greater than 1 O, OOO
, OO parts per million. Based on these soil cleanup goals and the ex-
isting PAH concentrationsdetected at the site, no soil remediationof PAHs would be necessary
in either area A or B.
E. Conclusion
Environmental fate and transport modeling of contaminants in the multimedia environment
provides an alternative means of developing and establishing cleanup goals for potential source
118 Kotun er al.
areas at hazardous waste sites. As was shown in this case, cleanup goals canbe derived from
modeling outputs that protect potential human and/or environmental receptors from contami-
nants as they become mobilized following release into the environment. The soilcleanup goals
derived for thissite were to protect both human and environmental receptors fromPAHs orig-
inating from two sourcelocations, with the most conservativesoil cleanup goals being derived
from both deterministic and Monte Carlo models for the protection of humans consuming
groundwater as drinking water. These soilcleanup goals were 2738 and 10,355 mgkg, respec-
tively. The uncertainties associated with applying Multimed to the derivation of soil cleanup
goals for this site are discussed in the following paragraphs.
In the deterministic models of steady-state conditions, literature valueswereused for
chemical and physicalproperties of individual PAHs. These values may not be appropriate for
the actual existing conditionsat the site. Many of the literature values were obtained from lab-
oratory conditions or field conditions different from those atthe site. Many site-specific con-
ditions may cause the chemical and physical properties and behaviors of the PAHs to deviate
from values reported in the literature. In addition, the model evaluates chemicals separately.
The behavior in the environment of chemicals that are constituents of mixtures, such as PAHs
in creosote, may be different from what their behaviorwould be if they were interacting indi-
vidually with the environment.
The MonteCarlo model of steady-stateconditions assumesa constant, nondecaying source
of large area and sufficient chemical mass to forcethe modeled system into steady-state con-
ditions and equilibrium, such thata constant downgradient groundwaterPAH concentration is
maintained at all times. In reality, however, the source strength may decay over time as PAHs
migrate away (downgradient) from the sourceor degrade naturally.
An uncertainty associated withthe Monte Carlo mode exists in the random generation of
values from a specified distribution. It is uncertain whether the model considers interdepen-
dencies thatmay exist betweenor among many of the input variables. For example, the organic
carbon partition coefficient (K,) may, in reality, change with the changing pHof a system.
This is probably ignored by the model, especially when K, values are entered as constant
input.
Another consideration for uncertainty also existsin Monte Carlo simulations. Since there
was a very limited base of site-specific data for each input variable, the uniform probability
distribution was best suited for the input variables because of the degree of uncertainty asso-
ciated with them. Hydraulic conductivity,for example, is estimated tofollow a log-normal dis-
tribution, and application of a uniform distributionmay not be appropriate, but due to the lack
of data for this parameter, it was the only option available.
Other overall uncertainties were associated with the use of the Multimed model for this
site. These include (1) the uncertainty resulting froma lack of sufficient aquifer-specificdata
for calibration of the model to actual conditions beneath the site; (2) the uncertainties that exist
in parameter estimation from literature values, especially for values presented fora particular
variable for differenttypes or classifications of unsaturated andsaturated zone materials (i.e.,
soils), noneof whichmay adequately match the materials in the unsaturated and saturated
zones at the site; (3) uncertainty associated with theselection of a representative location and
size of each source area;and (4) the uncertainty associated with source area geometry, since the
model assumed that the geometry of each source area at this site was square, which may not
represent the actual geometryof the area. Selection of the area geometry will affect how the
plume is modeled.
V. CASE STUDY W: DETERMINATION OF SOIL CLEANUP

GOALS PROTECTIVE OF GROUNDWATER QUALITY
USING ANALYTICAL SOLUTIONS
A. Introduction
During the 1980s, a large number of hazardous wastesites were investigated to determine the
potential impactsof these sites on human health and the environment. The detail with whichthe
investigations were conducted varies greatly fromsite to site. Databases for sites can be com-
posed of several to several thousand sample analyses and observations. Despite the reliability
of a given database, emphasis is currently on the remediation of sites having U.S. Environ-
mental Protection Agency (U.S.EPA) promulgated Records of Decision (RODS). Within a
ROD, remedial goals are established for those media presenting unacceptable risk upon expo-
sure or for any medium representing sources or potential sources of continuing contaminant
release.
Remedial goals designed to abate human health risks can be derived once the rate and
duration of exposure to a given medium have been determined. Rate andduration of exposure
are based onsite-specificinformation such as area demography and land use patterns. Exposure
is defined in the Public Health and Environmental Assessment (PHEA)section of the remedial
investigation (RI) report for any site. However, establishing cleanup goals protectiveof actual
or potential contaminant releaseis more difficult and may require somefate and transportmod-
eling, particularly in the case of soil contamination and groundwaterprotection.
Soil cleanup goals protectiveof underlying groundwater canbe derived by developing sim-
ple, logical models of site-specific contaminant migration from affected soils to groundwater
and, if necessary, to an alternate point of compliance (APC). An APC is a hypothetical bound-
ary beyond which contamination cannot extend at concentrations exceeding some minimum
performance standard. APCs are established byEPA and can extend to the nearest potential
household or be limited to the downgradient source area boundary. Once the APC is estab-
lished, the site-specific conceptof contaminant migration can then be approximated by the use
of site data and/or mathematical models.
The use of mathematical models to describe the movement of groundwater is not new.
Mathematical models representativeof groundwater flow regimes have been used by engineers
and scientists since the late 1800s [12]. Application of groundwater models to pollution trans-
port and management problems has become increasingly popular over the last twenty years due
to the enactment of legislation such as the Federal Water Pollution Control Act of 1972, the
Safe Drinking WaterAct (SDWA) of 1976, the Clean Water Act of 1977 (CWA), andthe Com-
prehensive Environmental Response Compensation and LiabilityAct of 1980 (CERCLA). The
complexity of the available groundwater models varies greatly. Selection of a model for use at
a site is therefore based on factors such as the complexity of the groundwater flow regime,the
importance of modeling resolution, and the data available to the engineer or scientist doing the
modeling.
Under relatively simple hydrogeological conditions or when simplifying assumptions about
the flow regime are appropriate, contaminant migration can be approximated by the useof
mathematical models such as analytical solutions or analytical models. The distinction between
the two is more than semantic. Analytical solutions solve a very simple process equation by
hand calculations. They require few site-specific analytical data and provide conservative es-
timates of contaminant transport. Analytical models solve more complex process equations
120 Kotun et al.
with the aid of a computer program. The data needs and the need to develop mathematical
solutions that describe boundary conditions for analytical models are more extensive and are
open to conjecture.
This section discusses the useof analytical solutions in the determination of soil cleanup
goals protectiveof underlying groundwater quality accepted by EPA, RegionV (EPA V), at an
active CERCLA site in Texas. The site is a former wood-treating facility that operated for over
50 years. Data necessary for the use of more complex analytical modelsare not available. All
process-related structures have been removed, andportions of the site are currently occupiedby
other industries.
The ROD issued for this particular site by EPA V specifies that all soils containing in ex-
cess of 700 ppm of carcinogenic polynuclear aromatic hydrocarbons(cPAHs) must be reme-
diatedtoprotectindividualspotentiallyexposed by directcontact(dermalcontactand
accidental ingestion). The ROD also specifies that the remaining soils must be remediated to
achieve the “no leaching potential” in order to protect underlying groundwater quality. Since
the underlying shallow aquifer is not currently usedas a drinking water supply and Texas leg-
islation currently prohibits the further development of groundwater for potable use in the area,
the attainment standard for cPAHs in groundwater is less than 10 ppb (not detected) at the
APC, designatedas the downgradient property boundary. Possible impacts on the deep aquifer
of an improperly abandonedwell thought to exist inthe southern portion of the site must also
be addressed. The deep aquifer is a potential drinking water source; therefore, an attainment
standard of 0.2 pg/L corresponding to the proposed maximum contaminant level (MCL) for
benzo[a]pyrene is warranted.
The site conceptual model of contaminant migration (site conceptual model) at the site uses
EPA’s Organic Leaching Model (OLM) [l31 to account for cPAH soil leaching andEPA’s Ver-
tical and Horizontal Spreading (VHS) model [l41 to account for dilution in the shallow satu-
rated zone afforded by dispersion. A two-dimensional horizontal flow model representing the
presence of a continuous solute line source representsthe potential migration (and subsequent
dilution) of cPAHs in the deep aquifer emanating from the improperly abandoned well.
Contaminant attenuation is afforded primarilyby the leaching portion of the site concep
tual model. Dispersion in the saturated zone is minimal becauseof the relatively shallow sat-
urated zone under consideration and proximity of the soil sourceareas to the APC. Attenuation
by leaching is also a controlling factorfor the potential impacts on groundwater quality inthe
deeper aquifer.
Derivation of soil cleanup goalsby these methods provided a timely, cost-effective alter-
native to complex numerical modeling. Furthermore, the conservatism of the results may ac-
count for someof the temporal and spatial variations inherent in even the simplest groundwater
flow domains not accounted for in complex models. Upon completion of the modeling effort
and a qualitative sensitivity analysis, site-specific data were obtained to verify the findings of
the leachateportion of the model that provided the majority of contaminant attenuation. These
data will be summarized and analyzed to ensure that the theoretical site concept of cPAH mi-
gration does not underestimate the site-specific potential for continuing release of cPAHs from
soils. If site data do show that the modeling resultsare underestimates or overestimates of ac-
tual conditions at the site, the model will be modified to account for the difference.
B. Purpose
The ROD issued in September 1988 for the site stipulates that during the initial stages of the
remedial design, contaminated soilareas will be remediated if they exceedeither the risk-based
soil cleanup goal of 700 ppm of cPAHs or the leaching potential-based cleanup goal (“no
Cleanup 121
leaching potential”). The leaching potential-based goal is defined as the residual cPAH soil
concentration that will not leach and impact groundwater beneath the site.
Although a detailed hydrogeological assessment was conducted at the site during the re-
medial investigation, chemical analytical data and data requirements for groundwater flow
modeling are limited. A visual soil investigation was attempted to determine the extent of con-
taminated soils, and only select samples of the visually impacted soils were analyzed for the
presence of cPAHs. The remedial investigation was concluded in 1986, and nofurther studies
were conducted.
The development of a remedial design work plan was initiated by one of the potentially
responsible parties (PRPs) in 1989 in responseto the promulgation of the ROD by EPA V. In
early 1991, acceptance of the Remedial Design Work Plan byEPA V was contingent upon
addressing the “no leaching potential.”) Meetings with the PRP and EPA V resulted in de-
fining the no leaching potentialas a total cPAH concentration in leachate emanating from con-
taminated soils not exceeding 10 pg/L at the downgradient property boundary. A detection
limit of 10 pg/L was chosen because the shallow aquifer is not categorized as a potential drink-
ing water unit because of its low yield and general water quality.If the aquifer were categorized
as a potential potablesource, the proposed MCL for benzo[a]pyrene would have been selected
as the minimum attainment standard for cPAHs. MCLsare enforceable standards for drinking
water suppliesor potential potable sources.EPA V was concerned not only with protecting the
shallow water-bearing unit fromfurther deterioration but also with the possible impact on the
deep aquifer, in which an improperly abandoned wellis thought to exist. An improperly aban-
doned deep well could act as a conduit fromthe shallow aquifer tothe deep aquifer. The deep
well was installed around 1912 but is no longer in service and has not been used since the late
1950s. However, records of proper abandonment do not exist. EPA V therefore stipulated that
soil cleanup goals protective of shallow groundwater qualitymust also be protective of the deep
aquifer, which is used as a supply of potable water in the immediate area of the site. A min-
imum attainment standardof 0.2 pg/L corresponding to the proposed MCLfor benzo[a]pyrene
was established as the minimum attainment standard for this water-bearing zone.
EPA V also concluded thatthe use of models if applicable would be acceptable but subject
to EPA’s review and final approval.
The purposeof this section is to present the rationale for the development of a soil cleanup
goal protective of groundwater quality in the shallow and deep aquifers using available site
information and analytical solutions that will withstand an EPA V review. Acceptance of the
soil cleanup goal by EPA V would provide the ROD-specifiedno leaching potential and result
in the completion of the remedial design work plan for the site.
C. Application
1. Development of the Site Conceptual Model
The conceptual model for the site is based upon information about the source areas and hy-
drogeology at the site presented in the final remedial investigation report. The regional geo-
logic setting for the site is the Quaternary Gulf Coastal Plain of Texas. This region comprises
a series of sedimentary depositional plains, the youngest of which is of recent, postglacial dep-
osition (Holocene deposits). Sediments of the Holoceneare deposited alongthe coast and in the
alluvial flood plains of existing river systems. The site is located specifically in the surface
sediments of the Beaumont Formation.
The average depthof the Beaumont Formation is 0-20ft below grade. The Lissie Forma-
tion lies below the Beaumont and extends to approximately200 ft below the surface. Thema-
jority of the historical site soil borings were drilled to a depth of 65 ft, although deeper borings
122 Kotun et al.
I.
I
I
l
I
I
I
I
I
I
I
I
I
I
I
I
l
I
I
I
l
Cleanup 123
were drilled to depths of200 ft below the surface. Sediments making up these units consist of
a top stratum of cohesive soils (sandy claysand silty clays) and a substratum of cohesionless
soils (silty sands, clayey sands, and poorly graded sands). Primary water-bearing zones and
their corresponding thickness encountered at the site are organized as follows: shallow zone
(10-21 ft), intermediate zone (115-127 ft), and deep zone (174-200 ft).A generalized cross
section of these zones is presented in Figure 7.
The 1986 RI report states that the shallow water-bearing units consist predominantly of
silty and clayey sands with occasional gradations to sand and clayey silts.The base of this unit
is irregular and slopes gently to the east. Shallow zone groundwater trends at the site generally
slope to the westat a gradient averaging about 20 ft/mi. Site surveys indicated that the shallow
zone extends continuously offsite to the west, toward a bayou. This drainage feature may as act
a groundwater discharge area, thereby influencing westward-trending gradients. A surface im-
poundmentlocatedoffsitealongtheeastpropertylinemaycauselocalizedgroundwater
mounding, which also would produce westward gradients in the shallow zone.
The hydraulic conductivityof the shallow zone was evaluated by conducting falling-head
field permeability tests at selected well locations. Table 26 presents the field hydraulic con-
ductivity test results for wells screenedin the shallow water-bearing zone. Soilsof the water-
bearingunit are alsotypedforfutureconsideration.Measuredfieldhorizontalhydraulic
conductivitiesfortheshallowzonerangedfrom 2.4 X to 2.2 X c d s e c andaver-
aged 8.3 X low4cdsec.
The next significant water-bearing unit is the intermediate water-bearing zone, which is
overlain by a clay layer and is not considered to be affected by historical site activities. Hy-
draulic conductivities for this zone are not currently available. The continuous nature of the
intermediate aquitard excludes this zone from the modeling effort.
The deep zone is also considered to be a confined water-bearing unit. However, historical
data indicate that a deep well was screened in this unit, and records of the well’s abandonment
are not available. Physicaldata are not available for this particular zone. It is believed that the
deep zone gradient slopes to the south-southwestat approximately 6 ft/mi.
Vertical seepage rates between shallow and intermediate water-bearing units are extremely
low because of the nature of the confining strata. However, a potential conduit between the
shallow zone and the deep may exist in the form of a leaking improperly abandoned well in the
southern portion of the site. For this reason, the deep water-bearing unit is a concern EPA of
V and is considered in the modeling effort.
Given the natureof the site and the characteristics of the underlying strata, contamination
of the shallow zone by infiltration of precipitation is the most obvious groundwater contami-
Table 26 Field Hydraulic Conductivity Test Results4hallow

Groundwater Zone
Field horizontal
hydraulic
Monitoring Soilconductivity
Screen
well type interval (ft) (cdsec)
MW0 1 Sand 9.0-21 .O 2.4 X 10-~
MW02 Silty sand 9.0-21 .O 4.5 X IO-^
OW07 Sand 11.0-16.0 4.5 X 10-~
OW08 Sand 14.0-19.0 2.2 X 10-~
Avg. 8.3 X
124 Kotun et al.
nation mechanism. Contamination reaching the shallow zone would in all likelihood move in
the westward direction of shallow zone groundwater migration. Vertical and horizontal dis-
persion would then occur, withvertical movement bounded below by the intermediate aquitard.
If the improperly abandoned wellexists, contaminants might alsoenter the deep water-bearing
zone in which the well was screened. Groundwaterin the deep water-bearing zonein which the
well was screened. Groundwater in the deep water-bearing zone trends toward the southern
property boundary.
The site conceptual model consists of three elements: (1) leaching of constituents of in-
terest (COIs) from affected soils, (2) migration and subsequent dispersion of the COIs with
respect to shallow groundwater flowdirection, and (3) migration from the shallow zone tothe
deep water-bearing unit throughthe open conduit and subsequent dispersion. The site concep-
tual model is presented in Figure 8. An important aspect of this conceptual model isthat it is
chemically conservative, assuming that the cPAHs are not biodegraded or adsorbed to soils
before, during, or after migration.
2. ConstituentMobility
Polynuclear Aromatic Hydrocarbons (PAHs), in general, are immobile constituents in envi-
ronmental media. Recent research shows that PAHs bind to soil surfacesas a result of their van
der Waals forces [15]. Van der Waals forces act solely between molecules within close prox-
imity of each other. As a rule, the larger the molecular size, the greater the van der Waals
forces. cPAHs, being generally larger than noncarcinogenic nPAHs, are even less mobile in
environmental media. Similarly,relatively low water solubilitiesand vapor pressures add to the
inherent environmental immobility of cPAHs.
A semiquantitative assessment of theoretical mobility developed by Laskowski et al. [l61
can be used to describe the immobility of cPAHs in the environment based onknown physical
and chemical constants. The basis for the assessment is an algorithm that utilizes water solu-
bility (S), vapor pressure (VP), and the organic carbon partition coeffkient (K,) of the con-
stituents to determine a relative mobility index (MI). The MI is defined as
MI = log [(S VP)&] (10)
A relative scale is then used to evaluate the MI derived for eachcPAH [17]. The scale is
a descriptive one, comparing a numerical MI to the categories extremely mobile, very mobile,
slightly mobile, immobile, and very immobile.
Description
indexMobility
>S mobile
Extremely
0 to 5 Very mobile
-5 to 0 Slightly mobile
-10 to -5 Immobile
<- 10 Very immobile
Mobility index values and the physical-chemical constants for the cPAH are presented in
Table 27. The MIS for the cPAHs range from valuesof -8.9 (immobile) for benzo[b]fluoran-
thene to - 11.7 (very immobile) for chrysene.
PAH mobility may be enhanced if these constituents bind onto dissolved organic macro-
molecules such as humic acids or suspended particulate organic matter in groundwaters. It is
important to note that in most soil-water systems, these macromolecules are, themselves, not
IMPROPERL Y ABANDONED NELL
III. 2-D HURIZONTAL

LINE SOURCE
\
/CUNTINUOUS SOLUTE
LINE SOUACE/
Figure 8 Conceptual model of potential containment migration. I, Organic Leachate Model (OLM); 11, Vertical and Horizontal
Spreading (VHS) model; 111, two-dimensional horizontal line source model (continuous solute line source).
126 Kotun et al.
Table 27 Physical-Chemical Constants and Relative Mobility Indices for cPAHs

Vapor Water Relative
mobility pressure solubility Mol wt.
Constituent (g/mol) (ppm @ 25°C)
Hg) (mm log K, index
Benzo[a]pyrene 252.0 0.0038 5.6 X (25°C) 6.74 -10.5

Benzo[a]anthracene 228.4 0.0057 (20°C) 2.2 X lo-' (20°C)
-9.6 5.30
Benzo[b]fluoranthene 252.3 0.014 5 X 10-7 ( 2 0-8.9
0 ~ ) 5.74
Benzo[k]fluoranthene 252.3 0.0043 5 X 10-7 ( 2 0-9.4
~ ) 5.74
Chrysene 228.3 0.0018 6.3 X lo-' (25°C)-11.7 5.30
Dibenzo[a,h]anthracene 278.4 0.0005 7 x 10-8 6.52 -11.3
Indenoil ,2,3-cd]pyrene 276.3 0.00053 7 x 10-8 -11.2 6.20
Source: U.S. EPA Aquatic Fate Process Data for Organic Priority Pollutants [ll].
mobile. Nevertheless, this site conceptual model considers that the cPAHs could potentially
migrate advectively, boundto mobile dissolved organic matter in the underlying shallow aqui-
fer and the deeper zones. Retardation will not be considered in order to account for the max-
imum cPAH mobility in groundwater at the site.
3. GoverningEquations
Element I . Contaminant Leaching. The potential concentrationof an organic constituent that
will leach from source area soils [C(l)] is estimated using the 95% confidence versionof EPA's
OLM. The OLMis a multiple regressionequation that is derived froma database of measured
leachate concentrations. The database is composed of TCLP data, EP-Tox data, and field
lysimeter results formany of EPA's Target Compound List (TCL) compounds.
The log form of the equation used to calculate the 95% percent C1 is
95% C1 = t0.05,~-2 * MSE [X', (X'X)"

X/,] (11)
where to.o5is the factor for the 95% CI, q - 2 is the number of degrees of freedom, MSE is
mean square error, and X,X', X,, X,' are various versions of the waste and leachate concen-
tration data matrix.
The OLM equation is
C(I) = 0.0021I(Cw)0.678(Sw)0.373 (12)
C, is the estimated concentration of an organic constituent in source area soils, andS, is the
water solubility of the constituent. Since benzo[b]fluoranthene is the most relatively mobile
cPAH as a result of its water solubility, the modeling effort will focus on this constituent.
Element I I . Dispersionin the Shallow Aquver. Thetransport of a constituent by shallow
groundwater to the APC results in dilution by vertical and horizontal dispersion processes.The
VHS model [l31 provides a conservative estimate of the dilution provided by these dispersive
transport phenomena and is used as the final element in the site conceptual model. The VHS
model equation is
CAE = C,,[erf [(Y'/~Y)'.~]

erf {X/[~(U,Y)~*~]}] (13)
where cAPCis the estimated constituent concentrationat the APC, c, is equal to C(l)developed
by OLM since dilution prior to transport is not a consideration, Y' is the width of the source
Cleanup 127
area parallelto the directionof groundwater flow,Y is the distance from the source area to the
APC, a,is the transverse dispersivity, and x is the length of the source area perpendicular to
groundwater flow.
The error function of some number z, erf(z), can be estimated using an approximation
method. The equation is an integral part of the VHS algorithm and can be expressed as
Z
erf(z) =
[Z' + (22/28)exp ( - 2 ~ ~ / 3 ) ] ' . ~
The calculated error function canbe checked against publishederror function values such
as those presented inEPA's Water Quality Assessment Document[l81 to ensure its legitimacy.
The VHS model is based on the dispersion-convection equation
In essence, a continuous source-contaminated parcel moving at a steady one-dimensional

velocity is subjectto a transverse spreading process.D, is the transverse dispersion coefficient,
y is the spatial coordinate collinear with the velocityof the contaminant V,,, and x and z rep-
resent the horizontaland vertical spatial coordinates perpendicularto groundwater flow direc-
tion. The problem is viewed as a two-dimensional semiinfinite medium bounded at the topby
z = 0, the flux boundary 6C/6Z = 0.
At y = 0,
where 2 and X represent the penetration depthat the waste area boundary and the width
of the
waste unit perpendicular to groundwater flow direction, respectively.
The solution to Equation (14) given the boundary conditions is
C(x,y,z)= erf
Z X
c(x7yJ) = [ 2(D,y/Vy)'.') erf ( 4 ( D , y / v ~ ) ' . ~ ) ]
This solution was first provided by Domenico and Palciauskas [l91 and was used in ob-
taining exclusions for solid wastes on a generator-specific basis. Applying for an exclusion in-
volvesapubliccommentperiodduringwhichmodification of the model issuggested.
Modifications to themodel were due to a change in the manner which in penetration depth(Q
is calculated. EPA agreed with the comments regarding the modificationof the 2 term. Since
Z is calculated differently, notation in the equation changes slightly. Modification in the cal-
culation of the Z term and notation changes account for the differences between Equations (13)
and (18). The Z term and its importance in this modeling effort are discussed in subsequent
sections of this chapter.
128 et Kotun al.
Element III. Dispersion in the Deep Aquifer. A direct conduit to the deep aquifer in the form
of an improperly abandoned well could exist in the south-centralportion of the site. Historical
records indicatethe presence and approximate locationof a deep well, and although U.S. Geo-
logical Services (USGS) boring logs exist, records ofthe well’s abandonment were not located.
A number of studies were conducted in 1986 to locate the improperly abandoned well.
Geophysical testing and excavation were undertaken in the area of the site described in the
company records. These investigations failed to locate the deep well conduit. However, the
study did reveal several magnetic anomalies that could correspond to the presence of the deep
well casing. Excavation was undertakenas a result of the magnetometric survey, but the exact
location of the well was never found. It is unlikely that this is a major pathway of cPAH mi-
gration at the site, and the uncertainty in the existence of the open conduit makes modeling this
particular pathway difficult. If the well does exist, it could be a conduit to the deep aquifer.
The approach used in estimating the potential impact on the deep aquifer considers two-
dimensional horizontal flowwith continuous solute line sources [18]. The aquiferis considered
to be homogeneous and isotropic. Benzo[b]fluorantheneis assumed to discharge continuously
and uniformly within the deep aquifer. Steady-state conditions are assumed, to maintain con-
sistency with other portions of the site conceptual model. The equation is
where C, is the acceptable concentration of COIs emanating from a source area that is pro-
tective of the shallow aquifer (pglL); Q is the flow emanating from the shallow aquifer as a
b is the saturated thickness of the deep aquifers (m);
result of the hypothetical conduit (m3/day);
p is the porosity of the deeper aquifers (dimensionless);D,, D, are the dispersion coefficients
in the x and y directions, respectively (m2/day);B = 2DJVd; V,, is the Darcy velocity (&day);
f3 is an estimate of retardation (dimensionless); V, is the seepage velocity (Darcy velocity) of
regional flow in the x direction (&day); x the distance from the source area to the APC (m);
y the distance between the centerline of the plume and the APC (m); and
4. Site-Specific ModelingInputs
The site conceptual model comprises three elements describedby analytical solutions predic-
tive of an approximate groundwater concentrationat an APC resulting from a soil concentra-
tion of cPAHs at a source area.
Given the performance standard (CAK), the VHS model is solved for each source area
capable of producing an impact on the shallow zone groundwater quality.
The VHS reduces to
CAR = CODF, DFH (20)
where CAE is the performance standardin the shallow aquifer(10 pg/L); and DF, and DF, are
the dilution factors derived from vertical and horizontal dispersion, respectively.
The equation is then rearranged and solved forC,, which is derived for eachsource area
of interest at the site. Then C, is entered into the rearranged OLM equation, which becomes
I .4149
Cleanup 229
C,, the concentration of the constituent in the soil, becomes the soil cleanup goal protec-
tive of the shallow aquifer at the APC and meets cAK.
The performance standard associated with the established soil leachingcriteria isthen as-
sessed with respectto the deep aquifer. Ifthe groundwater qualityin the deep unitis unaffected
at the APC, the performance standard established for the shallow zone is also protective of the
deep aquifers and no modification tothe soil leachingcriteria is necessary. If the groundwater
quality at the deeper aquifers' APC is affected, the no leaching potentialcriteria for the shallow
zone may be modified to also be protective of the deep aquifer. The performance standardfor
the deep aquifer is assumed to be the practical quantitation limit (PQL) ofany individual
cPAH.
The two source areas located in the southern portion of the study area are the most influ-
ential source areas (with respect to the shallow aquifer) by virtue of their size and their prox-
imity to the APC. The western property boundary was chosen as the APC for the shallow
aquifer because it is hydrogeologically downgradient of both potential source areas. The south-
ern property boundary was chosen as the APC for the deep aquifer for the same reason. The
source areas in the northern portion of the site seem relatively small and too far from either
APC to produce a significant impact on groundwater quality. Since itis possible that cPAHs
emanating from the northern sourceareas are additive, the two small areas are combined and
considered to be a single source of cPAHs to simplify the modeling effort. Combined, the
northern source areas may have some impact at the APC.
As discussed previously, the most conservative approachto modeling a mixture of cPAHs
is to assume that the total cPAH soil value is attributable to the occurrence of the single most
water-soluble cPAH and not a mixture of the seven constituents (e.g., the concentration of
benzo[b]fluoranthene (C,,,) is 700 m a g , and no other cPAHs are detected). This is an
extreme worst-case scenario, since the concentration of cPAHs in groundwater at the APC is
directly proportional to the constituent soil concentration at the source area of interest and
cPAHs typically occuras a mixture at the site as a result of past practices, notjust as individual
components.
Figure 9 presents the source areas, the location of the hypothetical abandoned well, and
the locations of the shallow zone and deep zone APCs used in the conceptual modeling effort.
The sourceareas were delineated duringthe 1986 site remedial investigationas those soils hav-
ing visible stainingbetween the 0 . 5 4 and 6.0-ft depths,an indication of cPAH contamination.
The 0.5-6.0-ft interval was selected because of its proximity to the shallow zone and its
potential to affect groundwater quality in that zone. Furthermore, the location of the hypo-
thetical improperly abandoned deep well is approximate, as excavation failed to identify its
exact location.
The remainderof this section discusses the numerical inputsto the algorithms and the sub-
sequent groundwater results at the APC as a function of constituent concentrations in soils at
the source areas.
5. ShallowAquifer
Three general areas were evaluated to determine soilcPAH concentrations that are protective
of the shallow aquifer at the APC. These are the southeastern, southwestern, and northern
areas. Each area its corresponding modeling inputs are discussed below.
Regional shallow groundwater trends indicate that groundwater beneath the site flows from
east to west, perpendicular to the southwestern source area. Estimated source width (l"),
source length (X), and distance to the APC (Y)are 25, 275, and 230 m, respectively. Only
unpaved areas were considered in calculating the source area dimensions, because pavement
would prevent infiltration of precipitation and subsequent leachingof cPAHs.
0
Figure 9 Approximate location of source areas and points of compliance. Hatching indicates areas in which visual staining was observed in P
3
subsurface soils. rp
.%
Cleanup 131
The source locatedin the southwestern portion of the site is closer to the APC than those
in the southeastern areas and should therefore have a greater effect on groundwater qualityat
the APC.Input estimates for the southwestern source area includewidth (Y’ = 45.7 m),
length (X = 69 m), and distance to the APC (Y = 47 m). The central area of the source is
pavedand is not considered part of the overall source area since migration of the cPAHs
by leaching from soils beneath the paved area will be negligible without the infiltration of
precipitation.
Groundwater inthe northern portion of the site also flows from east to west perpendicular
to the two source areas. The two source areas are combined to account for the potential co-
contribution of cPAHs to the shallow zone and simplify theestimation of a soil cleanup goal.
The source inputs for width (Y‘),length (X), and distance to the point of compliance (Y)are
111, 78, and 91 m, respectively.
6.DeepAquifer
To determine the potential impact of shallow zone groundwater concentrations on the deeper
aquifer, a number of assumptions must be made. For the sake of conservatism, it is assumed
that the improperly abandonedwell exists as a conduit to the deep water-bearing zone. Impact
on the deep aquiferis influenced by the integrity of the abandoned well and the physical char-
acteristics of the aquifers. Little site-specific information pertainingthe
to deep well conduit or
the deep water-bearing zones is available; therefore, hydraulic conductivity, horizontal gradi-
ent, porosity, and aquifer thickness must be estimated from the available literature.
The 5304 water-bearing unit corresponds to the base of the Chicot Aquifer in the Alta
Loma Sands.This layer is approximately 200-400 ft thick in the vicinity of the site and is fairly
homogeneous, being 60-80% sands. Hydraulic conductivities of lo-’ c d s e c and a porosity of
35% are considered to be typical of the formation [21].
The estimated Darcy velocity for boththe deep zones used in the modeling effortis there-
fore 1 X lo-’ cdday.
Steady-state flow from the hypothetical conduitis a function of the integrity of the well
and the availability of groundwater present in the shallow aquifer. A characteristic of the shal-
low aquifer at the site is its relatively low yield. Yields of 1-1.5 gallmin (gpm) are common.
Pump tests conducted in 1988 used a pumping rate of 1.25 gpm, and significantdrawdown was
observed in each of the observed wells. If shallow zone groundwater is flowing to the deeper
zones through the conduit, a trend toward the conduit would be apparent in the shallow zone
groundwater contours. Shallow zone groundwater contours presented in the RI report do not
indicate the presence of a significant trend associated with an open conduit losing 1.25 gpm to
deeper aquifers. Therefore,a conservative estimate of flow rate (Q)equal to one-tenth of the
1.25 gpm rate (0.125 gpm) is used as the maximum potential flow from the shallow zone
through the hypothetical conduit.
The exact location of the hypothetical conduit is also unknown. U.S.Geological Survey
records and magnetometric surveys indicate that the general location is believed to be in the
south-central portionof the site, approximately 55 m north of the southern property boundary.
D. Modeling Results and Conclusions

1. No LeachingPotential
The following paragraphs present the modeling results and conclusions for cPAH concentra-
tions in soil that are protectiveof the shallow water-bearing unitas well as the deep zone.The
results are presented along with the intricaciesof the modeling effort and a discussion of the
validity of the results from an analytical solution standpoint. Assumptions concerning the mo-
bility of cPAHs are formulated from a review of the respective MIS. Benzo[b]fluorantheneis
the most relatively mobile cPAH because of its higher water solubility. It has the greatest po-
132 Kotun et al.
tential to leach andaffect water qualityat a point of compliance. As stated previously, all mod-
eling efforts will therefore use benzo[b]fluoranthenephysicalandchemical data in the
determination of a total cPAH soil cleanup goal.
2.ShallowAquifer
The VHS model is used to estimate the dispersion of cPAHs in shallow zone groundwater.The
shallow aquifer is defined as the first 3 m of the saturated zone and is hydraulically connected
to the intermediate aquifer. The shallow zone and the upper intermediate water-bearing zone
communicate through the upper intermediateaquitard, which consists of an 11-30-ft layer of
interbedded clays, silty clays, and sandy clays. Since the VHS model assumes isotropic ho-
mogeneous conditions, it cannot be extended to describe constituent movement in the upper
intermediate aquitard; therefore, vertical dispersion cannot be extended beyond 3 m in the shal-
low aquifer. Domenico and Palciauskas [l91 defined Z by monitoring the contaminant plume at
the waste area boundary. This typeof monitoring datais not always availableor possible, and
commenters on the model suggest that a less arbitrary estimation of the Z parameter can be
calculated using vertical dispersivity and the width of the source area parallel to groundwater
flow directions. Constituent penetration at the downgradient source boundary is estimated with
the equation
z = (U~Y’)O.~ (22)
where Z is the penetration depth, uzthe vertical dispersivity, andY’the width of the sourcearea
parallel to the groundwater flow direction. The value of U, is estimated as 0.2 m [13].
Penetration depths of 2.24, 3.02, and 4.71 m were derived for the Southeastern, south-
western, and northern source areas, respectively. Penetration depths in the southwestern and
northern source areas exceed the effective depth of the shallow aquifer. Therefore, dilutionby
vertical dispersion is applicable only for the southeastern source area. Furthermore, vertical
dispersion for constituents emanating from the southeastern source area is completeafter 20 m
of travel.
Horizontal spreading provideslittle dispersion forCOIs from the southeastern source area
(due to the length of the source area perpendicular to groundwater flow direction) and the
southwestern source area (due to its proximity to the APC). Horizontal dispersion provides
some dilution for the combined northern source areas.The dilution associated with vertical and
horizontal dispersion is applied to the performance standard of 10 pg/L to determine the CO1
concentration in leachate from the source area. The leachate concentration is then substituted
into the OLM equation to determinethe soil concentrationthat is protective of shallow ground-
water at the APC.
Soil cleanup goalsfor cPAHs calculated forthe southeastern, southwestern, and northern
source areas are 250, 100, and 125 mgkg, respectively.
3. DeepAquifers
The potential impact of the lO-pg/L individual cPAH performance standard on the deep aquifer
can be estimated by assuming that the hypothetical deepwell conduit acts asa continuing line
source to the deep water-bearing zones.
The approximate locationof the abandoned wellis not directly downgradientof the south-
eastern source area, and since horizontal spreading does not occur to any significant extent
relative to the southeastern source area’s width, this area should not affect groundwater near
the hypothetical conduit. Also, the hypothetical conduit is upgradient of the southwestern
source area and is not located near the northern source areas; therefore, it should not be af-
Cleanup 133
fected by the leachate emanating from either of these source areas. Since 10 pg/L is the per-
formance standard for shallow groundwater, this concentration is used to represent the cPAH
concentrations entering the conduit.
Shallow zone groundwater entering the deep aquifer is limited by availability. As stated
previously, the flow rate used in the pumping test should be modified by a factor of 10 to ac-
count for the fact that shallow groundwater contours do notreflect an influence in the area of
the hypothetical conduit.
Well logs indicatethat the well was screened overa 15-m interval. Although the aquifer in
the vicinity of the site is thought to be about200 ft thick, dilution will be considered over only
the 15 m that represent the screened interval.
The results of modeling indicate that the lo$@ performance standard for the shallow
zone is sufficiently protective of the performance standard of 0.2 pg/L in the deeper water-
bearing unit.
4. Uncertainties
The site conceptual model consists of a series of assumptions and algorithms derived fromthe
1988 RI report and current EPA databases. As with any model,uncertainties in the output stem
from the variability in selected input parametersand the mathematicallimitations of describing
environmental transport phenomena. Every effort has been made in this modeling effort to
ensure that when uncertainties arise any error in the output will be conservative. This section
describes the major sourcesof uncertainty inherent to the site conceptual model for the site and
possible implications for the modeling outcome.
The site conceptual model is limited to describing transport phenomena associated with
Darcian flow characteristics of the underlying aquifer and subsequent Fickian transport of the
cPAHs in thesaturated soil matrix. If conditions other than these exist, the assumptionsof the
VHS model are violated. For example, if preferential flow pathways or zones of high perme-
ability exist in the saturated substrata, dispersion does not occur geometrically with respectto
the groundwater flowdirection. The applicabilityof the VHS model is therefore limited to de-
scribing constituent movement in the first 3 m of the saturated zone. Although thereis an in-
terconnection between the shallowzoneandtheupperintermediateaquifer, the model is
limited in its ability to describe potential dispersion of cPAHs through the upper intermediate
aquitard that separates the two zones. To this extent, the model assumes thata no-flow bound-
ary exists between the shallow zone and the deeper aquifers. This is a reasonable assumption
given site hydrogeological data and will not lead to over- or underestimation of contaminant
transport and subsequent attenuation.
The shallow aquiferis characterized in the RI report as being comprised of predominantly
silty materialsand clayey sands. This materialis relatively homogeneous, and preferential flow
pathways do not exist, with the exception of slickenslides, which occur regionally. The RI re-
port also indicates that the shallow zone is continuous beneath the site. The use of the.VHS
model should provide an adequate quantitative estimate of the dispersive processesat the site
in the shallow zone.
Limited dilution is afforded by the use of the VHS model, due to the size of the potential
source areas, their proximity to the AFCs, and the thickness of the shallow aquifer. This is
particularly evident in the southern portion of the site, where no dilution by vertical or hori-
zontal spreading is produced when cPAHsare modeled from the southwestern source area to
the western property boundary.
The assumption that cPAHs are chemically conservative and are not retarded by the or-
ganic carbon contentof the saturated zone soils producesa very significant level of conserva-
134 Kotun et al.
tism in the estimation ofcPAH transport ingroundwater. Similarly,high estimates of

permeability and porosity reduce the potential for underestimating migration potential from the
source areas.
The site conceptual model depends upon the size of the potential source area used in the
calculations of groundwater at the APC. Theseareas are approximated, and insufficient chem-
ical data are available to better
estimate the time and the size and shapeof the areas.The source
areas were estimated by a visual inspection of the soils (i.e., if a soil is stained, it is assumed
to contain cPAHs) completed in 1988 as part of the RI. Overestimation or underestimation of
the size of the potential source area could lead toan over- or underestimation of the source’s
effect on the underlying groundwater quality. Due to the conservative nature of the modeling
efforts, the underestimation would probably not be significant in the determination of the no
leaching potential.
The most significant sourceof uncertainty in the site conceptual model arises from the use
of the OLM to estimate leaching potential. Actual leaching of cPAHs could be greater or less
than leaching predicted by the OLM. Verificationof site-specific leaching potential by a com-
parison ofOLM estimates to actual TCLP analytical results will reduce this source of un-
certainty by providing site-specific soil leachate concentrations or a level of certainty to the
OLM values.
No site-specific information exists for the deep aquifer. Information on the zone is either
gathered from recent literature or inferred from trends occurring in overlying aquifers. The
greatest uncertainty in modeling potential constituent migrationto the deep aquifer is the es-
timation of flow through the hypothetical conduit from the shallow zone to the deep unit. The
existence of thispathway is questionable, as historical investigations failed to determine
whether the conduit exists, and trends in shallow groundwater do not indicate the presence of
a significant shallow groundwater sink in the approximate location of the well. If the conduit
it not open fromthe shallow zone to the deep zone,and flow will
does exist, in all likelihood is
be impeded by subsurface materials inside the former well or by the integrity of the remaining
well casing.
5 . Validationof the Site Conceptual Model

Examination of the site conceptual model indicates that the total cPAH action level is greatly
influenced by each constituent’s abilityto leach from site soils, not its dilution by dispersion.
Vertical and horizontal spreading account for a dilution factor of approximately 1.8 from the
southeastern sourcearea to the fence line. Vertical and horizontal spreading do not accountfor
dilution from the southwestern source area to the fenceline, suggesting that leaching fromun-
saturated soils is most influential in determining the soil cleanup goal.
As a result, EPA suggested that samples below the established direct-contact soil clean-
up goal of 700 mgkg should be analyzed for cPAHs and subjected to TCLP analysis. Results
obtained from the OLM portion of the site conceptual model could then compare to site-
specific soil leachate data. In addition, OLM values will be generated for the samples sub-
jected to TCLP The OLM value and the TCLP result for each cPAH can then be compared
for each sample collected from the site. The average difference between theOLM and TCLP
data could thenbe subjected to a paired t test at the 95% confidence levelto determine whether
the site-specific TCLP results are less than, equal to, or greater than the OLM results used
in the modeling effort for the determinationof the soil cleanup goal [22]. If the TCLP results
are less than or equal to the OLM results, then modification of the model is not required. If
the TCLP results exceed the OLM results, then the leaching portion of the site conceptual
model will be revisited to include site-specific leachingdata, and a new soil cleanup goal will
be developed.
E. SiteFieldInvestigation
As a result of the uncertainties associated with the modeling results (inparticular the leaching
portion of the site conceptual model), a Supplemental Field Investigation was implemented.
This investigation focused on better defining the source areas with respectto soil contamination
and determining site-specific leaching potential to compare to OLM results.The following sec-
tions present an overview of the field investigation.
1. Development of Area-Specific Soil Boring Locations
The f i t task associated with the soil boring program was to establish a sampling grid over
each potential source area. The locations of the soil boring grids were approved by EPA V in
September 1991 basedonthesourceareasdefinedinthe 1986 RI reportand in the site-
modeling effort.
The original grid' spacing for all four investigativeareas was approximately 1 0 0 ft by 100
ft. However, some sampling was done in areas not corresponding to grid loci, as a result of
field limitations or greater data needs in a given area. Limitations for this spacing were intro-
duced by the railroad right-of-way and paved areas. Boring locations were established at less
than the 100 ft by 100 ft grid due to asphalt paving (along the west side of the southeastern
area), site buildings, and property linesor fence lines.The boring affected by paving and a site
building was G-17. Borings G-51, G-52, and G-53 were located only 60 ft from brings G-13,
G-26, and G-28, respectively, becauseof the property or fence line. BoringsG-l through G-l3
and G-51 are located along the eastern property line. Figure 10 shows the four investigative
areas and their respective sampling locations.
2. DrillingMethodology
Each soil boring was drilled using the hollow-stem auger method of drilling with a truck-
mounted rig. Soil sampleswere collected continuously usinga 24-in. split-spoon device as the
hole was advanced to the termination depth of 6 l? at each boring location.
Samples were collected continuouslyso the soils could be classified with respect to tex-
tural compositionand the presenceor absence of visually identifiable potential site-related con-
stituents. Samples were collected using a 3-in. OD split-spoon sampler, logged in the field by
the site hydrogeologist, cornposited for the individual spoon sample interval, and placed in
clean laboratory-preparedjars with Teflon-lined lids for submittalto the analytical laboratory.
All soil samples were classified according to the Unified Soil Classification System.
Followingcompletion of each boring, the borehole was sealed to thesurfaceusing a
cementhntonite grout. The split-spoon sampler was cleaned after collection of each sample
using a soapy water bath followed by a clean water rinse. Between boreholes, and prior to
leaving the site, the drilling rig, hollow-stem augers,drilling rods, and associated drilling tools
were steam-cleaned at the on-site decontamination area. The cuttings from the drilling oper-
ations were contained on site in roll off boxes for eventual treatment or disposal.
3. ChemicalAnalysis
The soil samples collected from each depth interval of the grid boring locationswere submitted
to a certified laboratory for chemical analysis. The samples were analyzed for cPAHs using
EPA Method SW846 8270, a high-resolution gas chromatographic, low-resolution mass spec-
trometric (GCIMS) method of analysis. Mass spectrometric detection allows for nearly absolute
identification of the cPAHs as opposed to other methods of detection. Samples that exhibited
concentrations of less than 700 mgkg of cPAHs were also submittedfor TCLP extraction and
subsequent leachate and analysis for cPAH by Method SW846 8270 to determine the actual
leaching potential of the sample. An analytical sampling summary is presented in Table 28.
136
I
Table 28 Analytical Sampling Summary
Soil cPAH analysis TCLP/cPAH analysis
No. of Total No. Rinsate Lab No.ofTCLP Lab
Area brings of samples blanks blanks MSMSD Duplicates samples blanks MS/MSD Duplicates
Southeastern 53 162 8 11 9 4 158 9 8 1

Southwestern 16 48 2 4 3 4 46 4 3 4
Northeastern 13 39 2 1 4 2 39 3 4 0
Northwestern 5 15 1 1 2 I 15 1 2 1
138 Kotun et al.
As part of the study, a quality assurance/quality control(QNQC) sampling program was

completed that consisted of collecting matrix spikdmatrix spike duplicate samples and field
blanks. A laboratory auditwas also conductedby EPA to ensure the legitimacyof the analyses.
Site soil samples subjectedto TCLP extraction didnot produce detectable concentrations
of any cPAH inthe corresponding leachate. The majority of soil samples contained total cPAHs
in excess ofthe soil cleanup goals obtained by the modeling effort. Soils containing asmuch as
1200 mgkg of total cPAHs did not leach, suggesting that site leaching potential is at least a
factor of 4-12 times lower than predicted by the site conceptual model. Samples containing
more than 1200 mgkg total cPAHs were not subjected to TCLP extraction.
The following paragraphs and Figures 11-13 present a spatial presentation of source area
soil cPAH concentrations. Discussions concerning remediation are related to the direct-contact
soil cleanup goal of 700 mgkg total cPAHs since site-specific data suggest that this value is
also protective of the no leaching potential. Areas requiring remediation were delineated onthe
assumption that the extent of impact is midway between a “clean” point and an adjacent im-
pacted point. The volume of soils exceeding the remedial goal of 700 mgkg was calculated
based on the depth at which the exceedance was noted.
The analytical resultsof the samples collected from53 soil boring locations in the south-
eastern area were used to delineate the horizontal and vertical extents of soils for remediation
(Figure 11).The locations in this area that exhibited total cPAH concentrations greater than 700
ppm were grid locations G-60, G-5,and G-61; G-64,G-67, G-9, G-22, G-23, G-24, G-25; and
G-73. Soils delineated for remediation are confined tothe upper 2 ft, except for three locations.
Locations G-73 and G-22 show soils exceeding700 ppm total cPAHs inthe 2-443 interval, and
G-61 showed total cPAHs exceeding 700 ppm in the 0 - 4 4 interval. Approximately 2466-
2868 cu yd of soil in this area exceed the remedial goal.
A total of 16 soil borings were drilled in the southwestern area. The analytical results are
presented in Figure 12. Grid sampling locations G-80, G-81, G-82, G-83, G-35, and G-36 ex-
hibited totalcPAH concentrations above 700 ppm. Soil intervals delineated for remediationare
limited to a small portion of this area and are generally from 2 to 6 ft. Boring location G-83
exhibited cPAH concentrations above700 ppm in the 0-2 ft interval, boring G-81 exceeded the
remedial goal in the 2-4-ft interval, and borings G-80, G-82, G-35, and G-36 exceeded the
goal in the 4-64? interval. Approximately 626-1588 cu yd of soils in this area exceed the re-
medial goal.
In the northern area, grid samplings locations G-46 and G-87, between 0 and 2 ft, ex-
ceeded the risk-based criteria of 700 ppm for total cPAHs (Figure 13). Approximately 558-
1177 cu yd of soils present in this area exceed remedial goals.
No grid sampling locations in the northwestern area exhibited total cPAH concentrations
above 700 ppm (Figure 13). Remediation of soils in this area is therefore not necessary.
F. Conclusions
To determine soil cleanup goals for the cPAHs protective of underlying groundwater, a con-
ceptual model of potential constituent migration was developed. The site conceptual model
consists of two elements:(1) leaching of constituents from the potentially affected soils and (2)
migration and dispersionof the constituents with respect to groundwater flow direction.
The OLM was used to describe the leaching potential of the cPAHs present in the soil
(Element I), while the VHS model was selected to describe dilution associated with dispersion
of the cPAHs in groundwater (Element 11). The conceptualmodel is conservative (froma mod-
eling standpoint) in that biodegradation andretardation in soils and groundwaters are not con-
sidered.
-
0
SCALE (FEET1
50 100 1%.
Figure 11 Southeastern source area-total cPAH analytical results. (0)Soil sampling location (approximate). Hatching indicates estimated area with
Y,
soils exceeding 700 m a g total cPAHs. Total cPAH concentrations: 0-2 !
I,
500,2-4 ft, 685; 4-6 ft, 191.6. ND, not detected.
140 Kotun et al.
Figure 13 Northern source area-total cPAH analytical results. (0) Soil sampling location. Hatching indicates soils exceeding 700 rnglkg
total cPAHs. Total cPAH concentrations: 0-2 ft, 102; 2-4 ft, 81.8; 4-6 ft, 188.9. ND, not detected.
s
142 Kotun et al.
A semiquantitative sensitivity analysiswas performed on the results of thesite conceptual

model. Element I, leaching as predicted by the OLM, was the most influential portion of the
modeling effort. Element I1 had little impact on the final modeled results because of the shal-
lowness of the uppermost water-bearing zoneand the proximity of the potential sourceareas to
the alternative point of compliance (APC). As a result, leachate testing was performed to de-
termine whether the use of the OLM was representative of site conditions. EPA suggested the .
use of TCLP analyses of soil samples taken from each of the potential source areas.
Element I, represented by the OLM, is a multiple regression equation:
C[ = 0.000211 x ,F678(23) x WF373
where C, is the estimatedleachate concentration, C, is soil concentration, and W,is water sol-
ubility.
TCLP data collected to confirm the validity of Equation (23) with respect to site leaching
potential indicates that for cPAH soil concentrations below 1200 ppm (C, < 1200 mgkg) the
leachate concentration is below the limit of detection. Cl can therefore be expressed as
c, = 0 (24)
The first element of the conceptual model is therefore undefined from a practical stand-
point using site-specific leaching data, given that
where {x} is any number.

Site soils containing in excessof 1200 mgkg total cPAHs (C,) did not produce detectable
concentrations in their respective leachate(C,), and mathematicalcorrelation between soil con-
centration and site-specific cPAH leachate values beyond the previously stated relationship
could not be established. Soils with cPAH levels greater than 1200 mgkg were not submitted
for TCLP analysis.
Based on the site-specific conditions, the use of the OLM to describe leaching in the site
conceptual model of constituent transport was a conservative assumptionin lieu of site-specific
informationregardingconstituentleaching.Therefore, the ROD-specifieddirect-contact
cleanup goal of 700 mgkg total cPAHs is also protective of the no leaching potential for this
particular site.
In this particular case, spending the additional money to derive a site-specific estimate of
leaching potential resultedin a significant cost savingsfor the potentially responsible partyas
opposed to removal of soils based solely on the modeled results. However, it should not be
overlooked that the modeled results werealso adequately protectiveof the no leaching potential
established in the site ROD. Using the analytical solutions in determining a soil cleanup goal
at sites having smallersource areas or where less costly remedial alternatives are an option will
produce protectiveand cost-effective results.In any case, thedevelopmentof soil cleanup goals
using analytical solutions protective of underlying groundwater quality is necessary to focus
additional field investigations and data collection efforts when the protection of groundwater
quality from continued soil releasesis a priority.
REFERENCES
1. U.S. Environmental Protection Agency, Risk Assessment Guidance for Superfund. Vol. I , Human
Health Evaluation Manual, Washington, D.C., 1989.
Cleanup 143
2. Chu,M.M. L., and Chen, C. W., Evaluation and estimation of potential (Carcinogenic risks of
polynuclear aromatic hydrocarbons, Symposium on Polynuclear Aromatic Hydrocarbons in the
Workplace, International Chemical Congress of Pacific Basis Societies, 1984.
3. U.S. Environmental Protection Agency,Health Effects Assessment Summary Table (HEAST). 1991.
4. U.S. Environmental Protection Agency (Region I), Supplemental Risk Assessment Guidance for the
Superfund Program, 1989.
5. U.S. Environmental Protection Agency, Development ofStatistical Distributionsof Ranges of Stan-
dard Factors Used in Exposure Assessments,1985.
6. U.S. Environmental Protection Agency, Exposure Factors Handbook, 1989.
7. U.S. Environmental Protection Agency, National Oil and Hazardous Substance Pollution Contin-
gency Plan, 1990.
8. U.S. Environmental Protection Agency,Multimedia Exposure Assessment Model for Evaluating the
Land Disposal of Wastes: Model Theory and Application,1991.
9. U.S. Environmental Protection Agency, Office of Water, Drinking Water Regulations and Health
Advisories, April1992.
10. U.S.Environmental Protection Agency, Office of Water Regulations and Standards, Quality Cri-
teriafor Water, 1986.
11. U.S. Environmental Protection Agency, Mice of Water Regulations and Standards,Aquatic Fate
Process Data for Organic Priority Pollutants,1982.
12. Wang, H. F., and Anderson, M. F!, Introduction to Groundwater Modeling: Finite Difference and
Finite Element Methodr, W. H. Freeman, San Francisco, 1982.
13. U.S. EPA, VHS model, Fed. Reg., 50(229), 48897-48901 (Nov. 27, 1985).
14. U.S.EPA,OLMmodel, Fed. Reg., 51(145), 27061-27064 (July 29, 1986).
15. Lkagun, The Soil Chemistryof Hazardous Materials,Hazardous Materials Control Research Insti-
tute, Silver Spring, Md., 1988.
16. Laskowski, D. A., Goring, C. A., McCall, F! J., and Swann, R. L.,Terrestrial environment in en-
vironmental risk analysis for chemicals, in Environmental Risk Analysis Chemicals (R. A. Con-
waya, Ed.), Van Nostrand Reinhold New York, 1983.
17. Ford and Gurba, Methods of determining relative contaminant mobilities and migration pathways
using physicalchemical data, 1984.
18. US. EPA, Water Quality Assessment: A Screening Procedure for Toxic and Conventional Pollutants
in Surface and Groundwater,Part I1 EPA/600/6-85/0026, 1985.
19. Domenico, I? A.,andPalciauskas, V. V., Alternateboundariesinsolidwastemanagement,
Groundwater,20, 301-311 (1982).
20. Morgenau, M., and Murphy, G . M., The Mathematics of Physics and Chemistry, Van Nostrand,
Princeton, N.J., 1956.
21. Freeze, R. A., and Cherry F. A., Groundwater,Prentice-Hall, Englewood Cliffs, N.J., 1979.
22. Rosner, B., Fundamentals ofBiostatistics, 2nd d.,PWS, 1982.
23. Kreitler, C. W., Guevara, E., Granata, G., and McKalips, D., Hydrogeology of Gulf Coast aqui-
fers, Housbn-Galvestonarea, Texas, reprinted fromTrans. GulfCoast Assoc.Geol. Sci., Vol. 27,
Geologic Circular 77-4, 1977.
6
Designing to Prevent Pollution
James Lounsbury
National Roundtable of State Pollution Prevention Programs
Silver Spring, Maryland
1. INTRODUCTION: ENGINEERS IN A CHANGING ENVIRONMENT

In the annals of engineering folklore, it’s been said that Henry Ford required his suppliers to
ship raw materials on pallets of specified dimensions-an unusual requirement at the time
since pallets were always dumped or burned after use. Henry’s genius saw the opportunity:
dismantling the pallets provided made-to-order hardwood floorboards for his ModelT’s. This
simple idea eliminated the cost of floorboards and of the men and equipment needed to dispose
of used pallets. Environmental benefits were not explicitly considered-but they were there.
Ford reduced the amount of raw materials (trees) extracted from the environment and the hu-
man and energy resources neededto convert trees into pallets, and he also reduced the amount
of smoke emittedto Detroit’s air (if the pallets were to be burned) and the amount of ash to be
disposed of.
When the industrial revolution began in the 1850s, the United States was a land of abun-
dant resources, diverse markets, and transportation systems capableof moving raw materials
and finished products. Engineers were concerned with performance, quality, and maximum
yield. Their main objective was to make a profit by producing more and better goods and ser-
vices. Environmental considerations were not a significant factor in the manufacturing equa-
tion. We had seemingly infinite land and water resources capable of assimilating whatever
amounts of wastes were dumped. Adverse environmental impacts were not perceived as a se-
rious problem (although adverse impacts were, in fact, present). Therefore, there were few or
no environmental coststo consider.
The advance of manufacturing and the engineering sciences that supported the American
industrial base proceeded for about a hundred years before public awareness of environmental
pollution and health-related issues began to catch up.
It’s been only during the past 30 years that environmental quality has become a national
watchword. In the 1960s, “Keep American Beautiful” was a widely publicized effort to keep
our country litter-free. As urbanites inhaled more smog, and as rural citizens became more
145
146 Lounsbury
aware of dying rivers and contaminated drinking water wells,they began to seek solutions to
these problems throughthe legislative process. Beginning in the 1970s, the U.S.Congress em-
barked on a legislative agenda that brought environmental management to the forefront and
changed the ground rules for manufacturers forever. Forthe next two decades, industry andthe
government focused on managing wastes and emissions from factories, autos, and sewage treat-
ment plants by building bigger and better pollution abatementand control equipment designed
to remove pollutants from “end-of-pipe” discharges.As the economy has expanded,so has the
price tag for pollutioncontrol-now over $1 15 billion dollars per year. Kenneth Chilton, in his
1991 study Environmental Dialogue:Setting Priorities for EnvironmentalProtection, is quoted
by Mason [l] as stating that “to put these (EPA) costs into perspective, the percapita price for
pollution controls was more than $450 in 1990. A family of four, thus, spent more than $1800
in the form of taxes or higher prices for manufactured goods to pay for pollution abatement.”
As the costs of pollution control have continued to rise, both industry and government have
begun to respond to this startling price tag by finding innovativeways of reducing these costs.
Government is looking to expand beyond its traditional role of ensuring compliance with end-
of-pipe treatment and disposal regulations and is instead seeking nontraditional approaches to
prevent or reduce pollution generationup front by providing industry with technical informa-
tion and assistance outside the traditional regulation and enforcement realm. Government is
also looking for ways to modify its regulatory and enforcement processesto include better in-
centives for pollution prevention. At the same time, industry is looking for ways to work with
government in both of these areas to reduce the use of toxic materialsin products anddesigning
production processes thatgenerate less or no waste. These concepts,known as “pollution pre-
vention,” and “green design,” are the keys to integrating environmental protection and com-
petitive manufacturing in the 1990s and the next century and are the subject of this chapter.
Organization of This Chapter

This chapter provides a basic road map for engineering students to better understand
The evolution of environmental laws and regulations facingthe engineer
“End-of-pipe” pollution control versus “pollution prevention” and “green design”
Where to go for information on chemicals, pollution prevention, and green design
It is designed to provide the reader with general information andis presented with the un-
derstanding that the author is not engaged in renderinglegal, accounting, or other professional
services. If professional advice is needed, the services of a competent professional should be
sought. It should also be noted that some of the statutes and regulations discussed here are
regularly revised. As a result, the information in this chapter may be incomplete or subject to
contrary opinion. It would be wise for the reader to check on thecurrent status of any particular
statute or regulation before proceeding with related work.
II. EVOLUTION OF ENVIRONMENTAL LAWS AND REGULATIONS

By about 1970, the federal government responded to citizens’ concerns about environmental
problems by making environmental legislation a priority. The federal government acknowl-
edgedthatbettertoolswereneededtomanageenvironmentalproblems. Starting in1970,
Congress embarked on a decade of ambitious legislative activity inwhich it would enact
landmark legislation to improve water quality andair quality and protect our land and ground-
water resources.
This section provides a brief summary of the major statutes enacted since 1970. From the
summaries, the readerwill hopefully get a sense of the types of approaches pursued inthe law
Pollution
Designing to Prevent 147
and see that there has been a gradual shift in focus on how to best manage the environment.
This shift began with medium-specific (air, water, land, etc.) end-of-pipe pollution control and
has shifted slowly toward up-front pollution prevention and green design.
be obtained from various sources, including public libraries
Full texts of these statutes can
and publishers that specialize in environmental publications. A brief discussion of the regula-
tions promulgated by EPA that implement these laws is providedin the next section.
A. Summary of Key Federal Environmental Statutes Enacted

Since 1970'
In 1970, Congress established the U.S. Environmental Protection Agency (EPA) with the en-
actment of the Reorganization Act of 1970. This act consolidated the various environmental
management responsibilities that were previously dispersed throughout the executive branch
agencies, for example, Department of Interior (federal land management, mining), the Depart-
ment of Agriculture (pesticide registration), and the Federal Water Pollution ControlAdmin-
istration (development of scientific and technical information for protecting water quality).
EPA is charged with implementing most of the environmental laws passed by Congress,
although some functions still remain with other agencies. For example, the Department of In-
terior manages federally owned lands andthe Occupational, Safety and Health Administration
is responsible for workplace exposure to toxic chemicals. In general, EPA's job includes ( l )
developing the scientific and technical tools for assessing environmental impacts and risks that
may accompany society's activities (e.g., disposal of manufacturing wastes, disposal of mu-
nicipal sewage and solid waste, assessmentof automobile and other air pollutants affectingur-
ban populations), (2) publishing regulations that restrict actions that pose unacceptable risks
to humans and the environment, and (3) enforcing its regulations through civil and criminal
legal actions.
In 1970, Congress also enacted the National Environmental Policy Act (NEPA).NEPA
effectively required all federal agencies to consider the impacts on the environment before
taking any major federal action. NEPA was a key force, philosophically and legally, for all
future environmental decision making in the United States. It created anew decision-making
process and provided the opportunity for the public to be involved in reviewing all major
federal actions.
NEPA requires federal agenciesto analyze the environmental impacts of all proposed ma-
jor federal actions suchas building dams, leasing federal land for oil exploration, and building
interstate highways. NEPA further requires agencies to consider alternatives to the proposed
action, analyze the impacts of each, publish the agency's analysisof alternatives and recom-
mended course of action in an Environmental Impact Statement (EIS), and ensure that there is
an opportunity for public participation in the review of the EIS through written comments and/
or testimony in public hearings.NEPA specifies a process for reaching a decision. It does not
dictate any particular decision.
The Federal Water Pollution Control Act of 1972 (FWPCA) established goals for re-
storing andmaintainingtheintegrity ofwaters. The FWPCA,now theCleanWater Act
(CWA), has been amended several times to put in place several major programs, including
(1) technology-basedwastewatertreatmentregulations, (2) requirements for plant-specific
wastewater discharge permits and chemical-specific water quality criteria to use as a guide-in
writing the permits, (3) technology-based requirements for municipal sewage treatment plants
and a federally sponsored funding program to assist municipal governments in the construction
Government Institutes. Inc., Rackville, Md., 1990.

'Source material from Environment Srarures, 1990 d.,
148 bumbury
of sewage treatment plants, (4) area-wide water quality planning programs to ensure that all
pollution sourcesand institutions are considered in water quality protection,and (5) a specially
designed program to protect the nation's wetlands.
Congress amended earlier air quality legislation with the Clean Air Act in 1972. These
requirements, combined with amendments enacted in 1977 and 1990, cover a very broad array
of programs and requirements, includingthe establishment of ambient air quality standards and
the development of state implementation plans for a variety of pollutants, national emissions
standards for stationary sources of hazardous pollutants, requirements for ozone protection,
motor vehicle emission and fuel standards, and the prevention of significant deterioration of air
quality. The 1990 amendments are significant because they encourage the use of market-based
principles, including performance-based standards and emission banking and trading, provide
a framework for finding a cost-effective combinationof fuels and technologyto develop alter-
native clean fuels, promote the use of clean low-sulfur coal and natural gas as well as inno-
vative technologies to clean high-sulfur coal through the acid rain program, sufficiently reduce
energy waste andcreate enough of a market for clean fuels derived from grain and natural gas
to cut dependency on oil imports by 1million barrels a day, promote energy conservation'
through an acid rain program that gives utilities the flexibility to obtain needed emission re-
ductions through programs that encourage customers to conserve energy, and establishan im-
portant innovative approachto pollution prevention.
The 1990 CAA amendments require that EPA conduct a basic engineering research and
technology program to develop, evaluate, and demonstrate nonregulatory strategies and tech-
nologies for air pollution prevention. This signals that Congress had added prevention measures
to the end-of-pipe treatment approach previously addressed in the statute.
The 1990 CAA amendments also offer other pollution prevention incentives. One of the
most widely discussed and challenging is the opportunity for facilities to receive extended com-
pliance periodsin exchange for early and increased reductions of their hazardousair pollutants.
As a result, industry may find that source reduction measures are a more cost-effective ap-
proach to achieving emission standards for hazardous air pollutants.
The Safe Drinking Water Act was amended several times during the 1970s and 1980sto
improve the drinking water standard-setting process for consumptionof drinking water at the
tap. Standards are set considering both the cost and effectiveness of available treatment tech-
nologies. The SWDA amendments of1986required EPA to promulgate a total of 108 standards
for toxic chemicalsby 1991. They also require states to develop a program to protect the area
around wells (wellheads). This provision was enacted in response to findingsby EPA that 8000
drinking water wells in the nation were contaminated by thousands of sources, including land
disposal facilities, underground storage tanks,septic systems, underground injection wells, and
pesticide andfertilizer applications. The chemicals foundare widely used in common products,
including plastics, solvents, pesticides, paints, dyes, varnishes, and ink.
The Federal Insecticide, Fungicide and Rodenticide Act (FIFRA) was originally en-
acted in 1947 and has been amended several times to factor in new information and policies on
the effects of chemicals on human health and the environment. FIFRA requires manufacturers
of pesticides, herbicides, and related chemicals to comply with a registration process (or re-
registration process for pesticides registered before 1972). inwhich the manufacturer must
complete batteries of tests to ensure that when used properly a pesticide presents no unrea-
sonable healthor environmental risks.EPA is authorized to review test results and prohibit, ban
the manufacture of, or limit the use of existing or proposed products.
Over 50,000 pesticides have been registered since FFRA was originally enacted. How-
ever, significant advancesin the sciences of toxicology and risk assessment have occurred over
the past decade. These advances have led to concern over potentialrisks from previously reg-
Pollution
istered pesticides. Amendments to FIFRA in 1988 require previously registered pesticidesto be

reregistered under current, stricter procedures.
The Toxic Substances Control Act (TSCA) of 1976 includes very broad authorities that
require EPA to control the risks from over65,000 existing chemical substances on the market
(other than chemicals regulated under FIFRA) and to regulate the manufacture, processing,
distribution, and use of proposed new chemicals. Manufacturers must complete laboratory tests
and provide detailed information on the processes used to manufacture each chemical EPA to
for review. Based on its review, EPA has the authority to prohibit production, limit use,or ban
production of the chemical.
The Solid Waste Disposal Act (SWDA)of 1976, later renamed the Resource Conserva-
tion and Recovery Act (RCRA),radically changed the role of the federal government in solid
waste management. EPA promulgated guidelines in 1979 that prohibited the previously widely
accepted practice of open dumping and required the use of sanitary landfill standards to reduce
the potential for disease and restrict open access to garbage by humans and animals. Under
RCRA, EPA created the nation’s first “cradleto grave” hazardous waste management system
in which EPA identified the worst industrial wastes (about 2% of all industrial solid waste)and
set standards for tracking these wastes from generation to treatment to disposal and for disposal
of wastes in landfills.
In 1984, RCRAwasamendedwiththe HazardousandSolidWasteAmendments
(HSWA). HSWA prohibited the disposal of hazardous wastes on land unless they were first
treated using standards setby EPA for best demonstrated available treatment (BDAT) technol-
ogies. HSWA also directed EPA to launch a major new program to establish standards for re-
placing approximately 2 million leaking underground storage tanks containing gasoline and
chemical products.
HSWA was the first statute that explicitly shifted national priorities for waste management
from end-of-pipe pollution abatement and control to pollution prevention. (Note:The term used
in HSWA was “waste minimization.”) HSWA directed EPA to study the incentives and bar-
riers to a prevention-based approach because the Congress realized that the end-of-pipe ap-
proach of the past was not providing any significant reduction in the amount of waste generated
and managed even though the standards for end-of-pipe environmental controls were becoming
more strict.
The progress EPA made in the next several years in studying avenues to encourage pollu-
tion prevention provided some of the basis for pollution prevention legislation passed 1990. in
This is discussed in more detail at the end of this section.
The ComprehensiveEnvironmentalResponseCompensationandLiabilityAct
(CERCLA or Superfund) of 1990 established a landmark environmental program for the
cleanup of hazardous substances improperly disposed of on land. The enactment of Superfund
was a rude awakening for many U.S. companies. It has led to the discovery of 30,000 poten-
tially contaminated chemical dumps. Superfund established $9 billion
a fundto pay for cleanup
of sites where responsible parties cannot be foundor where they are recalcitrant. However,$9
billion is enough to pay for only a small fraction of the total sites eligible for cleanup. Super-
fund made companies liable for cleanup costs and damages, including wastes that the compa-
niesbelievedweresafelydisposedofbutthathadneverthelessresultedinenvironmental
damages. CERCLA required companies to pay taxes on feedstock raw materials (which were
the fundamental source of wastes discoveredto be causing damage in the ground) to support the
federal cleanup fund. Companies involved in Superfund cleanup found that they pay for im-
proper waste disposal in four ways. They pay for raw materials that became waste, the cost of
waste disposal, a feedstock tax to pay for cleanup,and cleanup costs (plus punitive damages in
some cases).
150 Lounsbury
Superfund was amended in 1986 with the Superfund Amendments and Reauthorization
Act (SARA). SARA strengthened all of the major portions of the cleanup program, forced
federal facilities to comply with the law to the same extent as any other facility, and reautho-
rized the cleanup fund and the feedstock tax on industry to support the fund.
The Emergency Planning and Community Right-&Know Act (EPCRA, also known
as Title I11 of SARA) was also enacted in 1986. The enactmentof EPCRA stems directly from
an incident involving the chemical release of methyl isocyanate from a pesticide plant in
Bhopal, India, in 1984 chat killed thousands of nearby residents and the release of methylene
chloride and aldicarb froma chemical plant in Institute, West Virginia, in 1985. EPCRA man-
dates that states and local communities prepare for chemical emergencies, requires facilities to
notify their states and communities of the presenceof an extremely hazardous substance andto
report spills or releases of such substances immediately, and requiresfacilities to report annu-
ally on the amounts of certain hazardous chemicals produced, used, and stored within the
facility if that amount exceedsa specified amount.
Facilities must also report to EPA annually on the amount of certain toxic chemicals they
release to the air, land, and water. EPA compiles this information in a publicly accessible da-
tabase called theToxic Release Inventory (TRI) and publishes an annual report describing the
reported releases. The TRI has had a very significant impact on the way industry views its
environmental responsibilities and accountability to the public.
The Pollution Prevention Act (PPA) of 1990 moved the government significantly forward
in its commitment to change the way it manages environmental protection. The PPA estab-
lished a national policy that
pollution should be prevented or reduced at the source whenever feasible; pollution that
cannot be prevented should be recycled in an environmentally safe manner whenever fea-
sible; pollution that cannot be prevented or recycled should be treated in an environmen-
tally safe manner whenever feasible; and disposal or other release into the environment
should be employed only as a last resort and should be conducted in an environmentally
safe manner.
The PPA requires EPA to considerpollutionprevention in itsrule-making activities,
provide grants to states for technical assistance to businesses seeking pollution prevention
opportunities, andmanage a computerizedtechnicalinformationclearinghouse on pollu-
tion prevention technologies that is available to the public. The PPA also requires facilities
that are required to report releases to the environment under EPCRA (Title I11 of SARA) to
also reporttheirprogress in pollutionpreventionto EPA eachyear,andrequires EPAto
issue a report to Congresseverytwoyears that describes the nation’sprogress inpollu-
tion prevention.
EPA is also charged with administering several other environmental statutes, which for the
sake of brevity are not described here. These include
The Marine Protection, Research and Sanctuaries Act of 1972
The Noise Control Act of 1972
The Radon Gas and Indoor Air Quality Research Act of 1986
The Asbestos Information Act of 1988
B. EnvironmentalRegulations
Most federal environmental statutes set broad goals and timetables for achieving these goals.
EPA is charged with the task of developing regulations that implement the law.
Pollution
The regulatory development process is describedin this chapter to emphasize the impor-
tant opportunity for the engineering community andfor individuals and companies to partici-
pate in the process and potentially contribute to the outcome of individual regulations.
The overall process for developing, proposing, and promulgating regulations isforthset in
the Administrative Procedures Act,a statute that applies to all federal agencies. Thereare two
basic but complex steps in the process. The first step covers the development of a proposed
regulation. EPA first determines what policy, economic, and technical factors are relevant to
the decision at hand and then generally proceeds with extensive engineering, toxicological,
economic, and other studies necessaryto arrive at a proposed approach. At the completion of
its studies, EPA proposes a regulation and solicits public comment on the methods and ratio-
nale used in its proposal.
The second major step includes completing whatever additional studies may be necessary
to adequately respond to public comments, incorporating relevant new information that may
affect the outcome, and promulgatinga final regulation. It generally takesat least two yearsto
develop and promulgate a regulation, depending on the complexity of the issues involved.
Each proposed and final regulationis published in the Federal Regisrer (FR),a daily gov-
ernment publication dedicated entirely to notifying the public of regulatory developments. A
compendium of all environmental regulations promulgatedby EPA is found in Title 40 of the
Code of Federal Regulations (40 Cm).
In addition to the regulations, EPA frequently publishes supplemental guidancethat pro-
vides additional technicalor procedural information relevant to understanding the compliance
requirements of the regulation.
C. States and Local Laws and Regulations

States and local governments also enact environmental laws and regulations. In many cases,
Congress directs EPA to establish federal regulations under a particular statute, then authorizes
EPA to delegate responsibility for implementing and enforcing a program to states that have
statutes and regulations that are at least as stringent as the federal program. In some cases,
state programs are more stringent than the federal program. It is not surprising to find differ-
ences in the ways states implement federal environmental laws.
Municipal governments also pass environmental laws and should be consulted regarding
matters particular to the municipality.
111. "END-OF-PIPE POLLUTION CONTROL VERSUS "POLLUTION

PREVENTION" AND "GREEN DESIGN"
End-of-pipe pollution control, which began with media-specific legislation of the 1970s and
1980s, has begun a shift in the 1990s to up-front pollution prevention and "green design.'' As
an expanding setof scientific, economic, and
a result of this shift, engineers today must address
technological factors if they wish to build better products and remain competitive,
Several initiatives under way in government and industry to foster this approach are dis-
cussed in this section.
A. Assumptions Underlying the Shift to Pollution Prevention and

Green Design
Much of the environment legislation enacted in the 1970s and 1980s was media-specific; that
is, each statute focused on either emissions to air, dischargesto water, or disposal on land.This
152 Lounsbury
approach arose froma general consensusthat industry shouldbe in charge of deciding how to
manufacture its products. The government's role wash to protect human health and the envi-
ronment and therefore should be limited to regulating emissions, discharges, and wastes after
they leave the manufacturing facility.
There were several assumptions built into this approach, however. It was assumed that if
the adverse impacts of waste disposal on the public increased, the public marketplace would
resist by making it more difficult for industries to site disposal facilities, which would in turn
drive up the costsof waste management. As the cost of waste managementrose, industry would
find an equilibrium point at which it was no longer profitable to generate and manage waste.
Consequently, business managers would be forced to find more efficient ways of producing
goods and services in order to stay in business.
In general, these wereprobablygoodassumptions,butseveralunanticipatedfactors
slipped into theequation. First, the study of the impactsof contaminants on human health and
the environmentwas not as advanced as manufacturing science and technology. Therefore, nei-
ther the government, the public, nor industry could fully evaluate the costs of the impacts of
waste management on the environment and assign a true cost to that activity.
Second, no one anticipated some of the outcomes of media-specific statutes. In general,
each of these statutes sets standards withoutconsidering relationships to other media. In some
cases, media-specific statutes have inadvertently promoted the shifting of pollutant releases
from one medium to another without reducing the overall generation of pollutants. For exam-
ple, some of EPA's air quality emissions'standards are based on end-of-pipe pollution control
technologies such as stack gas scrubbing. In the past, in order to achieve compliance quickly
and with certainty, manufacturers often chose to add a stack gas scrubber to the smokestack
rather than redesign their products and/or the production process to eliminate the source of the
toxic emission. Using a scrubber achieved compliance with air regulations by removing pol-
lutants from stack gases andtransferring these pollutants to scrubber wastewaters. What were
once air emissions, therefore, become water pollutants.
Similarly, to comply with Clean Water Act regulations, most manufacturers chose toadd
wastewater treatment plantsat the end of the pipe rather than redesign productsor processes to
reduce pollutants at the source. Thus, while wastewater treatment removed pollutants from
wastewater, it transferred these pollutants, in the form of sludge, to a waste that was usually
incincerated (thereby creating an air emissions problem) and/or was disposed of in landfills.
There is no doubt that the United States has made significant headwayin cleaning up the
environmentusing a media-specific approach. However,two significant problems arose as
a result:
1.End-of-pipe pollution control doesn't really solve the problem-it just moves it from me-
dium to medium.
2. Managing waste costs money and adds to the cost of production-often at the expense of
other opportunities.
As noted earlier, the cost of the end-of-pipe approach has risen to an estimated $115 billion
annually.
Figure 1 illustrates the amount of solid waste generated annually in the United States-
estimated at 13.2 billion tons per year.
In addition to generating solid waste, industry releases billions of pounds of toxic chem-
icals to the air and to deep underground injection wells each year. Some of these releases are
legally permitted releases, and some are not. The extent to which the unpermitted releases
cause a risk, if any, is not known. However, in all cases managing releases costs money.
Pollution
Figure 1 “Solid” wastes as defined under theResource Conservation andRecovery Act (RCRA).
(a) All RCRA wastes (billions of tons); (b) nonhazardous RCRA wastes (billions of tons). Much of the
solid waste produced in the United States is not directly generated by consumers. Municipal solid waste,
the focus of much public concern, represents less than 2% of all solid waste regulated under RCRA. In
contrast, industrial activities produce about700 million tons of hazardous waste (a) and about 11 billion
tons of nonhazardous wastes (b). Note: All numbers are estimates. The nonhazardous waste total has
been rounded to reflect uncertainty. Much of the “solid” waste defined under RCRA, perhaps as much
as 70%, consists of wastewater. The termshazardous and nonhazardous refer to statutory definitions of
Subtitles C and D of RCRA, respectively. The mining wastes shown in (b) exclude mineral processing
wastes; the oiYgas wastes in (b) exclude produced waters used for enhanced oil recovery; the “other”
category in (b) includes wastes from utility coal combustion. (Adapted from U.S. Congress, Office of
Technology Assessment, Managing Industrial Solid Wastes From Manufacturing, Mining, Oil and Gas
Production, andUtility Coal Combustion,OTA-BP-0-82, U.S. Govt. Printing Office, Washington, D.C.,
February 1992.)
A recent Chemical Manufactures Association survey indicates that about 20% ofnew
capital expenditures are now for pollution abatement and control [l]. Furthermore, as a re-
sult of the escalating costs associated with federal environmental regulations, a number of
petroleum refineries in the United States have closed. Increasingly, companiesare sacrificing
less profitable refineries in favor of those capable of absorbing the costs of complying with
environmental requirements. No new refineries have been built in the United States in the past
15 years [2].
By the mid-l980s, it had become clearto government and industry that the key to increas-
ingeconomiccompetitivenessandenvironmentalimprovementwaspollutionprevention.
There was compelling evidence that companies who were pioneers in pollution prevention were
saving money on waste management, generating less pollution, and improving their competi-
tive position as a result.
In 1984, Congress began a serious search for a preventive approach that would lessen the
costs of end-of-pipe management and reduce the amount of waste generated. In 1986, both EPA
[3] and the Congressional Office of Technology Assessment [4] published reports that explored
this issue. Both reports pointed to the need for government and industryto find new incentives
to reduce the amountof pollution generated and suggested specific approaches that should be
explored and implemented.
At thesametime,CongressbeganworkonCommunity Right-To-Know Legislation
(EPCRA), which helpedto spur citizen concern about chemical usein factories and chemical
releases to the environment. Citizens and public interest groups have become wiser in their
purchasing choicesand have greater accessto information on the effectsof toxic chemicals on
human health and the environment. Citizen groupsare placing increased pressure on industry
to reduce the useof toxic chemicals in consumer products and to recycle used productsto pre-
ventthemfromcausingharmandalsofromtakinguppreciouslandfillspace.Consumer
154 Lounsbury
sure has causedmajorcompaniestochangeproduct lines, use alternative packaging,and

design products composedof less toxic materials to meet public demand.
The combined effect of the government’s shift in priorities (from end-of-pipe pollution
control to up-front pollution prevention) and enhanced citizen awareness and involvement is
influencing the way the United States will conduct business in the future. The next sections
provide the reader with an overview of the types of programs that are under way.
B. PollutionPreventionPrograms
Pollution prevention is often discussed within the context of a widely accepted notion of a
“waste management hierarchy.” The waste management hierarchy places the highest priority
on reducing waste at the source of generation through the use of less toxic raw materials,
equipment changes, process redesign, and better housekeeping and materials management.
The second preference inthe hierarchy is reuse and recyclingof wastes that cannot be reduced
at the source. The third preference in the hierarchy is waste treatment, and the least preferred
alternative is disposal. It is important to note here that prior to the mid-l980s, federal envi-
ronmental legislation focused heavily on prescribing and regulating waste treatment and dis-
posal (the bottom of the hierarchy).
In the mid-l980s, in response to rising concern over the costs of environmental compli-
ance, some companies began seeking ways to reduce the amount of waste generated by man-
ufacturing operations withoutcompletelyabandoningandredesigningexistingproduction
processes. Many companies have implemented pollution prevention programs over the past10
years and have significantly reduced the costs of waste disposaland environmental compliance.
There are numerous successstories of firms with successful pollution prevention programs that
have found itcheaper and more publiclyacceptable to sell products undera pollution prevention
banner. The following are from Preventing Pollution in the Chemical Industry [5].
Amoco’s facility in Natchez, MS no longer uses xylene as process solvent. A team com-
posed of process engineers, researchers, andoperations personnel successfully founda way
to replace xylene with an aliphatic solvent. The resulting product quality met all analytical
specifications, the new process met all plant requirements, and the product exhibited im-
proved aesthetics and incorporated raw materials more efficiently, thus increasing product
yield. By making this change in the process, the plant realized direct solvent savings, de-
creased energy requirements, and decreased hazardous waste oil generation. The resultis
that the Natchez team has eliminated nearly 2 million pounds per year of toxic waste. The
team continues to work on its goal of reducing toxic emissions to 1% of the 1987 level by
1995. The next project will focus on eliminating ammonia wastes.
Dow Chemical Company’s chlorinated ethane products facility in Freeport, TX, pro-
duces raw materials usedin Saran Wrap plastic film, herbicides, and latex paints. The
waste reduction team realizedthat they could reduce the amount of product lost in a by-
productstream,aswell as improvethequality of theirby-producthydrochloric acid
stream. The team changed the production process to eliminate the use of excess ethylene,
which contaminated a hydrogen chloride stream during production.This reduction allowed
Dow to produce high quality hydrochloric acid. At this same facility, Dow improved the
separation of a by-product fromthe vinylidene chloride recovered during separation. These
waste reduction changes produceda high quality hydrochloric acid foruse at other facil-
ities. Ethylene and vinylidenechloride, which had been previously sent to a thermal oxi-
dizer as waste, are now recoverable products.
Many more companies are still in the early stages of identifying opportunities that will
reducewastegenerationandsavemoney or havenotyetbegun a program.Thefocus of
COST CATEGORIES
OTHER
0 LABOR
TRANSPORTATION
0 DISPOSAL
RAW MATERIAL
SIC20 81092 W 7 SKiP

STANDARD INDUSTRIAL CATEGORIES
510211 81050 - /
Figure 2 True Costs of Waste Generation and Management for 70 “typical” manufacturing plants in
the United States.
government efforts, described below, is to provide better incentives for firmsto begin pollution
prevention programs and to provide them with technical information and hands-on assistance
to get started.
Understanding how to reduce pollutant generation and save money is the key to building a
successful pollution prevention program in a company. Andthe first step to saving money is to
understand how to calculate the true costs of waste management. In many cases, companies
include only the costs of waste treatment, disposal, and transportation in their estimates of
waste management costs. The true costs of waste management, however, must also include the
value of materials contained in each waste stream generated (i.e., materials in waste streams
are raw materials that were not turned into product) and the labor, management, and energy
costs associated with the generation and management of “wastes.” The difference between
conventional calculationsof waste management (treatment, disposal, and transportation costs)
and the true costs of waste management can be dramatic. Figure 2 illustrates this difference.
Figure 2 shows that the true costs of waste management for70 “typical” manufacturing
facilities in the United States2are 85-95% greater than conventional cost estimates that focus
~~~ ~ ~
*In this analysis[6]. 10 “typical” plants weredrawn from eachof seven different Standard IndustrialCategories (SICS)
contained in the database of a private engineeringfirm that specializes in completing pollution prevention opportunity
assessments. The seven SICs included in the anlaysis were 20-food and kind& products; 22-textile mill products;
28“chemicals and allied products; 30-rubber and miscellaneous plastics products; 32“stone, clay, glass, and con-
crete products; ”fabricated metal products, except machinery and transportation equipment; and 37-transports-
tion equipment.
156 Lounsbury
only on the costs of treatment, disposal, and transportation. In conventional estimates, com-
panies do not consider the valueof the materials in the waste stream or other costs related to
managing wastes.
A look at the true cost of waste generation and management often compels companies to
complete an analysis of options for reducing these costs-a pollution prevention opportunity
assessment. A pollution prevention opportunity assessment consistsof
1. Identification of individual waste streams, their composition, and their origin in the pro-
duction process
2. Identification of theamountof raw materialpurchasedthatwaseventuallydiscarded
as waste
3. Estimating the value of the materials disposed of, using original purchase prices
4. Identification of allother costs associated with generating and managing each waste stream
5. Evaluation of options that would reduce the use and generation of the waste materials
After completing a pollution prevention opportunity assessment, many companies find

they have been using more materials than necessary, not managing inventory carefully, not
managing quality control carefully, using highly toxic raw materials when a safer substitute
could be used instead,or using and wasting costly materials “because we have always done it
that way.” In many cases companies find more efficient and cheaper ways to manufacture their
products and generate less waste with little or no investment of capital.
Figure 3 illustrates a true cost calculation for a typical waste stream.
To encourage more companies to pursue pollution prevention, EPA began building apol-
lution prevention program in 1987. At that time EPA focused its efforts on the prevention and
recycling of industrial solid hazardous waste.By 1988, EPA expanded its efforts to all agency
Treatment, storage, and disposal facility cost:

The plant generates 24,000 gal of waste coolantper year. Dis-
posal of the waste coolant at a treatment, storage, and disposal
facility costs $0.20/gal
24,000 gaYyr X $0.20/gal $4,800
Waste transportation cost:
The waste coolant costs $0.15 per gallon to transport to the
treatment, storage and disposal facility.
24,000 gaYyr x $0. Wgal $3,600
Wasted raw material cost:
The coolant becomes contaminated with oil and grease under
current operations and can no longer be used. The coolant was
purchased for $1 .00/gal.
24,000 gaYyr x $1.00/gal $24,000
Labor cost:
100 hours per year of plant labor time ($lO.OO/h&
100 hr X $lO.OO/hr $ 1.000
10 hours per year of management time ($20.00/hr).
10 hr x $20.00/hr $200
Other costs none
Future waste disposal liability costs unknown
Total coolant waste generation costs $33,600
Figure 3 Analysis of costs for waste stream 1: Waste coolants. (From Ref. 6.)
Pollution
programs and began working with states and industry to seek out new opportunities. EPA de-
veloped a publicly accessible computerized Pollution Prevention Information Clearinghouse
(free of charge to users) that contains hundredsof process-oriented examplesof pollution pre-
vention and recycling techniques. Information on contacting the clearinghouse is provided in
Section IV.
EPA developed a series ofuser guides to helpcompaniesbegintheirownpollution
prevention efforts. EPA's Facility Pollution Prevention Guide [7]is a field-tested handbook
for manufacturers that describes how to form internal teams, gather necessary process and
waste data, identifyin-plant opportunities, analyze costs andsavings,andset priorities
among projects.
In 1991, EPA initiated the 33/50 program-a program that encourages companiesto vol-
untarily commit to reducing pollutant generation 33% by the year 1992 and 50% by the year
1995. To date, over 600 companies have joined the program. This enthusiastic response indi-
cates that pollution prevention is an important opportunity to save money while gaining favor-
able public recognition by being good corporate citizens.
About 45 states have pollution prevention assistance programs in place. These state pro-
grams provide on-site technicalassistance, telephone information, and written guidebooks on
how to conduct an assessment of a plant's pollution preventionopportunities for many specific
waste streams. (These guidebooksare also listedin the Pollution Prevention InformationClear-
inghouse.) Many states provide an invaluable and uniqueservice to manycompanies that is free
and nomgulatory, saves money, and improves their public image.
The American Institute of Chemical Engineers and the American Institute for Pollution
Prevention have published an engineering workbookof ptactical pollution prevention problems
[8] that has been distributed to chemical engineering departments at universities throughout
the country.
The workbook provides problems in six areas:
Life cycle analysis (an analysis of a product life from conception through design, production,
use, and eventual disposal)
Identifying and setting priorities for managing pollutants from industrial sites
Selection of environmentally compatible materials
Design of unit operations for minimizing waste
Economics of pollution prevention
Process flowsheeting for minimizing waste
One of the problems is reprinted below.
Problem 153
ChemicalEngineeringTopics. Mass balances, engineering Economics
Pollution PreventionConcepts. Design of unit operations for minimizing waste, reducing
unit size to reduce waste.
Background. A facilitymanufacturessheetsofcompositematerialforuseinthe
aerospace andsporting goods industries.The composites are made by coating fiberglass or
Kevlar fabrics with the liquefied resin. As shown in Figure 4, the coating process takes
place in a pan containing the resin. The resin is dissolved in solvent, and a heat curing
process drives off excess solvent from the compositeto make the finished product. At the
end of each run, the resin pan must be emptied, rinsed, and cleaned. This results in a
'Allen et al. [S], p. 118.

Lounsbury
scrap prepreg
fiber
solvated resin waste

rinse solvent waste
Figure 4
hazardous waste (rinsate, leftover solvent, and resin), which is then either partially recy-
cled or incinerated.
Treater pans must be at least 10 in. wider than the product being coated to provide
clearance for machinery, but when the facility’s operating records were examined, it was
discovered that the pans were excessively wide. This results in unnecessary waste gener-
ation. Plant data for the percentageof production at each fabricheater pan width combi-
nation are given in the following table:
FabricwidthTreater pan widthPercent of

(in.) (in.) production
32 60 40
38 78 20
50 84 15
44 84 5
50 86 9
60 86 11
It is proposed that blocks molded to fit into the endsof the pans be used to ensure that
the effective treater pan width be exactly 10 in. wider than the fabric being coated. The
blocks would havea one-time costof $lo00 and would notrequire removalof the pans. An
Pollution
operator would only have to remove the last block and insert the block appropriate forthe
next run. Your task is to consider the economic viability of this option, given that in a
9-month period there are 1369 resin treater cleanouts. The panshave a wettedcross-
sectional area of 0.22 ft2, and the specific gravityof the resin is 1.1. The cost of the resin
in $1.64/lb; the cost of the incinerating resin waste is $0.14/lb.
Problem Statement. Neglect interest and calculate how long it would take for the
molded blocks to pay for themselves. Note that when the blocks are used, some inciner-
ation cost is avoided and less resin is thrown away. Ignore the volume of resin in the re-
circulation reservoir, and assumethat the amount of rinsing required is not changedby the
blocks. Also assume that all the waste is incinerated.
Solution to Problem 15
Average treater pan width (before reduction):
60 X 0.4 + 78 X 0.2 + 84" X 0.15 + 84" X 0.05 + 86" X 0.09
+ 86" X 0.11 = 73.6 in.
Minimum possible average treater pan width:
42" X 0.4 +
48" X 0.2 +
60" X 0.15 + 54" X 0.05 + 60" X 0.09
+ 70" X 0.11 = 51.2 in.
Cost of resin and incineration without the use of blocks:
m
9 mo (73.6 in.) (0.22
= $225,800/9 mo
ft2) (1.1) (-) (E)+ X $(1.64
Ib
0.14)
Cost of resin and incineration with the use of blocks:
9 mo (51.2 in.) (0.22 ft?) (1.1) (-)

m
= $157,000/9 mo
(E)+ X
$(1.64
lb
0.14)
Daily savings:
225,800 - 157,000 12 mo 1
( 9mo (
1 yr (365 gys) = $251/day
Payback period would be about 4 days.
(Note:The material for this problem resulted froma waste minimization audit sponsored by a
grant from the California Department of Health Services.)
EPA began developing a more focused approach to pollution prevention, known the as De-
sign for the Environment (DFE) program, in 1992. The program has several main facets that
focuson particular industries andprofessionalareas.Forexample,EPAhas initiated two
industry-specific projects:
1. The dry cleaning project exploresalternatives for dry cleaning processes. Industry groups
are active participants and are involved in comparative risk assessment, performance eval-
uations, and cost analysis of the various alternatives explored.
2. The printing project brings together several hundred printing companies in an effort to find
safer substitutes for the chemicals usedin the printing industry(e.g., inks, press washes).
The DFE programis also exploring design opportunities in crosscutting professional areas.
For example, an effort is under way to standardize "true cost" waste management accounting
I60 Lounsbury
for accountants in companies of all types. Another project looks at initiatives the insurance
industry could pursue to better factor pollution prevention opportunities into underwriters’
evaluations of corporate risks. Contacts for the DFE programare listed in Section IV.
C. Green Product Design
Several yearsafter the surge of pollution prevention programs,a growing numberof companies
have lookedto a more expanded viewof pollution prevention-“green product design.” These
companies are finding that “green” products-products that reduce the burden on the envi-
ronment during use and disposal-have additional marketing appeal to consumers. In contrast
to past practices, in which product performance and environmental compatibility were man-
aged at different points in the production process, manufacturing executives have targeted the
design stage of product development to satisfy both of these consumer demands.
A recent report published by the congressional Officeof Technology Assessment (OTA)[9]
explores the benefits of green designin depth andtargets the product design stage as the perfect
leveraging point for determining how to reduce environmental impact and compliance costs and
improve product quality and performance.
OTA cites a 1991 report by the National Research Council (NRC) that found that the qual-
ity of U.S.engineering design is generally poor. The report recommended that the federal gov-
ernment make engineering design a national priority to improve competitiveness. The NRC
concluded that the design stage determines 70% or more of the cost of product development,
manufacture, and use [IO].
The key elements of green design are simple to comprehend but challengingto implement
and consequentlyare the fundamental challenge to engineers of the future. OTA focuses on four
objectives of green design in its report [lo]:
Design for pollution prevention. Examples include reducing the use of toxic materials, in-
creasing energy efficiency, using less material to perform the samefunction, or designing
products so that they have a longer useful life.
Design for better materials management. Examples include making products that can be re-
manufactured, recycled, composted, or safely incinerated with energy recovery.
Design for remanufacturing and recycling. Recycling can reduce virgin material extraction
rates, wastes generated from raw material separation and processing, and energy use as-
sociated with manufacturing. It can also divert residual material from municipal waste,
relieving pressure on overburdened landfills.
Designfor cornposting and incineration. Designers canfacilitate composting by making prod-
ucts entirely out of biodegradable materials. For example, starch-based polymers (which
are inherently biodegradable)and easily composted and films can substitute for plastic in
a variety of applications.
Each of these design objectives represents an engineering challenge. Designing products
that meet all four elevates the challengeeven more. A look at the life cycle of products helps
explain the scope of green design.
Products affect the environment at many points in their life cycle (see Figure 5). It does not
take much imagination to see that engineering work is integral to each step of this process.
However, in the past, each step in the processwas often viewed independently from other steps
in the process. Engineers did not often communicate with each other along the way.Many
companies are now integrating the work of their product designers, raw materials suppliers,
purchasing department, manufacturing and maintenance operations, and public affairs depart-
ments and their customers to identify opportunities for improving product designs.
OTA found that design trade-offs are a major challenge.
“Stages of the Product Llfe Cycle
Materlalextraction Material processing Manutacturlng USe Waste management
t t t
R W 8 R8,llaflUfedWe Rem8
L I
Figure 5 Stages of the product life cycle. Environmental impacts occur all at stages of a product’s life
cycle. Design canbe employed to reduce these impacts by changing the amount and type of materials used
in the product, by creating more efficient manufacturing operations,by reducing the energy and materials
consumed during use, and by improving recovery of energy and materials during waste management.
(Adapted from D. Navin Chandra, The Robotics Institute, Carnegie Mellon University, personal com-
munication, March 1992.)
These choices often involve environmental dilemmas. Tradeoffs may be required, not
only between traditional design objectives and environmental objectives, but even among
environmental objectivesthemselves-for example, waste prevention versus recyclability.
As an illustration, consider the cross sectionof a modern snack chip bag [Figure 61.
The combination of extremely thin layersof several different materials produces a light-
weight package that meets a variety of needs (e.g., preserving freshness, indicting tam-
pering, and providing product information). The use of so many materials effectively
inhibits recycling. On the other hand, the package has waste prevention attributes: it is
much lighter than an equivalent package made of a single material and provides a longer
shelf life, resulting in less food waste. Even this relatively simple product demonstrates the
difficulties of measuring green design [lo, p. 81.
Some foreign competitors are making huge advances in green design. For example, OTA
points out in their report [lo, p. 121 that
several German auto companies, includingBMW and Volkswagen, have begun to explore
this system oriented approach. BMW recently built a pilot plant in Bavaria to study dis-
assembly and recyclingof recovered materials, andVolkswagen AG has constructed a sim-
ilar facility. The goal of the BMW facility is to learn to make an automobile out of 1 0 0
percent reusable/recyclable parts by the year 2000. In 1991, BMW introduced a two seat
roadster model with plastic body panels designed for disassembly and labeled as to resin
type so they may be collected for recycling. [See Figure 7.1
D. OtherFederal Efforts
Other federal agenciesare developing new approaches to green design and environmental pro-
tection. In 1992, the Federal Trade Commission issued guidelines
to help reduce consumer confusion and prevent the false or misleading use of environ-
mental terms such as “recyclable,” degradable,” and “environmentally friendly” in the
advertisingandlabeling of productsinthemarketplace. ...
Theguidelines are also
162 Lounsbury
Machinability
Copolymer Adhesion
Molsture barrier
Polypropylene Stillness
Clarhy
Puncture resistance
Copolymer Ink adheslon
Inks quallly Oraphlcs
Polyethylene lnteriamlnar adhesion

Barrier lo oxygen,
Alumlnum metallzatlon moisture. and l!ght
Copolymer Metal adhesion
Stiffness
Polypropylene Molsture barrier
Seal Integrlty
Copolymer Hot seal strength
Easy opening
Tamper evidence
Figure 6 The cross section of a snack chip bag illustrates the complexity of modern packaging. The
bag is approximately 0.002 in. thick and consists of nine different layers, each with a specific function.
While such complexity can inhibit recycling efforts, it also can reduce the overall weight of the bag and
keep food fresher, thus providing waste prevention benefits. (Source:Council on Plastics and Packaging
in the Environment.)
Figure 7 BMW roadster constructed of plastic body parts that can be dismantled and recycled.
ollution
intendedtoreducemanufacturers' uncertainty about which claimsmightlead to FTC

law-enforcement actions, thereby encouraging marketersto produce and promote products
that are less harmful to the environment. . . . The guides do not rigidly define environ-
mental terms. Instead, through specific guidance and a seriesof examples of both accept-
able and deceptive claims, the guides set out the different meanings thatbemight conveyed
by the useor omission of particular language describing environmental features. The types
of claims addressed by the guides include recyclable, degradable, compostable, recycled
content, source reduction, refillable, and ozone safe[l 13.
The guides are not themselves legally enforceable.

However, the laws theyare intended to sup-
port are.
Table 1 provides a brief summary of some of the key programs under way at the fed-
eral level.
W. WHERE TO GET INFORMATION ON TOXIC CHEMICALS,

POLLUTION PREVENTION,AND GREEN DESIGN
In designing any project, engineers need to knowwhich chemicals to be concerned about.
Thousands of chemicals are in use in the marketplace today. Hundreds of those chemicals are
regulated by the federal andstate governments. Although engineers need notbe expert on the
environmental impactsof materials used in engineering projects, they should be aware of the
chemical make-upand properties of materials in use and whether or not the chemicals used are
regulated or of some environmental concern.
Information on the human health and environmental effects of toxic chemicals is obtained
from animal studies, controlled epidemiological investigations of exposed populations, and
clinical studiesor case reports of exposed humans. Other information available on the adverse
effects of human exposure comes from experimental studies in systems other than whole ani-
mals (e.g., isolated organs, cells, subcellular components). EPA's Integrated Risk Information
System (IRIS), preparedand maintained by the U.S. EPA, is an electronic database containing
health risk and U.S. regulatory information on specific chemicals. IRIS contains descriptive
and numerical informationin several forms, including(1) chemical fileson long-term oral and
inhalation and noncarcinogenic health effects, (2) EPA regulatory action summaries, (3) sup-
plementary data on acute health hazardsand physicalkhemical properties, and (4) background
documents describing the rationales and methods used in arrivingat the results shown in the
chemical files.
Further information on IRIS canbe obtained by contacting
User Support
EPA Office of Environment Criteria and Assessment
Cincinnati, Ohio
Telephone: (5 13) 569-7254
A list of chemicals currently subject to regulation under the Community Right to Know
Act ispublished byEPA [12]. Chemicalsnotincludedonthislist may or maynot be
of concern.
Information concerning the amounts of toxic chemicals released to the environment on a
national, state, or facility-specific basis can be found in EPA's Toxic Release Inventory. In-
quiries can be made by contacting
164
Lounsbury
TRI Representative
Specialized Information Services
National Library of Medicine
8600 Rockville Pike
Bethesda, MD 20894
Telephone: (301) 496-6531
Information on pollution prevention, including
case studies, publications, training and ed-
ucational materials, programs, and legislation, and industry-specific fact sheets, can be ob-
tained by contacting
Pollution Prevention Information Clearinghouse
U.S. EPA
Pollution Prevention Division
401 M Street SW
Washington, D.C. 20460
Telephone: (202) 260-2602
Information on EPA's Design for the Environment Program canbe obtained by contacting
Office of Pollution Prevention and Toxics
U.S. EPA
401 M Street SW
Washington, D.C. 20406 Telephone: (202) 260-0981
or EPA's Pollution Prevention Information Clearinghouse (PPIC) (see address above).
Information on pollution prevention canalso be obtained by contacting state pollution pre-
vention programs. These contacts are listed below.
State Pollution Prevention Contacts

Alabama Hazardous Waste Division
HAMMARR PO.Box 8913
241 Mineral Ind. Bldg Little Rock, AR 72219-8913
University of Alabama (501) 570-2861
PO. Drawer G California
Tbscaloosa, AL 34587-9644 Toxic Substances Control Program
(205) 348-4878 Department of Health Services
Alaska Alternative Technology Division
Pollution Prevention Program PO.Box 942732
Department of Environmental Conservation Sacramento, CA 94234-7320
PO. Box 0 (916) 322-2822
Juneau, AK 99811-1800 Colorado
(907) 465-2671
Waste Minimization Assessment Center
Alaska Health Project Colorado State University
431 W. 7th, Suite 101 Mechanical Engineering Department
Anchorage, AK 99501 Fort Collins, CO 80523
(907) 276-2864 (303) 491-5317
Arkansas Pollution Prevention Office
Arkansas Department of Pollution Control Office of Health and Environmental
and Ecology Protection
166 Lounsbury
Colorado Department of Health Idaho

4210 E 11th Avenue, Room 350 Hazardous Materials Bureau
Denver, CO 80220 1410 N. Hilton Street
(303) 331-4510 Boise, ID 83706
Connecticut (208) 334-5879
Connecticut Hazardous Waste Management Illinois
Service Office of Pollution Prevention
900 Asylum Avenue, Suite 360 Illinois EPA
Hartford, CT 06105-1094 2200 Churchill Rd.
(203) 244-2007 Springfield, IL 62706
Delaware (2 17) 782-8700
Pollution Prevention Program Department Hazardous Waste Research and Information
of Natural Resources and Environmental Center
Control One East Hazelwood Drive
PO. Box 1401 Champaign, IL 61820
Dover,DE 19903 (217) 333-8940
(302) 739-3822
Indiana
Florida
Office of Pollution Prevention and Techni-
Hazardous Waste Reduction Assistance
cal Assistance
Program
Indiana Departmentof Environmental Man-
Department of Environmental Regulations
agement
h i n Towers Building
105 S . Meridian St.
2600 Blair Stone Rd.
PO. Box 6015
Tallahassee, FL 32399-2400
Indianapolis, IN 46206-6015
(904) 488-0300
(317) 232-8172
Georgia
Iowa
Hazardous Waste Management Program
Waste Management Authority Division
Land Protection Branch
Department of Natural Resources Waste
Environmental Protection Division
Management Authority Division
Georgia Department of Natural Resources
Wallace State Office Bldg.
Floyd Tower East, Suite 1154
Des Moines, IA 50319
205 Butler Street SE
(515) 281-8489
Atlanta, GA 30334
(404)656-2833 Iowa Waste Reduction Center
75 BRC
Hazardous Waste Technical Assistance
University of Northern Iowa
Program
Cedar Falls, IA 50614-0185
Evironmental Health and Safety Division
(319) 273-2079
Georgia Technical Research Institute
Atlanta, GA 30332 Kansas
(404) 894-3806 Department of Health and the Environment
Hawaii Forbes Field, Building 740
Solid and Hazardous Waste Branch Topeka, KS 66620
(913) 296-1603
Hawaii State Department of Health
5 Waterfront Plaza, Suite 250 Kentucky
500 Ala Moana Blvd. Kentucky Partners
Honolulu, HI 96813 Waste Reduction Center
(808) 543-8226 Ernst Hall, Room 312
University of Louisville Minnesota Technical Assistance Program

Louisville, KY 40292 Box 197, Mayo Bldg.
(502) 588-7260 420 Delaware St. SE
Louisiana University of Minnesota
Minneapolis, MN 55455
Alternative Technologies Research and De-
(612) 625-9471
velopment
Department of Environmental Quality Minnesota Office of Waste Management
PO. Box 44066 1350 Energy Lane
Baton Rouge, LA 70804 St. Paul, MN 55108
(504) 342-1254 (612) 649-5494
Maine Mississippi
Bureau of Oil and Hazardous Materials Mississippi Technical Assistance
Control Program
Department of Environmental Protection Mississippi State University
State House Station #l7 Department of Chemical Engineering
Augusta, ME 04333 PO. Drawer CN
(207) 289-2651 Mississippi State, MS 39762
(601) 325-8454
Maine Waste Management Agency
Office of Economic and Community Waste ReductionWaste Minimization
Development Program
State House Station #l30 Department of Environmental Quality
Augusta, ME 04333 PO.Box 10385
(207) 289-6800 Jackson, MS 39289-0385
Maryland (601) 961-5241
Hazardous Waste Program Missouri
Maryland Department of the Environment Environmental Improvement and Energy
2500 Broening Highway, Bldg. 40 Resource Authority
Baltimore, MD 21224 225 Madison Street
(301) 631-3343 PO.Box 744
Jefferson City, MO 65102
Technical Extension Service
(314) 751-4919
Engineering Research Center
University of Maryland Department of Natural Resources
College Park, MD 20742 Waste Management Program
(301) 454-1941 PO.Box176
Michigan Jefferson City, MO 65102
Office of Waste Reduction Service (314) 751-3176
Department of Commerce Montana
309 N. Washington St., Suite 103 Department of Health & Environmental
Lansing, MI 48909 Sciences
(517) 335-1178 Cogswell Bldg., Room B-102
Minnesota Helena, MT 59620
(406) 444-2821
Minnesota Pollution Control Agency
Hazardous Waste Division Nebraska
520 Lafayette Road Pollution Prevention Office
St. Paul, MN 55155 Department of Environmental Resources
(612) 643-3497 PO. Box 98922
168 Lounsbury
Lincoln, NE 68509-8922 Columbus, OH 43266-0149

(402) 471-4217 (614) 644-3492
Nevada Oklahoma
Small Business Development Center Pollution Prevention Technical Assistance
Room 41 1 PrOgraIIl
Department of Business Administration Oklahoma Departmentof Health
University of Nevada lo00 NE 10th Street
Reno, NV 89557 Oklahoma City, OK 73152
(702) 784-1717 (503) 229-5913
New Hampshire Oregon
Waste Management Division Hazardous Waste Reduction Program
Department of Environmental Services Department of Environmental Quality
' 6 Hazen Drive 811 SW 6th Ave.
Concord, NH 03301 Portland, OR 97204-1390
(603) 271 -290l (503) 229-5913
New Mexico Pennsylvania
Hazardous Waste and Remediation Center for Hazardous Materials Research
Bureau University of Pittsburgh Applied Research
1190 St. Francis Drive Center
Santa Fe, NM 87503 320 William Pitt Way
(505) 827-2926 Pittsburgh, PA 15238
New York Department of Environmental Resources
Bureau of Pollution Prevention PO. Box 2063
NYDEC Harrisburg, PA 17 105-2063
50 Wolf Road (717) 787-7382
Albany, NY 12233-7253 Rhode Island
(518) 457-7267 Hazardous Waste ReductionSection
North Carolina Office of Environmental Coordination
Office of Waste Reduction Department of Environmental
North Carolina Departmentof the Management
Environment, Health, and 83 Park Street
Natural Resources Providence, RI 02903
PO. Box 27687 (401) 277-3434
Raleigh, NC 27611 South Carolina
(919) 571-4100 Center for Waste Minimization
Ohio Department of Health and Environmental
Ohio Technology Transfer Organization Control
77 S. High Street, 26th Floor 2600 Bull Street
Columbus, OH 43215 Columbia, SC 29201
(614) 466-4286 (803) 734-4715
Pollution Prevention Section Hazardous Waste Management Research
Division of Solid and Hazardous Waste Fund
Management Institute of Public Affairs
Ohio EPA University of South Carolina
PO. Box 1049 Columbia, SC 29208
1800 Watermark Drive (803) 777-8157
South Dakota Agency of Natural Resources

Waste Management Program 103 S . Main Street
Department of Environment and Natural Waterbury, VT 05676
Resources (802) 244-8702
Division of Environmental Regulation Virginia
523 East Capitol Avenue Waste Minimization Program
Pierre, SD 57501-3153 Monroe Building, 1lth Floor
(605) 773-3153 101 N. 14th Street
Tennessee Richmond, VA 23219
Bureau of Environment (804) 37 1-87
16
Department of Health and Environment Washington
150 9th Ave. N Waste Reduction, Recycling, and Litter
Nashville, TN 37219-3657 Control Program
(615) 741-3657 Department of Ecology
TexaS Mail Stop PV-l1
Waste Minimization Unit University of Washington
Texas Water Commission Olympia, WA 98504-7541
PO. Box 13087, Capitol Station (206) 438-7541
Austin, TX 78711-3087 West Virginia
(512) 463-7761
Generator Assistance Program
Texas Hazardous Waste Research Waste Management Section
Center West Virginia Department of Natural
Lamar University Resources
PO. Box 10613 1356 Hansford Street
Beaumont, TX 77710 Charleston, WV 25301
(409)880-8768 (304) 348-6350
Center for Hazardous and Toxic Waste Wisconsin
Studies Bureau of Solid and Hazardous Waste
Texas Tech University Management
PO. Box 4679 Department of Natural Resources
Lubbock, TX 79409-3121 Box 7921 (TS/3)
(806) 724-1413 Madison, W1 53707-7921
Utah (608) 266-9259
Department of Environmental Quality Wyoming
288 North 1460 West Solid Waste Management Program
Salt Lake City, UT 84116 Department of Environmental Quality
(801) 538-6121 122 W. 25th Street
Vermont Herschler Building
Vermont Waste Minimization Program Cheyenne, WY 82002
Hazardous Waste Management Section (307) 777-7752
V. SUMMARY
The challenge for engineers of the future is to ask the right questions about what chemicals
are
How will productsbe used? Have we considered
in the products that industry designs and sells.
the safest possible materials for this use?How will products be reused or recycled after their
useful life? How will products eventually be disposed of?
I70 Lounsbury
REFERENCES
1. Mason, A. M., The New Environmental Age, ENR, Pittsfield, Mass., 1992.
2. U.S. Department of Energy, Petroleum Supply Annual 1990, DOE-EIA-0340 (90-91), p. 82.
3. U.S. EPA, Office of Solid Waste, Report to Congress: Minimization of Hazardous Waste, EPA/
530-SW-86-033,Washington,D.C.,1986.
4. Congress of the United States, Office of Technology Assessment, Serious Reduction of Hazardous
Waste, OTA-ITE-318, Washington, D.C., 1986.
5. Anon., Preventing Pollution in the Chemical Industry, Chemical Manufacturers Association, Wash-
ington, D.C., 1992.
6. EPA: Waste Generation Costs, Office of Solid Waste (Waste Advantage, Inc., contractor), Wash-
ington, D.C., 1991.
7. U.S. EPA, Office of Research and Development, Facility Pollution Prevention Guide, EPA/600/
R-92/088, Cincinnati, Ohio, 1992.
8. Allen, D. T., Bakshani,N.,Pollution Prevention: Homework and Design Problemfor Engineering
Curricula, Rosselot, K. S., and Department of Chemical Engineering. University of California. Los
Angeles, Calif., 1992.
9. U.S. Congress, Officeof Technology Assessment,Green Productsby Design: Choicesfor a Cleaner
Environment, OTA-E-541, U.S.Govt. Printing Office, Washington, D.C., October 1992.
IO. National Research Coouncil,Improving Engineering Design: Designing for Competitive Advantage,
National Academy Press, Washington, D.C., 1991.
11. Federal Trade Commission, Washington, D.C., F7C News, 1992.
12. U.S. EPA, Office of Pesticides and Toxic Substances, Title I11 List of Lists: Consolidated List of
Chemicals Subject to Reporting Under the Emergency Planning and Community Right to Know
500-B-92-002,1992;
13. U.S.. EPA, EPA PollutionPrevention1991:ProgressonReducingIndustrialPollutants, epa
21:3003, Washington, D C , 1991.
7
Biochemical, Genetic, and Ecological
Approaches to Solving Problems During
irt sitzt and Off-site Bioremediation
0.A. Ogunseitan
Universiry of California
Irvine, California
1. INTRODUCTION
The manipulation of biological organismsor their components for complete or partial purifi-
cation of contaminated ecosystems is an old technology the application of which has increased
tremendously due to elucidation made possibleby recent advances in molecular genetics, bio-
chemistry, and the ecologyof microorganisms. In orderto derive maximum environmental and
industrial ecological benefits from current remediation biotechnology, it is important to iden-
tify and solve specific problems that remain both for basic research forand
field practice. This
chapter presents realized and potential problems confronting current attempts to implement en-
vironmental bioremediation schemes, and research approaches to solve these problems. The
focus of the chapter is on problemsof molecular and organismic dimensions.
The biodegradation of many natural and anthropogenic chemicals present in the environ-
ment is inevitable dueto the versatility of microbial metabolic capabilities and the ubiquity of
microbial populations in the global ecosystem. It is mainly because of these two factors that
thebiogeochemicalcycling ofmany elementson earth continues. However, advancesin
chemistry-based and industrial engineering-based technologies in this century resulted in the
manufacture and wide distribution of several hazardous and recalcitrant chemical compounds.
The reliance of society on domestic waste purificationby microorganisms appeared to be mis-
placed when it came to dealing with the new wave of industrial chemicals. Because the pol-
luting chemicals accumulated in unchanged form, biomagnified, andremainedtoxicinthe
environment, specific limitations placed on natural chemical cycling processes canbe identi-
fied. First, it seemed that the rate of evolutionary processes responsible for the development
of new metabolic functions in microbial communities lagged behind the rate and sophistica-
tionwithwhichnovelchemicalcompoundswererecombinedfornewindustrialproducts.
Second, the rate of enzymatic functioning in situ (intracellular, or secreted into the contami-
nated milieu) is not rapid enough to catalyze the degradationof chemical compounds for which
a biochemical pathway already exists. Finally, these polluting compounds are extremely toxic
and therefore prevent microbial growth and significant catabolic activity.
171
172 Ogunseitan
Seminal research on the environmental fate of hazardous industrial chemicals concentrated

on gathering data on recalcitrance and half-lives in various ecological milieux [1,2] and on
ecotoxic effects [3,4]. Data on the capacity of soil bacteria to degrade polynuclear aromatic
hydrocarbons and several pesticides began to appear about 30 years ago [5,6]. Most of those
studies were conducted to demonstrate the occurrence of biodegradation in natural microbial
communities, partly by using sterilized controls and by elucidating the degradative mecha-
nisms in pure cultures of bacteria [7]. Approximately 20 years ago, biodegradation became
established as a promising mechanism through whichat least the concentration of recalcitrant
compounds in the environment may be lowered. Following that period, research activity fo-
cused on identifyingthe responsible enzymes and intermediate compoundsin the degradative
pathway of many polluting compounds [8,9]. Those studies used a combination of sophisti-
cated techniques, including chromatography and radiolabel tracing [10,1l]. Concurrent with
the period of intense biochemical analysisof degradative pathways was the availability of tools
for genetic analysisof degradative strains. Itwas recognized that several degradative pathways
were encoded on extrachromosomal genetic elements (plasmids), a fact that facilitated inten-
sive genetic analyses[12]. Restriction maps were produced, degradative operonswere cloned,
and the mechanisms linking gene expression, enzyme activity, and chemical degradation were
established [ 121. It became possibleto recruit degradative genes from various microorganisms
into single “broad-spectrum” degradative strains [13,14]. Genetically engineered strains are
now available for the degradation of compounds previously thought to be beyond microbial
degradative potential, but government regulation issues concerned with ecological fate and
long-term environmental safety prevent the application of genetically engineered organismsfor
hazardous waste bioremediation in the open environment [15]. With the extensive documen-
tation of biodegradative processes and the availability of powerful degradative strains, the stage
was set for application and commercialization of biodegradation technology. Initial attempts in
this direction met with limited successmainly because of inadequate understandingof ecolog-
ical interactions that control microbial catabolic processes [16]. In addition, genetically engi-
neered organisms could notbe used because only limiteddata were available on the ecological
fate of such organisms [16]. The last decade was then characterized by a flurry of research
projects dealing with the ecological aspects of biodegradation, including limiting concentra-
tions of pollutants [17], survival of degradative microbial populations[18], genetic interactions
in the degradative community and ecological fate assessment of natural and engineered deg-
radative organisms [19, 201, and the effects of physical-chemical environmental parameters on
biodegradation rates [21]. Most of these research projects were based on an agenda designedto
answer specific questions concerning the limits of biodegradation and policy formulation by
regulatory agencies [22].
The implementationof environmental bioremediation using microorganisms or their prod-
ucts in situ or off-site (in reactors or landfills) necessitates that problemsposed by three major
disciplines be surmounted. These disciplinesare biology, engineering and geology, and legis-
lation. This chapter deals with issues based only on the biological issues, namely, biochemical,
genetic, and ecological parameters. It is anticipated that provision of comprehensive solutions
to these problems will facilitate the tackling of engineering and biogeochemical problems as
well as lighting the path toward the solution of government regulatory problems. Environmen-
tal bioremediation now encompasses the treatment of contaminated soils, groundwater, river
and lake sediments, stabilization ponds, and seawater and proximal shoreline environments. In
most cases where proposals for bioremediation are being considered, cost, time, ease of im-
plementation, and compatibility with physicalor chemical remediation technologies are among
the factors to be considered.
Approaches to Problem Solving I73
II. BIOCHEMICAL LIMITATIONS AND SOLUTIONS

For practical purposes, there are ten major classes of chemicals that constitute environmental
problems amenable to biotechnical solutions. These ten classes are pesticides, halogenated al-
iphatic hydrocarbons, halogenated ethers, polychlorinated biphenyls, monocyclic aromatic hy-
drocarbons,phthalate esters, polycyclicaromatichydrocarbons,nitrosamines,metals,and
inorganic compounds suchas nitrates, phosphates, and sulfates (see Table 1). Several chemical
and mathematical modelsas well as empirical data have been generated to predict the biodeg-
radative fate of many chemicals in environmental systems. The functions of a well-integrated
bioremediation scheme include increasing the rates of biodegradation, containmentof pollutant
and degradative product mobility, and achievement of low residual levels.
In many situations, the site to be remediated contains a heterogeneous mixture of several
groups of chemicals. Before a decision is reached to implement bioremediationof a contami-
nated environment, it is important to conduct an initial biochemical feasibility study. Analysis
of the chemical componentsof the waste site or effluent can be conducted using oneor more
chromatographic techniques. The in situ biological componentsof the waste samplescan usu-
ally be analyzed by microscopic and plating techniques to determine whether the site or sam-
ples are sterile. More specific analysis ofmicrobial populations can be done by selective
cultivation on chemicals known to be present in the waste material.
It is during this period that potential biochemical impedimentsto successful bioremedia-
tion can be identified. Perhaps the most important biochemical impedimentof bioremediation
is representedby the species identityof the contaminating chemical inthe target environment.
There are an estimated 86,000 chemicals in international commerce [23], with an annual in-
crement in this number of about 1000 new chemicals [23]. Partial toxicological data exist for
only 2195 of these chemicals[23]. Various combinations of these chemicalsmay be present in
the 260 million metric tons of hazardous waste generated annuallyin the United States [24].
The problem is compounded by the fact that data on potentialand rates for environmental bio-
degradation of organic compounds exist for only about 350 chemicals (see Table 1).
Once the chemical components to be targeted for bioremediation are known, several fac-
tors concerningthe biochemical properties of the chemicalsmust be considered before thepo-
tential rate of bioremediation can beestimated.
1. Water solubility, which directly affects access to microbial enzymes or cellular uptake.
2. OctanoVwater partitioning coefficient (Kw), which affects chemical mobility andsorption
to soil particles, which may or may not enhance biodegradation depending on the parti-
tioning properties of degradative organisms.
3. Hydrolysis under varying conditions of pH, temperature, moisture levels, and ionic ex-
change capacity. (Initial physical-chemical hydrolysis of certain compounds may enhance
biodegradation by increasing the affinity of microbial enzymes.)
4. Potential for photolysis, which may act in concert with biodegradative enzymes for effi-
cient chemical degradation, for instance, in the case of halogenated polynuclear aromatic
hydrocarbons [23].
5. Potential for volatilization, which may determine the accessibility of chemicals to degra-
dative bacteria and suggest design plans for the bioremediation facility.
6. Toxicity, radioactivity, and reactivity of the chemicals, which may select for nonbiodeg-
radative microbial populations and therefore render the management of bioremediation fa-
cilities difficult.
Text resumes on page 188.

Table 1 Environmentally Important Chemicals of Anthropogenic Origin or Redistribution with Potential for Biological TreatmenP s
Maximum measured or estimated
aqueous biodegradation half-life
(hr) in unacclimated samples
Biodegradation Genetic
Chemical Aerobic Anaerobic pathway Enzymes determinants Organismsb
Acenaphthene 168 4320 Established Oxygenases Cloned
Acenaphthylene 1440 5760 Deducible Oxygenase Cloned
Acephate ND ND Deducible Demethylases Cloned
Acetamide 168 672 Established Oxidases Cloned
Acetone 168 672 Established Dehydrogenases Mapped
Acetonitrile 672 2688 Deducible ND ND
Acetophenone ND ND Deducible ND ND
2-Acety laminofluorene 4320 17280 Deducible Oxygenases Mapped
Acridine ND ND Deducible ND ND
Acrolein 672 2880 Deducible ND ND
Acrylic acid 168 4320 Established Dehydrogenases Mapped
Acrylonitrile 552 2208 Deducible ND ND
Aflatoxin B1 672 2688 Deducible Hydrolases Cloned
Alachlor ND ND Dechlorination Hydroxylation ND
Aldicarb 8664 15240 Established Demethylases Mapped
Aldrin 14200 168 Established Dehalogenases Cloned
Ally1 alcohol 168 672 Deducible ND Cloned
2-Aminoanthraquinone 672 2688 Hydrolases Oxygenases Cloned
CAminoazobenzene 672 2688 Deducible ND ND
Chinobiphenyl 168 672 Hydroxylase Oxygenases Cloned
1-Amino-2-methylanthraquinone 672 2688 Established Hydrolases Map@
Amitrole 4032 16128 Deducible ND ND
Aniline 312 672 Established Oxygenases Cloned 0
Do
o-Anisidine 4320 17280 Deducible ND ND E
p-Anisidine 672 2688 Deducible ND ND 1
2.
Anthracene 1lOQ0 44160 Established Oxygenases Cloned c.L
n
3
Approaches to Problem Solving 175
Table 1 Continued
Bromodichloromethane ND ND Established Monooxygenases Cloned B
Bromoethylene 4320 17280 Established Monooxygenases Cloned B
Bromoform 4320 17280 Deducible Monooxygenases Cloned B
CBromophenyl phenyl ether ND ND Deducible ND ND ND
Bromoxynil octanoate 528 21 12 Deducible Dehalogenases Map@ B
1,3-Butadiene 672 2688 Deducible Oxidases Cloned B
Bufencarb ND ND Deducible ND ND ND
1-Butan01 168 1296 Established Dehydrogenases Cloned B
Butralin ND ND Deducible ND ND ND
Butyl acrylate 168 672 Established Dehydrogenase Mapped B
Butyl benzene phthalate 168 4320 Deducible ND ND ND
Butyl4chlorodiphenyl oxide ND ND Deducible Oxidoreductase ND ND
Butyraldehyde 168 672 Established Dehydrogenase Cloned ‘ B
Cadmium ND Bioprecipitation Established Phosphatases Cloned B
Camphor 168 672 Established Oxygenases Cloned B
Captan 1440 5760 Established Dehalogenases Cloned B, F
Carbaryl 720 2880 Established Hydrolases Cloned F, B
Carbon tetrachloride 8640 672 Established Dehalogenases Cloned B
Catechol 168 672 Established Oxygenases Cloned B
Chloramben ND ND Deducible Dehalogenases Cloned B
Chlorbromuron ND ND Deducible Dehalogenases Cloned B
Chlordane 33264 168 Established Dehalogenases Cloned B
Chloroacetic acid 168 672 Established Dehydrogenase Cloned B
0
2-C hloroacetophenone 672 2688 Deducible ND ND ND 2
Chlorobenzene(s) 3600 14400 Established Oxidoreductases Cloned B F
Chlorobenzilate 840 2688 Deducible Hydrolases ND ND 2.
Chlorobenzoate 144 672 Established Oxygenases Cloned B, F 5
Tabfe 1 Continued
DDT 137000 2400 Established Dehydrodehalogenases Mapped B, F
Dalapon 1440 5760 Established Dehalogenases Mapped B
Decabromophenyl ether 8760 35040 Deducible ND ND ND
Diallate 2160 8640 Deducible Demethylases ND ND
Dialifor ND ND Deducible Thiolase ND F
4,4'-Diaminodiphenyl ether 4320 17280 Deducible Oxygenases ND ND
Diamidofos ND ND Deducible Amidases ND F
2,CDiaminotoluene 4320 17280 Established Hydroxylases Cloned B
Diazinon ND ND Deducible Thiolases ND F
Dibenz[a,h]anthracene 22560 90240 Deducible Oxygenases ND ND
Dibenzofuran 672 2688 Established Hydroxylases Map@ B, F
1,2,7,8-Dibenzopyrene 8664 34656 Deducible 0xygenases ND ND
Dibromochloromethane 4320 4320 Established Monooxygenases Cloned B
1,2-Dibromo-3-chloropropane 4320 17280 Deducible Monooxygenases ND ND
Dibutylnitrosamine 4320 17280 Deducible Deaminases Mapped B, F
Di-n-butyl phthalate 552 552 Established Oxygenases Cloned B
Dichlofenthion ND ND Deducible Thiolases Mapped F
1,2-Dichlorobenzene 4320 17280 Established Dehalogenases Cloned B
3,3-Dichlorobenzidine 4320 17280 Deducible Hydroxy lases ND B
4,4'-Dichlorobiphenyl 4320 17280 Established Dehalogenases Cloned B
Dichlorodifluoromethane(Freon- 12) 4032 16128 Deducible Monooxygenases Cloned B
I ,ZDichloroethane 4320 17280 Deducible Monooxygenases Cloned B
l,%Dichloroethylene 4320 17280 Established Monooxy genases Cloned B
Y
m
Table 1 Continued
~

2,4Dimethylphenol 168 672 Established Demethylases Mapped B
Dimethyl phthalate 168 672 Established Demethylases Mapped B
Dimethyl sulfate 672 2688 Established Sulfurylase Mapped B
Dimethyl terephthalate 672 2688 Deducible Oxygenases Cloned B
Dimethyl tetrachloroterephthalate 2208 8832 Deducible Dehalogenases Cloned B
Dimilin ND ND Deducible Amidases ND ND
1,3-Dinitrobenzene 4320 300 Deducible Oxygenases ND ND
4,6-Dinitro-o-cresol 504 170 Deducible Dehydrogenases Cloned B
2,CDinitrophenol 63 12 170 Deducible Dehydrogenase Cloned B
Dinitmtduene(s) 4320 300 Established Monooxygenases Cloned B
Dinoseb 2952 360 Deducible Dehydrogenases Cloned B
Di(n-octyl) phthalate 672 8760 Deducible Oxygenases Cloned B
1 ,CDioxane 4320 17280 Deducible ND ND ND
Diphenylamine 672 2688 Established Deaminases Cloned B
Diphenyloxide ND ND Established Oxygenases Cloned B
Disodium methanearsonate ND ND Deducible Dehydrogenases Cloned B
Disulfoton 504 2016 Deducible Demethylases M> ND
Diuron ND ND Deducible Urease, Oxygenases Mapped B, F
Dursban ND ND Deducible Thiolases Mapped F
Endothall ND ND Deducible Dehydrogenases Mapped B, F
Endrin ND ND Deducible Dehalogenases Cloned B
Ethion ND ND Deducible Thiolases Mapped F
Endosulfan 336 1344 Deducible Dehalogenases Cloned B 0
Epichlomhydrin 672 2688 Deducible ND ND ND 23
Ethanol 26 I04 Established Dehydrogenases Cloned B 51
2-Ethoxyethanol 672 2688 Deducible Dehydrogenase ND ND

3
Table 1 Continued
Hexachloronaphthalene 8760 35040 Deducible ND ND ND
Hexachlorophene 7872 31488 Deducible Dehalo(hydro)genases ND B, F
Hydrazine 168 672 Deducible Oxidases ND ND
Hydrazobenzene 8640 4320 Deducible Oxygenases Cloned B
Hydrocyanic acid 4032 16128 Deducible Oxidases Mapped B
Hydroquinone 168 672 Established Dehydrogenases Cloned B
Imidan ND ND Deducible Thiolases Mapped F
Indeno[l,2,3-~d]pyrene 17520 70080 Deducible Oxygenases ND ND
Ipanzine ND ND Deducible ND ND ND
Isobutyl alcohol 173 692 Established Dehydrogenases Cloned B, F
Isobutyraldehyde 168 672 Established Dehydrogenases Cloned B, F
Isocil ND ND Deducible ND ND ND
Isophrone 672 2688 Deducible Demethylases MaPM B
Isoprene 672 2688 Established Oxidoreductases Cloned B
Isopropalin 2520 360 Deducible ND ND ND
Isopropanol 168 672 Established Dehydrogenases Cloned B
4,4'-Isopropylidenediphenol 4320 17280 Deducible Dehydrogenases ND ND
Isosafrole 672 2688 Deducible ND ND ND
Kepone 17280 69 120 Unknown ND ND
Lasiocarpine 672 2688 Deducible Oxidoreductases ND B
Lead Bioprecipitation Established phosphates Cloned B
Leptophos ND ND Deducible Thiolase, dehalogenase Cloned
Linuron 4272 17088 Deducible Dehalogenses ND
Malathion 1236 4944 Established Thioiases Mapped
Mecoprop 240 4320 Established Dehydrogenases Cloned
C
.-
0
Table 1 Continued
z
Mirex ND ND Established Bioaccumulation ND A
Michler’s ketone 672 2688 Deducible Dehydrogenases ND B
Mitomycin C 672 2688 Deducible Mutagenldehydrogenases ND ND
Monolinuron ND ND Deducible Oxygenase, urease Map@ B, F
Monuron ND ND Deducible Oxygenase, urease Mapped B. F
Mustard gas 672 2688 Deducible Dehalogenase Cloned B
Naphthalene 480 6192 Established Dioxygenase Cloned B, F
1-Naphthol 168 672 Established dehydrogenase Cloned B, F
a Naphthylamine 4320 17280 Established Oxygenases Cloned B
Nickel Bioaccumulation Established Capsule-binding Mapped B
Nitral i n ND m Deducible Peroxidases Mapped F
Nitrapyrin ND ND Deducible Dehalogenase ND F, B
Nitrates Biomass uptake Denitrification Established Nitrate reductase Cloned B
Nitrilotriacetic acid 672 2688 Established Dehydrogenase Cloned B
5-Nitro-o-anisidine 672 240 Deducible Deaminase, oxygenase Mapped B
Nitrobenzene 4728 300 Deducible Oxygenases ND B
CNitrobiphenyl 672 240 Deducible Oxygenases Cloned B
Nitrogen mustard 4320 17280 Deducible Dehalogenases ND B
Nitroglycerin 168 672 Deducible Dehydrogenses ND ND
ZNitropbenol 672 672 Established Dehydrogenases Mapped B
2-Nitropropane 4320 17280 Established Monooxy genase Cloned B
N-Nitrosodiethanolamine 4320 17280 Deducible Dehydrogenases Mapped B
N-Nitrosodiethylamine 4320 17280 Deducible Monooxygenases Cloned B
N-Nitrosodirnet hylamine 4320 17280 Deducible Monooxygenases Cloned B
N-Nitrosodiphenylamine 816 3264 Deducible Dioxygenases Cloned B
N-Nitrosodipropy lamine 4320 17280 Deducible Monooxygenases Cloned B
N-Nitroso-N-ethylurea 4320 17280 Deducible Ureases Mapped B, F
a
a
186 Ogunseitan
Tetraethyllead 672 2688 Deducible ND ND ND
Thallium Biosorption Deducible ND ND A b
ND ND ND 8
Thiabendazole
Thioacetamide
4,4Thiodianiline
168
672
672
2688
Deducible
Deducible
Deducible
Oxygenases
Hydrolases
Oxygenases
ND
ND
ND
ND
ND
s
2-
Thiourea 168 672 Deducible Ureases ND ND 2
Tillam ND ND Established Ester hydrolases Mapped F s
'a
Toluene
Toluene-2,Wiisocyanate
528
672
5040
2688
Established Oxygenases Cloned B a
o-Toluidine 168 672
Deducible
Established
Oxygenases
Oxygenases
Cloned
Cloned
B
B
f
Toxaphene ND ND Deducible Dehalogenases ND ND 3
Triaziquone 672 2688 Deducible ND ND ND T
I ,2,4-Trichlorobenzene 4320 17280 Established Dehalogenases Cloned S'
B b
1,l ,I-Trichloroethane 6552 26208 Established Monooxygenases Cloned B
Trichlororethylene 8640 39672 Established Monooxygenases Cloned B
Trichlorofluoromethane 8640 34560 Deducible Monooxygenases Cloned B
Trichlorofon 1080 4320 Deducible Dehalogenases Cloned B
2,4,5-TrichlorophenoI 16560 43690 Established Dehalogenases Cloned B
2,4,5-Trichlorophenoxyaceticacid 480 4320 Established Oxygenases Cloned B
1,2,3-TrichIoropropane 8640 34560 Established Monooxygenases Cloned B
1,1,2-Trichloro- 1,2,2-trifluoroethane 8640 34560 Deducible ND ND ND
Triclopyr ND ND Deducible Dehalogenases ND ND
Trietazine ND ND Deducible Hydrolases ND ND
Trifluralin 1422 672 Established Dehydrogenase Mapped B, F
1,2,3-Trimthylbeneme 672 2688 Established Demethylases ND ND
2.4.6-Trinitrotoluene 4320 4320 Established Oxygenases Cloned B
Tris (2,3-dibromopropyl) phosphate 168 672 Deducible Dehalogenases ND ND
Uracil mustard 672 17280 Deducible Dehalogenases ND ND
Uranium Bioaccumulation Established Cytochrome oxidase Cloned B
Vinyl chloride 4320 17280 Established Monooxygenase Cloned BF, A
Warfarin 672 2688 Deducible Decarboxydases ND ND
Xylenes 672 8640 Established Dealkyl. oxygenase Cloned B
2,6-Xylidine 4320 17280 Deducible Oxygenases ND ND
Z i C Bioaccurnulation Established Exopolyrners Cloned B
~~ ~~
'Chemicals representing typical classes of toxic environmental pollutants (65 classes) are set in bddface type. Inorganic chemical pollutants are set in bo&ifbce i t d c s .
bB = bacteria; F = fungi; A = algae. ND = no data available.
zv
Source: Compiled from Refs. 12. 23, and 28-35.
188 Ogunseitan
Table 2 Biochemical Limitations and Potential Solutions in Environmental Bioremediation

Potential Limitations
HighlyheterogeneouschemicalSeparatechemicalsbyphysical or chemicalmeansbefore bib
species component remediation off-site.
Target individual chemicals for biodegradationor detoxification,
starting with the most biologically available.
Explosive,radioactive, or other-Dilutechemicalstobiologicallytolerablelevels.
wise
toxic
chemicals
Use
composting and solid-phase
systems
for
containment.
Use immobilized cell or cell-component slurry reactors.
Chemical
species
Biochemical
of enzyme
andcatalysis
modeling.
undocumented biodegradative Pilot biodegradation assessment studies utilizing sterile sample
pathways controls and chemical analysis to characterize degradative
products.
Insoluble chemicals Vary pH for solubility.
Physical fragmentationfor better distribution and accessibility to
microbial populations.
Increase moisture levels and consider using wetting agents.
Increase temperature.
Sorbed chemicals Desorbing agents, e.g., surfactants.
Chemicalsimpermeable to
cells
Immobilized
enzyme reactors.
using intracellular enzymes,or
limiting membrane transport
Solutions to some of thesebiochemicalimpedimentsto successful implementation of

bioremediation are presented in Table 2. Several problems that arise from the biogeochemical
properties of the polluted ecosystem targeted for bioremediation can be solved by integrating
other physical and chemical remediation technologies with biological treatment. In some cases,
solutions may include deciding betweenin situ or off-site bioremediation, betweenthe use of
naturally occurring organisms and exogenous strains, and between treatment with living cells
and treatment withcellular components such as free enzymes, membranes, or heat-killed cells.
The implementation of some of these solutions requires considerably more research, for ex-
ample, in the use of immobilized enzymes for treatment of heterogeneous wastes.
111. GENETICLIMITATIONS AND SOLUTIONS

Most microorganismshave short generation timesand reach high populationdensities in small
spaces. Therefore the rate of evolution of new traits is rapid relative to that of multicellular
organisms. Bacteria especiallyare metabolically versatile andcan catabolize or resist the toxic
effects of a wide variety of environmental chemical contaminants. Within the past three de-
cades, the tools became available for detailed analysis of the genetic basis of the metabolic
versatility of bacteria. This resulted in the cloning of a wide variety of enzymatic capabilities
in various groups of bacteria and some fungi (see Table 1).
As the genetic clones became available, fragmentsof DNA able to identify (through hy-
bridizations) specific groups of degradative bacteria were generated [25,26]. As part of the
initial assessment study usually conducted prior to full implementation of bioremediation, a
gene probe analysis is recommended, in addition to phenotypic assays for specific biodegra-
dation reactions. l)q)ically, samples from the contaminated ecosystemare serially diluted and
plated on selective media to determine the populationdensities of total heterotrophicand bio-
Solving
Approaches to Problem 189
degradative bacterial populations.A gene probe analysis (usually colony hybridizationto a ra-
diolabeled DNA fragment from the biodegradative operon) is then performed on the isolated
colonies. The proportion of total bacteria that exhibitthe degradative phenotypeis then com-
pared to the proportion of bacteria containing the characterized biodegradative genes. ' b o
types of important information can be obtained from such genetic potential assessment study.
First, a correlation between the proportion of bacteria exhibiting chemical degradation and the
proportion of bacteria containing the gene(s) of interest indicates an already selected popula-
tion of degraders, and this will simplify attempts to maintain the biodegradative population and
enhance degradative activityby nutritional or inducive stimulation. On the other hand, if there
is a wide discrepancy betweenthe phenotypic assessment data and the proportion of bacteria
containing the specific genes, it may be that there is considerable diversityin the biodegrada-
tive population or that the biodegradation is mediated by a consortium of organisms and co-
metabolic activities encoded by heterologous genetic operons. In the latter case, a detailed
laboratory investigation of the ecological interactions between the biodegradative organisms
will be helpful in designing a strategy for maintaining the composition and efficiency of the
biodegradative consortium.
In cases where microorganisms showing phenotypic biodegradative activity cannot be iso-
lated and the gene probe analysis indicates that there is significant genetic potential, then two
conclusions may be reached. Oneis that the biodegradative genes are present in the population
but the genes are not being expressed intoa catabolic phenotype. Sucha lack of gene expression
may be due to lack of induction by necessary catabolite chemicals (e.g., salicylate and naph-
thalene for naphthalene degradation). Inductionof gene expression may therefore be activated
by the addition of intermediate chemicalsof the degradative pathway thathave been shown to
be capable of genetic induction[27]. Alternatively, chemical or physical means may be usedto
make the parent substrate more biologically available to induce enzyme production.
Finally, there may also be cases where neither genotypic nor phenotypic biodegradative
activities can be demonstrated. This may occur where the polluting chemical is too toxic to
microorganisms, not availablefor biological metabolism, or simply too exotic for biodegrada-
tion. It is in such instances that bioaugmentation,or seeding with exogenousbacteria, becomes
necessary. There are currently many strains of bacteria registered for their biodegradative or
detoxifying capabilityin commerce. Thesestrains of microorganisms usually must be grown to
high cell densities in the laboratory and released intothe contaminated environment toinitiate
bioremediation. Qpically, the process hasto be repeated frequently, with intermittent addition
of nutrients to help maintain the cell density, because thereare several ecological factors that
may limit the population of exogenous species in stressed environments. In additionto seeding
with naturally occurring biodegradative bacteria isolated from a different habitat, the use of
genetically engineered organisms may be the final choice in bioremediation. The use of ge-
netically engineered organisms requires several preliminary investigations of ecological and
public health safety but remains a viable environmental remediation strategy. In cases where
contained bioreactors canbe installed (e.g., in groundwater pump-and-treat processes), immo-
bilized genetically engineered organismsmay be used. Limitations thatmay arise from genetic
insufficiency and potential solutions to these limitations are summarized in Table 3.
W. ECOLOGICALLIMITATIONS AND SOLUTIONS

The technology of environmental bioremediation depends on ecological investigations of bac-
terial metabolic diversity. However, research on ecological approachesto solving problems that
may arise during in situ bioremediation has focused on ecological risk assessment of the en-
190 Ogunseitun
Table 3 Genetic Limitations and Potential Solutions in Environmental Bioremediation

Potential Limitations
~ ~~ ~ ~~~ ~~~ ~ ~ ~ ~~ ~~
Heterogeneous chemicals requiring Molecular breeding of versatile microorganisms using sample

diverse degradative operons of contaminated materials.
Direct cloning for recruitment of operons in single strain.
Biodegradative bacteria and genes Seeding with genetically characterized biodegradative bacteria.
absent from contaminated site Off-site bioremediation with genetically engineered bacteria.
Biodegradative genes present Add chemical inducers of genetic operons.
but rate of bioremediation slow Chemically or biologically remove biodegradation intermedi-
because genes are not expressed ates possibly involved in feedback inhibition.
at optimal
vironmental release of genetically engineered organisms. In the process of assessing risk, im-
portant aspects of microorganism dispersal, mechanisms of gene transfer, and organism sur-
vival in natural environments were investigated [19,20].
Problems of ecological significance thatmay arise during bioremediation andthe potential
solutions to these problemsare listed in Table4. On an ecosystem scale, serious contamination
problems result because of chemical mobility inthe environment. Contaminant migration in the
natural ecosystem may occur by transport into groundwater, seepage into coastal regions, and
partitioning into river, lake, or ocean sediments. Although these problems are tightly linked to
biochemical properties of the contaminating chemicals, they are also attributable to physical-
chemical characteristics of the ecosystem surroundingthe source of polluting chemicals. The
repercussions of such chemical mobilitymay bring about extensive ecological damage and ren-
der the implementation of bioremediation difficult. In cases where chemicals are suspected to
be mobile in receptive ecosystems, the immediate solution would rely on engineering imper-
meable barriers.
In both in situ and off-site bioremediation, ecological impedimentsmay arise concerning
the organisms involved in the environmental bioremediation. There are three classes of eco-
logical impediments to be dealt with: (1) the initial population density of biodegradative or-
ganisms and applicable genotypes, (2) the nutritional and aeration status of the contaminated
environment, and (3) the stability of naturally occurring or seeded populationsof biodegrada-
Table 4 Ecological Limitations and Potential Solutions to Environmental Bioremediation

ns Potential Limitations
~ ~~~ ~ ~ ~
Highly mobile chemicals in the Install physical barriers prior to deliberate bioremediation activity.
environment rates
Degradative bacteria absent or Bioaugmentation (seed with laboratory-grown degradative bacte-
present at too low popula- ria). Degradative bacteria can be isolated preferably from the
tion densities contaminated site for reintroduction in high cell densities.
Off-site bioremediation using genetically engineered organisms.
Degrader population low Biostimulate with nutrients.
Minimal aerobic zones limiting Add hydrogen peroxide or other electron acceptors.
bioremediation
Predation of degradative bacte- Monitor and replenish degradative population frequently.
rial population by protozoa
or phages
tive organisms. It is important to monitor these three factors before and during the implemen-
tation of bioremediation. Population densities of microorganisms are usually monitored by
plating and microsocopic techniques, while oxygen levels are determined by electrochemi-
calprobes and adjusted with hydrogen peroxide additions provided the biodegradationor bio-
transformation process is carried outby aerobic organisms. The levels of nutrients are usually
monitored by analyzing the concentrationsof nitrogen sources (ammoniaor nitrates) and phos-
phates using colorimetric of chromatographic techniques. Nutrient levelsmay be adjusted by
adding commercially available nutrient preparations to reach an optimum balance between the
components. Biodegradative populations can also be depleted through predation by larger mi-
croorganisms or viruses. Predation canbe better controlledin contained reactors during off-site
bioremediation. Where specific degradative strains are employed, virus-resistant varieties can
be selected and used.However, in most cases, a constant supply of degradative organisms may
have to be added to maintain the population density at levels not affected by predation.
1 . Alexander, M., Biodegradation: problems of molecular recalcitrance and microbial fallibility,Adv.

Appl. Microbiol., 7, 35-80 (1965).
2. Alexander, M.,Biotechnological report: non-biodegradable and other recalcitrant molecules,Bio-
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3. Autian, J., Structure-toxicityrelationship of acrylicmonomers, Environ.Health Perspect., 11,
141-152 (1975).
4. Ogunseitan, 0. A., and Odeyemi, O., Effects of lindane, captan, and malathion on nitrification,
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trichloro-1,l-bis@-chlorophenyl) ethane (DDT), J . Agric. Food Chem.. 25, 327-329 (1977).
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8
Commandments of Waste Management
Donald K. Walter
U.S. Department of Energy
Washington,D.C.
1. INTRODUCTION
Waste: v. to use, consume, or expend carelessly or thoughtlessly without need;n. a worth-
less or useless byproduct. (Webster’s, 1984)
Wastesfrommanufacturing,agriculture,mining, oil and gas production,andmunicipal
sources (residential, commercial, and institutional) must be managed. The preferred manage-
ment technique, all other things being equal, is source reduction; however, wastes are inevitable
in any activity.A waste management system is usedto collect, transport, and manage the dis-
posal of waste. The management system may include any combination of disposal on land, in
air, or in water, or utilization as fuel or material. In each case the economic, environmental,
and energy issues mustbe considered in a life cycle analysis. Today, most people believe that
the common method of waste managementbyis discard to the environment, usuallyto a land-
fill, although incineration (discardto the air) and discardto water are also practiced.Yet, his-
torically humans have used wastes for productive purposes. Cities are, in part, constructed
from older structures. Even today estimates are 50% that of the primary metal used annually in
the United States is produced from scrap and wastes.A limited database of information exists
for evaluating the relative merits of these options, particularly as they relate to industrial
wastes. The largest body of knowledge is for municipal solid waste (MSW).
There are significant environmental advantages to the productive use of wastes. Using
wastes productively reduces their discardto the environment and displaces other fuels or raw
materials with their associated concerns. Despite such environmental advantages, permitting
is often delayed or projects rejected because of misperception, the lack of comparative fuel
cycle based data, the need for improved technology, and high first cost versus excellent life
cycle cost.
The consequences of any decision relating to economics,environmentalconcerns, or
energysystemsmustconsider the fullbreadth of theimpactsincludingmining,refining,
193
194 Walter
7.8
Leaend
1.4
Figure 1 Waste disposal in the United States (in billions of tons).
collecting, transporting, utilizing, and, ultimately, waste disposal.For example, the conversion
of MSW into energy reducesthe amount of waste goingto landfills by W%,reduces landfill gas
emissions identified as greenhouse gasesby a factor of 15, reduces the need for other conven-
tional energy sources and their associated emissions, and provides an indigenous energy source
while producing air emissions (at lower than the rates for criteria pollutants for some displaced
alternatives) and benign ashfor disposal. Recycling reduces the amount of waste going to land-
fills, eliminates landfill gas emissions associated with biodegradablematerials, and may con-
serve conventional energy sources and their associated emissions but produces air emissions
from added transportation and manufacturing.
11. THE RESOURCE

There are a variety of sources of information on waste generatedin the United States although
they are generally inadequatefor estimating potential for reducing or using the waste resource.
Basedonan analysis of available data from a variety of documents, Americans generate
roughly 14.7 billion tonsof solid wastes per year. By far the greatest portion of these wastes are
classified as nonhazardous manufacturing wastes, accounting for just under 60% of the total
waste stream by weight. Hazardous waste, which is the focus of most data collection efforts,
represents roughly 6% of the total. The balance of industrial wastes are agricultural, oil and
gas, and mining wastes.
Figure 1 presents the estimated amount of each waste stream and its contribution to the
total. The total of 14.7 billion tons representsa reasonable conjectureof the total industrial and
municipal wastes generatedin the United States, but it is by no means a precise figure because
of a number of imperfections in the data collection and analysis.
A. IndustrialWastes
There are two impediments to calculating the total industrial solid waste stream.
First, waste is
not easily defined. A waste at one firm may be a raw material at another. Federal and state
governments have adopted regulations that specifycertain materials (generally those that are
classified as toxic or hazardous) as wastesor pollutants even though they have utility and are
reused. The principal regulation for solid wastes,
the Resource Conservation and Recovery Act
(RCRA), defines solid wasteas solid, semisolid, liquid, or gaseous with a few exceptions such
as municipal sewage sludges. In addition, RCRA splits wastes into hazardous and nonhazard-
ous categories. While perhaps adequate for regulating wastes, these definitions may omit or
Commandments
Management of Waste 195
exclude large groups of wastes (such as agricultural and “nonhazardous” wastes). They also
lack consistency, as substances are often added to or subtracted from these lists. Still, these
definitions are commonly used by the trade associations and government agencies that collect
data. Their surveys usually concentrate on waste materials that are deemed hazardous or are
suspected of being so.
A second obstacle is that the collection of waste data is not centralized or comprehensive.
To calculate the total amount of waste, several data sources must be consulted. One reason for
this is that the Environmental Protection Agency (EPA), whoseefforts to collect waste data are
the most comprehensive in the United States, collects information on waste generation and
disposal along program lines established by legislative edict. The Office of Air and Radiation,
Office of Water, Office of Solid Waste, and Office of Toxic Substances individually and in-
dependently track the wastes governed by their programs, as follows:
Air emissions governed under the Clean AirAct are tracked in the Officeof Air and Radiation.
Water discharges regulatedby the Clean Water Act are recorded by the Office of Water.
Information on the solid wastes governedby RCRA can be found in the Officeof Solid Waste.
Data on toxic chemical releases reported under
the Emergency Planning and Community Right-
to-Know Act are collected in the Office of Toxic Substances.
These officesdo not normallycoordinate their data collection and analysisefforts, though data
on some materialsare collected by more than one office.The data on RCRA hazardous wastes
may be gathered on a wet weight basis, so a significant amount of water is included in those
totals. The waste generation information collectedby other officesis on a dry weight basis, so
comparison and coordinationof the data are difficult.
An effort to determine the amount of waste generated in the United States must begin by
selecting the wastes to include. The working definition of industrial waste can be confined
primarily to solid wastes regulated under RCRA. The contributions of other wastes are less
significant ona weight basis. For example, wastes emitted to air thetotal about 20 million tons,
not including the normal constituents suchas carbon dioxide, oxygen, and nitrogen, less than
0.2% of the total estimated waste stream. Although discharges to water are significant in terms
of volume and weight, the actual amount of waste is a very small fraction of the total; the
discharges are essentially water with relatively minor amounts of contaminants. In addition,
most, if not all, of the toxic substances for which disposal data are recorded by the Office of
Toxic Substances are also regulated under RCRA and total about 6 million tons. Therefore,
wastes found in air and water and toxic wastes were not included in calculating the annual gen-
eration of industrial waste.
In addition, there are other factors that inhibit the calculation of the industrial waste
stream. The following information is important to understanding how the 14.7 billion ton es-
timate was derived.
In a 1988 report to Congress on solid waste disposalin the United States [l], EPA reports an
estimated annual generationrate of 7.8 billion tons ofindustrial nonhazardous waste. In its
analysis, EPA includes wastes generated by utilities, namely electric power generating and
water treatment facilities.
The amount of oil and gas wastes generatedin the United States is reported in another report
to Congress [2]. This document reports estimates made by EPA and by the American Pe-
troleum Institute. EPA’s estimates of the amount of drilling waste generated in the explo-
ration, development, andproductionof crudeoilandnatural gas werechosenfor
inclusion. The amountof water generatedin these activities is also reported, but was omit-
ted fromthe calculation as it is predominantly water witha high saline content andis often
1% Walter
Legend
0 Rubber and Leather

Textiles
wood
~00dwa~te
Yard Waste
Glass
Metals
Miscellaneous
Figure 2 Municipal solid wastecomponents.
discharged to surface waters, used for agriculhral purposes, or consumed in the produc-
tion process.
Each of the surveys fromwhich data were taken was conducted once, so the estimates recorded
in Figure 1 are snapshots of the waste generationin a single year. A complicating factoris
that the data refer to practices in different years. In addition, much of the data are now
close to 10 years old.
The total 1.4 billion tons of mining wastes excludes coal mining wastes, which were not in-
cluded in Ref. 3.
In Ref. 1 , EPA reports that 2 billion tons of feedlot wastes are generated annually. The amount
of these wastes that were used as fertilizer on fields in unknown. No estimate of crop res-
idues is included.
The 750 million tons of hazardous waste reported in Ref. 4 includes wastes regulated under
RCRA as well as wastes regulated under the Clean Water Act. Much of this waste is mixed
with water; however, the relative percentages of wastes and water are unknown.
The 196.7 million tons of residential, commercial, and institutional waste reported in Ref. 5
represents 1990 data.
Some of these limitations are a result of the data collection methods used. EPA's goal is to
protect human health and the environment; data on the characteristics and amountof waste are
collected in its efforts to determine risk. Thus, waste generationdata are largely a by-product
of EPA's attempts to meet its goals. EPA's methods and priorities limit the breadth of the data
and its usefulness for quantifying the amount of waste generated in the United States.
B. Municipal Solid Wastes

EPA has funded studies of MSW generation for at least 20 years. In 1960, each person in the
United States produced approximately2.7 lb of trash per day. Today, this numberhas increased
to approximately4.2 lb per person per day fromresidences, commercial businesses,and public
institutions such as schools and hospitals. Reportsare that the average Japanesediscards 2.5 lb
per day and the average Norwegian l .7 lb per day, although it is not clear that these data have
the same basis as for the United States. There is evidence, particularly from Europe in the
1970s, that MSW generation changes with the change in Gross Domestic Product (GDP).
These estimates are based on industry output of consumer goods multiplied by an estimated
Commandments
discard rate for each commodity. The estimated production from these sectors was just under
200 million tons per year in 1991.
As noted, industry produces large quantities of waste eachyear. The majority of this waste
istreatedanddiscarded in landfills,generallyonindustrialproperty,althoughsignificant
amounts are reused in industrial processesand are not recognized as waste. A fraction of in-
dustrial waste is discarded in the same sanitary landfills that receive residential, commercial,
and public waste. There has been no estimate of the quantity of this industrial waste since
EPA's 1973 first reportto Congress which indicated that a total of80 million tons per year of
industrial waste was discarded. There have been significant changes in the industrial sector
since that report, suchas the diversionof hazardous and toxic wastes from industry to control
technology and special landfills. The industrial waste that is discarded in municipal landfills is
estimated at 70 million tons per year.
Not all of the 200 million tonsof residential, commercial,and institutional waste discarded
is recoverable for productive use. From existing data, currently50 tons per day (TPD) is the
smallest facility size that is considered economic. Some smaller facilities(as small as 6 TPD)
have been built and operated successfully in special circumstances such as in prisons and
other government installations. A 50-TPD plant serves a population of 25,about
000.The avail-
able population 'data of the Bureau of the Census report standard municipal statistical areas
(SMSAs) with populations of 50,000 or more. The latest available census data are for 1990,
when about75% of the U.S. population lived within SMSAs. Given the steady increase pop- in
ulation in SMSA from 1950 (56.1%)to 1980 (74.6%), the 1990 SMSAdata should show that
about 80% of the population lives in SMSAs.
Municipal solid waste is very heterogeneous and varies in composition from day to day,
season to season, and location to location. Further, the quantity produced varies throughout
the year, with most produced in the summer. Figure 2 shows typical constituents found in the
waste stream.
C. Thou Shalt Have the Waste at Thy Disposal

The first of the commandments of waste management seems to be unnecessary after the dis-
cussion of the very large quantities of waste that exist in the United States. However, those
wastes can be dispersed and not available in the quantities required to construct an economic
project. The U.S. Department of Energy planned and was about to enter into an agreementto
test a technology in an industrial plant. The project was canceled when the industry determined
that it had less than half of the waste required.
In another case, a municipality planned and constructed a waste-to-energy plant that was
sized at 1000 TPD. Only after operation began did the city discover that it had only about 400
V D . Therefore the plant cost2.5 times as much to operate as the city had expected. The city
implemented a number of measures to increase the amount of waste available. Several unde-
sirable events occurredas a direct result, including lawsuits, fatal accidents, unexpected costs,
and poor technical performance.
D. Thou Shalt Not Covet Thy Neighbor's Waste

me second of the commandments seems as unnecessary as the first, yet every material be-
lieved to be worthless acquires valueas soon as the owner believes that someone else desires
it. Basically this commandment states that, all other issues being equal, the productive use of
the available waste should not be delayed while attempting to negotiate an arrangement for
added resources.
198 Walter
111. ECONOMICS
The increasing volume of waste, declining capacity of disposal systems, and increased regu-
lation and cost have contributedto significant increasesin the cost of waste disposal. Various
reports, including those published in Waste Age by the National Solid Waste Manufacturers
Association, indicate that disposal costs have increased dramatically from about $lO/ton in
1978 to over $150/ton today in some parts of the country.
A. IndustrialWaste
Little is published on the cost of the disposal of industrial wastes. The cost of toxic and haz-
ardous waste disposal isknown to be high and increasing. In addition, the personal liability of
owners and managers of firms is increasing. Each proposed new environmental law imposes
even more stringent requirements. As a result, capital expenditures and operating costs for in-
dustry have increased dramatically. One estimate is that every inch of paper added to regula-
tions has increased industrial expenditures for environmental control by $10 million per year
[7]. In general, industry does not assess the costs of environmental control but rather installs
whatever end-of-the-pipe control is specified as the best available control technology by reg-
ulation. This limits their liability and negative press. A few companies search for more eco-
nomic waste reduction technologies or new waste utilization systems. For example, when faced
with the need to reduce emissions of volatile organic carbons (VOCs), 3M entered into an
agreement with the US. Department of Energy (DOE) to develop a Brayton cycle heat pump
system that condenses the solvent from the waste. The VOC then is reused in the process.
While incinerationof the VOC and recovery cost the same today, anticipated future regulations
will make recovery the more economic solution.
B. MunicipalSolid Waste
A municipal solid waste disposal management system may include anycombination of sanitary
landfill, energy production, and recycling. Historically the collection and transportation of
MSW accounts for 75%of the total cost of the waste management system. Landfill' costs are
increasing dramatically as more stringent standards are imposed. Further, the costof transpor-
tation of waste is increasing dramatically as large cities run out of landfill space and the will
to site new landfills and, as a result, resort to long haul for disposal. The actual cost of, and
accounting for, any element of the management system varies widely. Some jurisdictions in-
clude the chargesin the general tax baseand indicate zero costfor waste management. Others
operate as a utility and include all charges in their costs. Most operate with a combination of
the two systems. Collection seems to cost in the vicinity of $100 per ton.
EMW disposal facilities charge a tipping fee that is designed to cover the costs of the dis-
posal system. As for collection, the accounting methods vary. Frequently, the cost of capital
amortization and formation, postclosure expenses,and similar costsare not included in landfill
fees. Typically, all of the costs of a waste-to-energy plant are included in the budget. Unlike
most municipal capital improvements, energy-from-waste facilitiesare typically financed from
tax exempt revenue bonds that cover all the costs related to the project. The tipping fee in the
'In 1976. when RCRA amended the Solid Waste Act, an estimated 30,000 landfills were in operation. By 1988, that
number had been reduced to 6034, with EPA projecting that 2000 of these would be closed within 5 years. In fact,
that has not occurred, and the capacity of landfills has remained relatively constant. While fewer new landfills have
opened than old ones have closed, the new ones tend to be large high-capacity regional unitswhile those closing tend
to be small.
Commandments
plant, energy and materials sales, and interest pay all operating, bond amortization, debt ser-
vice and other reserves, and other costs of the facility.
Tipping fees in energy-from-waste plants vary from$6 to $66 per ton with an average of
$33 according to GAA 1991 data. One landfill has published tipping fee (disposal) rates of
($21.40/ton for district residents, $63.30 for state residents out of the district, and $850 for
out-of-state trash. Recently EPA reported the annual cost of disposal of a ton of waste in a
landfill as $46/ton and for disposal in an EMW plant as W/ton.
The added cost of collecting and transporting recyclable materials, particularly where
separate curbside collection is used, is highly variable. Costs as high as $1100/ton have been
estimated, although an average of $100-200/ton seems to be more reasonable. Where source-
separated materials are delivered to a central location, there is little increase in cost, if the cost
to the individualis ignored. The valueof recycled materials varies with the region of the coun-
try and the specific recyclable. Some, such as aluminum beverage containers, have had positive
values for muchof their history. Others, such as used paper, have very volatile markets. Some
proponents of recycling suggest that the cost of collection and the tipping fee in a landfill
should be subtracted to arrive at a net cost of recycling. However, few if any locations have
managed to recycle sufficient wasteto reduce the cost of the collection or landfill operations.
In such instances, the use of offsetting costs is not appropriate.
Currently, the value of the energy produced or conserved by MSW utilization is approx-
imately $1.8 billion per year(oil at $20/barrel). Additional economic and energy savings would
be realized by reducing the amount of raw materials and feedstocks used in production of re-
cycled materials. The energy conservedby recycling is valued at about $0.9 billion. National
security can be enhanced by providing an augmented domestic energy source.
C. Markets
There is a large variety of markets for the productive use of wastes. However, these can be
roughly divided into materials markets for recycling and markets for energy.
Materials markets economics depends upon the value of the raw material displaced and
to a significant extent the value of the energy displaced by the raw material. Thus one of the
better recyclable materials is aluminum, where recycling displaces 281 GJ/ton [8]. As noted,
aluminum can stock currently sells for $480/tOn in the northeast. In general, the more pure
the recyclable, the higher the price. Thus, can stock, which is at most two alloys, is more
valuable than other aluminum scrap, which is a mixture of alloys. To reuse mixed scrap, it ’
must be assayed and blended, and other elements, such as pure aluminum, must be added to
achieve the desired alloy. Some recyclable materials have had very volatile markets through-
out their history. Old newsprint went from $40 ($ 1974) per ton in July 1974 to no value in
September. In November 1989 it was selling for $40 ($ 1989) to zero in February 1990. Some
selected current prices are listed in Table 1. Because of the volumes of elements in municipal
waste, used paper is the most recycled product. There is not enough known about industrial
waste recycling to make any specific comments. However, 5040% of the energy used in the
pulp and paper industry is from its waste, and the steel industry uses scrap for about 60% of
its U.S.output.
There are three feasible energy markets; fuel, steam, and electricity. The most common
market is for electricity. The most economic market is for steam. Steam priced at a total of fuel
andcapitalcostsisworthabout$0.0095/mJ($9/MBtu),while electricity is $0.0215/MJ
($O.O75/kWh). However, the capital costs for a steam plant are 10% less, and three times as
much steam is produced per unit of input energy. As fuels, natural gas and oil are worth about
$0+002/MJand coal about $0.001/MJ. Wasteis a solid fuel and as such can only be used in a
200 Walter
Table 1 Average RecyclableMaterialPrices for Three Regions ($/ton)

West
Commodity South Northeast
Old newsprint -$ 25 $ 5 $10
Used aluminum beverage containers $480 $490 $450
Other aluminum scrap $400 $480 $400
Glass $ 13 $ 37 $ 28
Steel cans $ 15 $ 15 $ 21
Source: Recycling Times [9].
coal-fired boiler with today’s technology. Therefore, steam is the preferred energy product from
waste, but matching to an industrial steam load is difficult. Except where an industry is using
its own wasteor a city has a district heating system,electricity is the preferred energy product.
Even where the waste is recovered as biogas froma landfill and fuelor natural gas markets are
feasible, most of the gas is used to produce electricity. Today about 80% of all waste used for
energy produces electricity.
D. Thou Shalt Not Produce Anything No One Wants To Buy

The third of the commandments is essential even for businesses. One firm won the right to
construct a municipal waste plant producing refuse-derived fuel but did not have a market for
the fuel. As a result the design was changed to a fuel technology that was developmental but
for which there was a market. The technology demonstration could not be upgraded rapidly
enough to correct the problems, and ultimately the project failed.
E. Thou Shalt Honor Thy Economics

The fourth of the commandments pertains primarily to municipal waste. One city used mu-
nicipal resources to collect recyclables and private collectors for nonrecyclable trash. Each
home owner selects and directly pays a private collector. The city provides landfillservices to
the private collectors. The citypays for collecting newspaperand must pay a processor to take
the recyclable paper. In addition, the removal of the recyclable paper fromthe landfill did not
change the cost of operating the landfill, so that the cost of disposal in the landfill increased.
Any city trash sent tothe landfill was chargeda higher tippingfee, as were the citizens through
the private collectors. The situationwas made worse when some of the collectors determined
that it was cheaper to haul waste to a distant landfill.
F. Thou Shalt Not Expect Gold in Garbage

The fifth of the commandments recognizes that wastes have no valueor even have a negative
value until the producer believes that someone else might want the material. Inaddition, many
people in cities believe that they will make money from their garbage.
IV.
ENVIRONMENT
W a s h can be managed three ways: They can be reduced at the source, they can be used, or
they can be discarded. With all things equal, the best solution is to avoid producing them
(source reduction). This implies that raw materials are used more efficiently.
Any waste disposal system has the potential to make discharges to the air,land, or water.
For example, a natural organic waste discardedon the land will degrade to acids and eventually
Commandments of Waste Management 201
Table 2 Ultimate Analysis of Selected Fuels (% dry weight)

MSW Wood coal
Carbon 48.9 39.5 74.3
Hydrogen 5.9 5.0 4.9
Oxygen 43.3 29.5 7.8
Sulfur 0.01 O.l(O.1-0.2) 3.7 (0.5-4)
Nitrogen 0.03 0.5 1.4
Chlorine 0.01 0.4(0.2-0.5) 0.06(0.06-2)
to biogas, stoichiometrically, a mixture of equal molecules

of carbon dioxideand methane. The
acids will increase the solubilityof heavy metals, while bothof the latter are gases that affect
the global climate. The same organic material could be burned to produce air emissions in-
cluding carbon dioxide and sulfur, chlorine, and nitrogen compounds. In water, organics rot,
consume oxygen, and produce acids that have adverse environmental impacts.
A. IndustrialWaste
A significant amount of the waste discarded by industry is reused. The wastes that are reused
save the environmental degradation caused by input material acquisition, reduce energy use and
its associated impacts, and reduce the impacts of end-of-the-pipe control and final disposition.
For example, when paper is produced by chemical pulping, lignin is dissolvedto free cellulose
and hemicellulose fibers. In addition, the pulping chemicals and lignin combine to produce black
liquor. Originally, black liquor was dischargedto the nearest stream. A combinationof the in-
creased costof chemicals and energy and environmental regulation sparked the development of
recovery boilers. These units use lignin as a fuel to produce energy and recover chemicals for
reuse. Since ligninand waste wood and bark (from paper making and burning)are low sulfur,
chlorine, and ash fuelsand are renewable, theyare less polluting than the fossil fuels displaced.
Tables 2 and 3 list the ultimate and proximate composition of some wastes and fossil fuels.
As noted previously, relatively little is known of industrial waste management, and the
types of wastes between and within industries are very varied. Therefore, detailed discussion is
difficult. Industry has long used home wastes (producedin the plant or factory, e.g., leftover
metal from ingots) and prompt wastes (produced in the next level manufacturing facility, e.g.,
aluminum can scraps) when it was economical to do so. Within the context of the industrial
waste program of the Departmentof Energy, industry is displaying great interest in the reduc-
tion or substitution of hazardous and toxic wastesto simplify and reduce environmental costs.
For example, Motorola and DOE are sharing equally the development of a replacement for the
volatile organic compounds (VOCs) used to clean circuit boards. By using a nitrogen blanket
and adipic acidas a combined flux and cleaning agent, VOCs have been displaced and clean-
liness standards retaihed. In a separate program, DOE and EPA are cooperating to apply ex-
isting technology to industrial waste minimization. For example, the federal government, the
Table 3 ProximateAnalysis of Selected Fuels (%)

MSW Wood coal
Moisture 50.0 25.1 13.1
Volatiles 40.3 43.8 27.9
Fixed carbon 9.7 6.1 51.1
Ash .02 25.O 7.9
202 Walter
State of Texas, and FMC Company cooperated to demonstrate the recovery of methanol from
hydrogen peroxide production. The methanol is used to clean catalyst and is contaminated with
dilute quantities of hydrogen peroxide, which makes it hazardous. By steam stripping the hy-
drogen peroxide, 98% of the methanol can be returned to the process instead of being sent to
a hazardous waste facility for destruction. Another example from the same program is PPG,
which applied reverse osmosis to clean machinery wash water and reduced hazardous waste
disposal by 95%, reduced fresh water consumption by 4 4
0
O,O O Vyear, and improved the effi-
ciency of its operations.
B. MunicipalWaste
As for industrial wastes, source reduction theis preferred waste management technique for mu-
nicipal postconsumer wasteif all other things are equal. Municipal waste is very complex. An
increase in one wastemay result in the reductionof another. The Chamberof Commerce of the
United States estimates that for every pound of packaging added to the municipal waste stream
in the 1980s, 2.7 lb of food waste was eliminated. Some of the added packaging was plastic,
which does not degrade ina landfill but does not produce acids and therefore does not increase
and reduces highly degradable food waste. However, there are attempts to reduce the amount
and type of packing. For example, recently, under public pressure, some fast food stores have
replaced Styrofoam serving boxes with multilayer paper and plastic boxes on the basis that
Styrofoam does not degrade in landfills and takes excessive space. However, the disposal of
nonbiodegradable materialsin landfills reduces the toxicity of leachates (decreases metal sol-
ubility) and reduces the need for landfill space (Styrofoam is weaker and less likely to bridge
than the multilayerpapedplastic replacement). In addition, Styrofoam can be recycled into sty-
rene or burned, whereas the multilayer paper can only be burned.
The comparison of the environmental emissions from landfill, recycling, and fuel is not
simple. For example, glass can be landfilled with no resulting net emissions except for the
transport of the glass to the landfill.When recycled, the transportation emissions are dramat-
ically increased, but energy consumption (generally in the form of natural gas)is reduced, thus
reducing associated air emissions.
Landfills emit biogas and many trace chemicals through their surface to the atmosphere.
Stoichiometrically, biogas is a mixture of carbon dioxide and methane in equal numbers of mol-
ecules. In practice, carbon dioxideis more soluble in water, forming carbonicacid, and there-
fore more methane is emitted. These two gases are the largest contributorsto global warming
emissions. Various estimates have been made of the comparative methanekarbon dioxide glo-
bal warming gas effect. Currently EPA is using a 25 times estimate. Rainfall and other water
that penetrates the landfill produces leachate, which then enters groundwater. In the degrada-
tion process the natural organic waste landfills form acids. Most heavy metals are more soluble
at pH less than 5 or greater than 12. Mixed waste placed in a landfill is neutral to slightly
acidic. The combination of acid rain and degradation of the organics can reduce the pH of a
mixed waste landfill to less than 5 and result in leachate that occasionally exceeds EPA stan-
dards for lead and cadmium. MSW combustion ash has a pH of about 11.
Leachate from an MSWcombustion ash landfill has been tested for 4 years. Leachate sam-
ples have rarely exceeded drinking water standards (100 times more stringent than leachate
standards). In addition, the pH has stabilized, and the amount of heavy metals in the leachate
has begun to decrease.
The effect of recycling on the environment is not well understood. The majority of the
available data are anecdotal. It is known that, most often, recycling increases vehicular emis-
sions over the other forms of MSW disposal management even compared to raw material ac-
Table 4 GreenhouseGas Emissions

CO, CH,' Equiv. CO,
Landfillb 1 1 26
Fuel 2 2
Recycle 0.15 0.15 3.9
'CH, is 25 times as reactive as CO2
bFifteen percent ofshort fiber is landfilled.
quisition. Wood used for paper manufacture is50% moisture and about2.5% extractives (sap,
etc.) that do not become part of the product paper. When kraft paper is produced, the lignin
(12.5% of wet wood) is dissolved to free the cellulose and hemicellulose fiber for paper pro-
duction. Thus less than 35% to no more than 47% of the raw wood feed becomes paper, and
industry naturally locates closerto the wood source to minimize transportation costs. One no-
table exception is boxboard, which is virtually 100% manufactured from waste paper and there-
fore tendsto have plants near cities. Recycled paper results in deinking slops (again except for
boxboard and cardboard, where color is immaterial) and short fiber for landfill. Considering
the 15% short fiber that results from remanufactureof paper and is landfilled, recycling paper
produces more net greenhouse gas emissions than burning allof the paper (see Table4). The
net environmental effects of recycling plastics and inorganic materials are almost unknown.
There are some environmentaldata available to indicate concern for zinc from galvanized steel
and VOCs from paint on cans.
Combustion of MSW produces air emissions. With modern pollution control equipment,
including electrostatic precipitators, bag houses, and acid gas scrubbers, these emissions are
reduced to meet control standards. At the present time, EMW emission standards are more
stringent thanthoseforcoal or Therefore, modern MSW combustionplantsproduceless
criteria air emissions than fossil fuel plants producing the same energy. Particulates are 10
times lower, sulfur oxides 15 times lower, and nitrogen oxides about the same, with a small
increase in chloride emissions compared to most coal. With some coals, the chlorine content is
high and chloride emissions exceed thoseof MSW. Similarly coals haveheavy metal contents
that on occasion exceed those of MSW. MSW combustion does result in measurable dioxins in
the stack gas; however, those emissions are lo00 times lower than state allowable limits, are
less than the dioxin measured in the input waste, and degrade to below detection limits in 8 hr
or less in sunlight. Where checks have been made, there has been no detectable dioxin at
ground level around operating plants. There are no specific standards for chloride, carbon di-
oxide, and dioxin emissions from fossil fuels. Measurement of the chlorine content of coal is
just being initiated. Prior U.S. measurements did not detect dioxin in the air emissions of coal
'For example, an Alexandria, Virginia, plant usesdirect injection of limestone into the boiler box for acid gas control
and electrostatic precipitators for particulate control. The resultant emissions include0.063 Ib of particulate, 0.26 Ib
of sulfur oxides, 0.10 Ib of nitrogen oxides, 0.47 Ib of hydrogen chloride and 0.05 Ib of carbon monoxide, all per
million Btu. In addition, the plant releases0.006 Ib of dioxin per year per million Btu. These are all currently or about
to be criteria pollutants from EMW plants. The plants with the moreefficient scrubber systems for sulfur and chlorine
control increasesulfur and chloride removal efficiency by 10 percentage points (from60 to 70% and from 80 to 90%.
respectively). The comparative standards for emissions from fossil plants are 0.2 Ib of particulate, 2.6 Ib of sulfur
oxide, and 0.9 Ib of nitrogen oxide emissions per million Btu. Carbon monoxide and non-methane hydrocarbon emis-
sions from waste-toenergy processes are comparable or lower. In one plant in Commerce City, California. the nitrogen
oxide emissions from the plantand the hauling of the ash to a landfill are less than the nitrogen oxide emissions from
the trucks required to haulthe raw waste to the landfill. The air in an Indianapolis plantis cleaner since an EMW plant
was put into operation.
204 Walter
plants, although dioxinhas been detected in the emissions from coal combustionin the United
Kingdom. There has been very little comparison of the emissions of EMW and those of fossil
fuel plants. When emissions are compared for the landfill, recycling, and energy production
from MSW, combustion is more attractive than presumed.
C. Thou Shalt Honor All Thy Environment

The sixth commandment demandsthat all of the effects on the environment be considered, not
just those in the immediate vicinity of an activity. In effect, the replacement of “not in my
backyard” (NIMBY) by “in someone else’s backyard” (ISEBY) is not acceptable.
V. ENERGY AND TECHNOLOGY

A large variety of thermal, physical, chemical, and biological technologiesare available to use
wastes productively. The appropriate technology depends onthe state of the waste (solid, liq-
uid, or gas), the type of waste (organic or inorganic), and the end product (material or fuel).
Organic wastes canbe used economically as fuels or as raw materials; that is, they can produce
or conserve energy. Inorganic wastes can only be used as raw materials. Ingeneral, the thermal
technologies produceeither energy or gaseous or liquid fuels. The physical and chemical tech-
nologies produce raw materials for recycling, products, or solid fuels. The biochemical tech-
nologies produce gaseous or liquid fuels or chemicals.
A. IndustrialWastes
Significant amounts of industrial waste have been reused for generations. About 60% of our
domestic production of steel is from scrap, which saves an estimated 1.3 X 10l8 J (1.2 X 10’’
Btu) per year. Also, significant quantities of scrap iron and steel are exported and returned as
finished products. The closer the scrap is to the point of production, the more likely itis to be
used. In contrast, U.S. junkyards have a 17-year supply of scrap steel, mostly from discarded
automobiles and appliances.
The precise technologyfor reusing scrap is highly dependent onthe nature of the scrap. If
it is organic likewood pallets andplastics, it may be burned or reused as material. For example,
to the extent possible, industry reuses wooden pallets and shipping materials. At some point
these can no longerbe used, and if sufficient quantities are available they are burned for plant
energy. If there is not enough material for economic use as a fuel, they are discarded. In a
program in the late 1970s, DOE developed a technology to burn atactic polypropylene, a waste
from the production of polypropylene. A commercial-scale plantwas constructed andoperated
successfully. Later, changes to the process increased the output of product per unit of input.
There was no longer sufficient waste to warrant investment in a recovery unit. Sincethe early
1980s when utilities were required by law to purchase excess electricity, industries have in-
creased their use of organic wastes to cogenerate steam and electricity for process use, with
excess electricity sold to utilities. In fact, a new business has developedthat takes wastes and
either cogenerates steam for sale to industry and electricity for sale to utilities or simply gen-
erates electricity for sale. In terms of the efficiency of fuel use, cogeneration is the preferred
technology sinceelectricity generation is 2 0 4 0 % efficient (depending on the fuel and thesize
of the facility) and cogeneration can approach 80% fuel efficiency.
As discarded, waste paper has an energy content of 17.4-20.8 &/kg (7500-9000 BNlb).
Using postconsumer paperas a feedstock to make new paper saves 0-4.4 &/kg (0-2000 Btu/
Management of Waste
Commandments 205
lb). Plastics have an energy contentof about 46 d l k g (20,000 BNlb). There are no consistent
data on the energy savings from recycling plastics.
Inorganic materials can only be used as raw materials for a process. The technology used
and the energy conservedare dependent on boththe type of material andits relative purity. For
example, U.S.automobile aluminumis alloyed with strontium to make it ductile. Foreign car
makers use antimony for the same purpose. When melted for reuse, the two alloying metals
combine to cancel the desiredductile effects. A method to neutralize one is in development to
protect this valuable scrap market. Although the energy savings fromthis particular scrap have
not been traced, they can be assumedto approach the IO-MJ savings from recycling aluminum
can stock.
B. Municipal Waste
Municipal solid waste can be converted to energy by thermal or biochemical technologies. The
commercial thermal technologyis combustion to produce steamfor industry, hot water for dis-
trict heat, or electricity for the grid. MSW may be burned as received in specially designed
facilities on a hearth (typically 25-50 metric tons/day per unit)or on inclinedgrates (typically
250-1000 metric tons/day per unit). In addition, solid fuel canbe produced mechanically. This
refuse-derived fuel (RDF) can be burned in a specially designed boiler on a traveling grate
(typically 400-1000 metric tons/day). RDF is also used as a substitute for coal, preferably in
a grated boiler but typically in a suspension-fired boiler. Limited research is developing new
technologies that produce fuelgas or liquid transportation fuels or new forms of RDF such as
densified and powdered RDF. The former can be stored for longer periods and marketed to
multiple users; the latter can be used as a substitute for oil in boilers designed for heavy oil.
Current commercial combustionfacilities are 65-796 efficient in producing steam (fossil fuel
facilities are 8 8 4 0 % efficient) mainly dueto moisture and inorganic content. In contrast, a low
moisture and low ash waste such as paper or dry wood has a calculated efficiency of 89%.
Biochemical conversion technologies use organisms to produce specific fuels. For example,
a complex consortium of organisms found in nature will reduce cellulose and other carbohy-
drates to simple sugars, organic acids, and finally biogas. Currently, commercial biochemical
conversion is limited to the recovery of biogas from landfills and sewage treatment. Future re-
search could completethe development of technology to produce biogas or ethanol from mu-
nicipal waste or selected components.
Recent measurements of the energy content of as-received MSW indicate that approxi-
mately 11.6 d l k g (5000 BNlb) of energy is contained in each poundof MSW [up from 10.4
&/kg (4500 BNlb) in recent years].
Municipal solid waste management can conserve energy by remanufactureof specific com-
ponents into new materials. Certain inorganic components(steel, aluminum, and glass) canbe
separated by source separation of mechanically, magnetically, by density, size, shape, electro-
statics, etc.) and recycled into new materials. Certain organic components (specific gradesof
clean paper and specific plastics) can be recovered and remanufactured. Since high purity is
necessary for materials to be recycled, source separation is the preferred recovery technique.
Research is required to economically recover componentsother than steel from mixed waste.
The amount of energy conserved is different for different commodities. For eximple, the re-
cycling a pound of aluminum conserves 242 &/kg (100,000 BNlb) while recyclinga pound of
glass conserves about 3.8 &/kg (1500 BNlb) [lo]. In addition, the conservation of energy
within a commodity may be different. For example, recycling old newsprint into new newsprint
conserves about 4.6 d l k g (2000 BNlb) while recycling cardboard into new cardboard saves
about 2.3 &/kg (1000 BNlb).
206 Walter
Currently thereare approximately 150 waste-to-energy facilities in the United States. They
vary from mass-burn facilities where MSW is burned as received, through facilities that pre-
pare a fuel for use in existing boilers, to those that recover recyclables. Over90%of the energy
generated from these facilities is from the burning of waste. There are a large number of re-
cycling programs and 50 or more materials recovery facilities (MRF). Based on GAA, EPA,
and DOE databases, currently about 0.29 X 10l8joules (0.28 X lo’’ Btu) of primary energy
is produced by burning, about 0.16 X lo’*joules (0.15 X lo’’ Btu) 0.15 quad is conserved by
recycling, and about 0.05 quad from landfillgas (LFG) is being recovered from about 100 land-
fills. About 80% of the energy produced from burning is electricity, with the remainder being
steam or hot water for industry or district heating. The recycling mostly conserves electricity
in aluminum production. About 80% of LFG is used to produce electricity, while the rest is
used as boiler fuel or cleaned to pure methane for use as substitute natural gas.
C. Thou Shalt Honor All Thy Technology

The seventh commandment notes that there are a number of ways to use wastes. In many ways
the productive use of waste is more important than the way the waste is reused.
VI. LIFECYCLE
For sound waste management decisions, the life cycle of the systemmust be considered. Waste
must be collected fromthe point of generation, transported to a point of reuse or disposal, and
used as fuel or raw material, with any resulting waste discarded.
It is difficult to determine the appropriate bounds for a life cycle analysis forthe disposal
of waste and the appropriate comparative data. Should the life cycle be bounded by the ac-
quisition of the raw material (by miningor recovery of recyclable)or by the manufactureof the
mining equipment, or even earlier in the recovery of raw materials for the mining equipment?
Experience indicates that, given the accuracy of the data available, going beyond the acquisi-
tion of the raw materials does not improve accuracy.
A. An Example
Since much of the data are either missing or anecdotal, an example is provided toillustrate the
complexities of the analysis, provide a method of consideration, and indicate missing data.
Since most data are available for MSW, the example concerns thelandfill, recycling, and burn-
ing of paper. With few data available on a methodology to trade off impacts, the economic,
environmental, and energy effects of each option are considered separately. The appropriate
start for MSW management would seemto be at the point of discard for waste paper andin the
forest for virgin paper. But in keeping with a necessary themethat there seemto be exceptions
to any rule for MSW management, one special consideration is needed. Should the waste have
entered the system at all? Again, this is an issue that has life cycle connotations but is one
where few data exist. For example, a current belief is that reducing packaging will reduce the
amount of waste. However, the estimate is that for every pound of packaging added in the
1980s, 2.7 Ib of food waste was avoided. Therefore, it may not be advisable to avoid packag-
ing, plus packaging can be recycled or used as fuel.
1. Landfill
Profile. Waste paperis collected from the generator at the door as part of MSW management.
There is no separation, and thereis a single collection vehicle with a crew of one to three.The
collection vehicle transports the mixed waste either to a landfill for disposal or, if more eco-
Management of Waste
Commandments 207
nomic, to a transfer station for repacking into a larger vehicle to be transported to a landfill.
Landfill is considered the baseline against which the other options are compared since most
MSW and postconsumer waste paper is landfill. As a result, certain costs and impactsare not
discussed under landfill. Expected changes in the system for the other options are discussed.
For example, the emissions fromtransportation fuels are significant and include carbonmon-
oxide nitrogen oxides, particulates, volatile organiccarbons, carbon dioxide, and, from diesel
fuel, sulfur oxides. Transportationis a major pollution sourceand therefore is important. Any
significant increase in miles driven results in a significant increase in air pollution.
Economics. The costs of collection, transportation, and landfill vary from location to loca-
tion. Past estimates indicate that 75% of the cost of waste management is in collection and
transportation with the remaining 25% for landfill. The cost of landfill has been increasing
rapidly as new environmental requirements to reduce the impact of emissions are implemented.
The highest reported cost of landfill of mixed waste is $150/ton. EPA recently estimated the
cost of landfill at $45/ton. Landfill of waste paper has no advantage over mixed waste and
should cost the same or potentially more since paper occupies more volume per tonthan
mixed waste.
Environment. Landfills emitair emissions including carbon dioxide and methane (greenhouse
gases) and trace organics. In one DOE study, over 50 different trace organic emissions were
measurable in landfill gas. The long-term, difficult-to-estimate environmental concern is leach-
ate, potentially with increased heavy metal content, entering groundwater. Modern landfills
require liners and leachate treatment for control;however, science indicates that landfill liners
will breech, the only question is when.
Energy. In 1976, DOE examined the total energy consumptionin the collection of trash. The
study indicated that the energy used by MSW collection was minor. Landfills do degrade nat-
urally to produce a gas that is half carbon dioxide and half methane. Thisgas can be captured
and used as a boiler fuelto produce steam and/or electricity, used in an engine to produce elec-
tricity, or cleaned to remove the carbon dioxide and used assubstitute natural gas for the pipe-
line system or as a vehicle fuel. Theefficiency of theconversion of organics to LFG is
estimated to be 32%; that is, 5.8-7.0 d / k g (2500-9000 Btu/lb) would be recovered as biogas.
2. Use for Recycling
Profile. Paper is collected separately from other wastes. In general,as for all recyclables, the
more pure the paperis, the more valuable itis. Thus, to maximize value, used newsprint,card-
board, and mixed paper should be kept separate although the same truck can beused to collect
them. The collection must be by curbside pickup,in the same or a separate truck, for maximum
recovery, although deliveryto a central point by each resident is also feasible. No matter which
is used, vehicles tendto travel added miles. Transportation to the remanufacturing plantis gen-
erally long in comparison to the landfill or use as energy options.
Economics. Curbside collection is costly. There are few careful estimates of the cost of sep-
arate collection for paper recycling. It appearsthat separate curbside collection costs from$100
to over $200 per ton. A method to describe the costof separate delivery of recyclable material
to a recycling center has not been developed.The current price for used paper is listed in Table
1. In 1990, one city burned half of its used paper to earn enough to recycle the other half. At
the same time the expansion of markets for used newspaper is capital-intensive. A deinking
plant alone costs $60-90 million for a 250 todday capacity. A full-scale plant built from the
ground up will cost over $1billion.
Environment. Transportation is important when considering environmental issues, and very
little is known about recycling. Two examples are available. Both Wilmington, Delaware and
Walter
Hartford, Connecticut ship their newsprint to ThunderBay, Ontario, a distance of 1500 miles,
for recycling. In contrast, a boxboard plant inSpringfield, Massachusetts obtains its waste pa-
perand cardboardsupplylocally.Intoto, transportation emissions canbe expectedtobe
greater for recycled paper than for either landfill or use as a fuel and greater than those from
obtaining wood to make virgin paper.
A second issue is the value of the wood used for virgin paper. Often, paper recycling is
advertised on the basisthat recycling a ton of paper saves 17 trees. But what 17 trees are saved?
They are not from virgin or primeval forest but rather from tree farms or from forest manage-
ment. In the formercase, the tree farm has completed growth andis beginning to recycle car-
bon dioxide; that is, the loss of tree weight in branches and leaves is balanced by the annual
growth of the tree. In addition, seven trees are replanted for every one harvested. In thelatter
case, the removal of trash trees results in a more vigorous forest.
It is difficult to compare MSW disposal management environmental impacts. There is rel-
atively little consistently gathered comparable information. Transportation effects are not in-
cludedsincereasonableinformation is not available; however,they are major. If paper is
landfilled, each two molecules of carbon are degraded to one molecule of carbon dioxide(CO,)
and one moleculeof methane (CH,). Theseare the two most significant greenhouse gases, with
a molecule of CH, 20-100 times as reactive as a molecule of CO,. If landfill gas is used as a
fuel or flared, then the molecule of CH, is converted toa molecule of CO2 and four molecules
of water. In addition, some volatile organic carbonsare emitted. The length of time needed for
the degradation to occur is not well defined but is less than 100 years, which is very short in
comparison to fossil fuels, which represent carbon captured eons ago.
If paper is burned, then every two molecules of carbon become two molecules of CO,.
If paper is recycled, several changes to the system occur. Fifteen to twenty percent of the
fiber is too short to reuse and is landfilled. Here it degradesto COz andCH,. In addition, 65%
of the energy to produce paper is obtainedfrom wood waste, which is no longer available and
is replaced with fossil fuel. The wood that would otherwise be used to produce paper remains
in the forest. However, this wood is either from forest managementor from a tree farm that is
replanted after harvest. In either case, the trees will use more CO2 than the forest primeval,
since the latter has completed its growth.
Table 4 summarizes greenhouse gas information. Transportation effectsare not included.
Energy. Since the paper must travel a longer distance, energy consumption is higher. The en-
ergy savings from recycling paper depends upon the type of paper used and the product. For
example, when used newsprint is recycledinto new newsprint, about 4.6 d l k g (2000 Btu/lb)
is saved. When the same used newsprint is recycled into boxboard, there is no net savings.
When cardboard is recycled intonew cardboard, there is a savings of 2.3 mJkg (1000 Btu/lb).
These savings are all in the manufacturing plant.
3. Use as a Fuel
Profile. Paper is collected as part of mixed waste, and there are no changes to the collection
system. Thetransportation distance to an energy plantis generally shorter than or equal to that
for a landfill. As paper is burned, ash is produced and must be transported to either a landfill
or a site to be utilized. There is no significant leachate, since there is no organic material to
degrade and produce the acid necessary to dissolve heavy metals.
Economics. There is a significant savings in vehicle maintenance costs since the vehicles use
a concrete tippingfloor rather than dirt landfill roads. The oneestimate is from theearly 1980s
when New Orleans reported a $500,000 annual savings. MSW energy plants have high capital
cost. However, between the tipping fee and the income from energy and material sales, the
plant earns enough to pay all the costsof construction and operation, including amortized cap-
Management of Waste
Commandments 209
ital costs, interest during construction, debt reserve,operations, maintenance and repair, etc. If
financed with revenue bonds, the financing has no effect onthe city’s general obligationbond
authority and rating. EPA estimates the average tipping fee in an energy plant as $42/ton in-
cluding ash disposal.
Environment. There maybe a change in vehicle emissions depending on the total vehicle
miles driven; however, most energy plants are at the site of the landfill or closer to the center
of collection so that transportation emissions are either the same or at best slightlyless than the
baseline. However, in one case, a net decrease in NO, emissions was reported as a result of
transportation. That plant was between the landfill and the collection district. The ash weighed
about 75% less than the raw waste. Removal of three fourths of the trash trucks from theroad
between the energy plant and the landfill reduced more NO, emissions than the energy plant
produced. If only the paper fraction is considered, then only about 1% of ash would remain
as waste.
When burned, MSW produces emissions of particulates; sulfur oxides (SO,), nitrogen ox-
ides (NO,), and hydrogen chloride (HCl) (acid gases); volatile organiccarbons, including di-
oxins and furans;and metals. All of these canbe andare controlled. About80% of MSW plants
produce electricity, and since55% of overall electricity production inthe United States is from
coal, the latter is the dominant fuel displaced. When MSW is burned to produce electricity, it
produces 22 tons less pollution per megawatt per year than coal using current environmental
regulations for each fuel for comparison. The majority of the pollution displaced is SO, and
particulates. The amount of NO, produced is about the same. HCl and dioxin are increased
compared to those for many coals. However, there are some coals with relatively high chlorine
contents thatwould be expectedto exceed MSW dioxin and HClemissions. To put dioxin emis-
sions in perspective, the 20-MW Alexandria, Virginia plant produces about 3 g of all isomers
of dioxin3 annually. The same basic statements are true for heavy metals.
Although the discussion aboveis for coal combustion,if all the facts wereknown the same
could be said for oil.
Energy. The energy costs of transportation are either equal to or slightly less than for the
landfill disposal option; however, any savings would be negligible. When burned, paper pro-
duces energy. Paper contains about SO00 Btdlb. Since it haslow ash and low moisture, it burns
efficiently. There are no furnaces burning pure paper to produce energy; however, from calcu-
lations developed to estimate the efficiency of fossil fuel combustion processes, if pure paper
were burned, it would be about 89% efficient. Therefore, burning 1 Ib of paper will produce
about 15.5-18.6 r d k g (6700-8000 Btullb) of energy.
B. Thou Shalt Not Believe in Total Resource Recovery

The eighth commandment, simply stated, is that waste is bound to occur in any system, and
true waste must be discarded.
C. Thou Shalt Consider the Life Cycle

The last of the commandments is that life cycle economic, environmental, and energy costs
must be considered when decisionsare made for the management of municipal solid waste. If
%hlorinated dioxin has 72 isomers that vary in the number of chlorine atoms and their placement in the molecule.
2.3.7,8-Tetradibed,ioxin is the most dangerousof the chlorinated dioxin molecules. The next most significant mol-
ecule is 100 times less dangerous. Further, dioxin is degraded by sunlight, with concentrationsdropping below detec-
tion limits in 6-8 hr.
210 Walter
Table 5 EnergytoRemanufactureVersusFuelEnergy [ d l k g (BWlb)]

Energy to Energy
saved
in
manufacture
remanufacture
energy
Fuel
Paper
Newsprint 4.6(2000)
62.8(27,100) 19.7(8500)
Cardboard 2.3( 1ooO) 17.4(7500)
Boxboard 0 (0) 17.4(7500)
Plastic
Steel 49.0 0 (0)
Aluminum 281.0(100,000) 0 (0)
Glass 2.9 0 (0)
there is one thing to remember, it is that everything goes somewhere.For energy, economics,
and the environment, we must think in very broadterms. Few understood when very tallsmoke
stacks were constructed onelectric generation plants in the Ohio River valley to disperse pol-
lution as far as possible, that those plants would be later found to be responsible for acid gas
depositions on the eastcoast and in Canada. We must honorofallour environment and not just
the part in our backyard.
There's a significant energy supply and a significant energy demand reduction opportunity
available to the nation. Supply and demand are not opposites; they are complements. Both
must be pursued. Experience is provingthat the use of waste as fuel and as a raw material are
complementary. Introducing both intothe solid waste management system improves each. Re-
moving grass and other wet yard waste for composting and cans and bottles for recycling ac-
tuallyimprovescombustion.Where there are recycling and energy markets for paperand
plastic, the recovery for both uses is enhanced. The construction of oversized energy plants
seen in the late 1970s has not been repeated, and the conflict between energy and recycling
does not exist.
Table 5 summarizes energy values. Should we bum all our waste? No. Should we bum
some of our waste? Yes. Should we recycle all of our waste? No. Should we recycle what we
can? Yes. Can we do without a landfill? No. The most useful system combinesthe advantages
of use as fuel and use as raw material to minimize discards.
REFERENCES
1. EPA, Report to Congress: Solid Waste Disposal in the United States, Vols. 1 and 2, EPN530-SW-
88-011, Office of Solid Waste, U.S. Environmental Protection Agency, Washington, D.C., 1988.
2. EPA, Report to Congress: Management of Wastesfrom the Exploration, Development, urd Pro-
duction of Crude Oil, Natural Gas, and Geothermal Energy, Vol. 1 , Oil and Gas, EPN530-SW-
88-003A, preparedbyVersar, Inc., forthe U.S. EnvironmentalProtectionAgency,Washington,
D.C., 1987.
3. EPA, Report to Congress: Wastesfromthe Extraction andBenefication of Metallic Ores, Phosphate
Rock, Asbestos, Overburden from Uranium Mining, and Oil Shale, EPN530-SW-85433, Office
of Solid WasteandEmergency Response, U.S. EnvironmentalProtectionAgency,Washington,
D.C., 1985.
4. EPA, National Screening Survey of Hazardous Waste "keatment,Storage, Disposal, and Recycling
Facilities, 1986, EPN530-SW-88411, Office of Solid Waste, U.S. EnvironmentalProtection
Agency, Washington, D.C., 1988.
5. EPA, Characterization of Municipal Solid Waste in the United States 1960-2000 (Update 1990).
1992, PB88-232780; EPN530-SW-88433, Franklin Associates, Ltd., Prairie Village, Kansas.
6. EPA, First Report to Congress, Resource Recovery and Source Reduction, Feb. 22, 1973.
7.Benson,R.A., Los AlamosNationalLaboratory, Los Alamos, NewMexico,personalcom-
munication.
8. Alter,H.,andDunn,J.J., Jr., SolidWasteConversiontoEnergy, MarcelDekker,NewYork,
1980.
9. Recycling Times,Biofuels: renewable fuels for the future, The Markets Page,
Recycling Times,Nov.
17, 1992, Solar Energy Research Institute, Golden, Colo., 1992.
10. DOE, A Review of Comparative Energy Use in Materials Potentially Recoverablefrom Municipal
Solid Waste, DOE/CS/20167-12, U.S. Dept. of Energy, Washington, D.C., 1982.
ADDITIONAL READING
ANL (1983). Institutional Issues,Concerning Energyfrom Municipal Waste: A Status Report,Rep. No.
ANUCNSV-TM-123, Argonne National Laboratory, Argonne, 111.
Bogner, X. X. (1988). The US.Londfill Gas Resource: h - C o s t Biogasfrom Municipal Solid Waste,
ANUCNSV-TM-206, Argonne Natl. Laboratory, Argonne, 111.
DOE (1988). Five Year Research Plan, Biofuels and Municipal Waste, 1988-1992.
EL4(1992). ManufacturingEnergyConsumptionSurvey:Consumption of Energy,1991, DOE/
EIA-0512(91), Energy Information Administration, U.S. Dept. of Energy, Washington, D.C.
EPA(1985a). ReporttoCongress on theMinimization of HazardousWaste, EPN530-SW-86433,
Office of Solid Waste and Emergency Response, U.S. Environmental Protection Agency, Washing-
ton, D.C.
EPA (1985b). Summary of Data on Industrial Non-Hazardous Waste Disposal Practices, EPA Contract
No. 68-01-7050, Work Assignment No. 11, Office of Solid Waste and Emergency Response, U.S.
Environmental Protection Agency, Washington, D.C.
EPA (198%). Waste Generators and Treatment, Storage, and Disposal Facilities Regulated Under RCRA
in 1981, Office of Solid Waste, U.S. Environmental Protection Agency, Washington, D.C.
EPA (1986). Waste Minimization: Issues and Options,EPA Contract No. 68-01-7053, Task No. 17, Pre-
pared for theU.S.Environmental Protection Agency by Versar, Inc. and Jacobs Engineering Group,
Washington, D.C.
EPA ( 1989a). 1985 National Biennial Report ofHazardous Waste Generators and Treatment, Storage, and
Disposal Facilities Regulated Under RCRA,Office of Solid Waste,U.S. Environmental Protection
Agency, Washington, D.C.
EPA (1989b). Office of Research and Development, Office of Environmental Engineering and Technol-
ogy Demonstration, Dec. 22, 1989, Drafr Municipal Solid Waste Research Agenda, unpublished,
U.S.Environmental Protection Agency, Washington, D.C.
EPA (1991).National Survey of Hazardous Waste Generators and Treatment, Storage, Disposal, andRe-
cycling Facilities in 1986,EPN530-SW-91-060, Office of Solid Waste and Emergency Response,
U.S. Environmental Protection Agency, Washington, D.C.
GAA (1991a). Resource Recovery Yearbook, Directory & Guide, Governmental Advisory Associates,
Inc., New York.
GAA (1991b).Materials Recovery and Recycling Yearbook, Directory& Guide, Governmental Advisory
Associates, Inc., New York.
Hasselriis, X. X. (1984). Refuse-Derived Fuel Processing,Butterworth, Boston.
Hocking, X. X. (1991). Paper versus polystyrene: a complex choice, Science, 251, 504 (Feb. 1, 1991).
Mishkin, X.,and Friedland, X. (1990). What the new EPA rules mean, Solid Waste Power, 4(1), 10.
Mitre Corporation (1978).Energy Conservation Waste Utilization Research and Development Plan, The
Mitre Corporation, Bedford, Mass.
Office of Technology Assessment (19XX).Energyfrom Biological Processes,Vol. 2, Technical and En-
vironmental Analyses,Superintendent of Documents, Stock No. 052-003-00782-7, U.S. Govt. Print-
ing Office, Washington, D.C.
Sussman, D., Director, Washington o f f i c e , Ogden Martin Corporation, and Walter, D. K.,Director,
Waste Material Management Division, U.S. Dept. of Energy (1990). Personal communication. The
212 Walter
experience at Ogden Martin plants is that the energy content of waste at Ogden facilities is incr
to SO00 BWIb and higher.As a result, the Alexandria plant(seefootnote 2) now receives 800 tons/
day in lieu of the design 900.
U.S. Bureau of the Census (1990). Stutisticul Abstructs of the United Stntes, 110th e d .
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ton, MA.
9
A Proactive Approach to Environmental
Management: Meeting Environmental
and Competitive Challenges
William E. Schramm
Oak Ridge National Laboratory
Oak Ridge, Tennessee
Stella S. Schramm
University of Tennessee
Knoxville, Tennessee
1. INTRODUCTION
American industry faces bothnew constraints and new opportunities. Over the past 20 years,
Americans have become increasingly concerned about environmental degradation and more
supportive of effortsto protect the environment. Government has responded to public pressure
with far-reaching regulation restricting industry’s access to collectively owned resources such
as air, surface water, and groundwater. Practices that threaten individuals or these collectively-
owned resources may be restricted even when conducted on private property. Such practices
include the generation, use, treatment, storage,or disposal of inherently dangerous materials.
Concurrent with these heightened environmental constraints, new international competitive
challenges and limits on resourcesare increasing the performance pressure on firms.
Conventional approaches to these challenges are proving to be limited in their effective-
ness. Political lobbyingto block environmental regulationsor to raise barriers to foreign goods
has become less effective as the environmental movement has become more politicallypow-
erful and as the concept of free trade has become more widely accepted. In addressing envi-
ronmental objectives, industry has historically focused on end-of-pipe control (i.e., pollution
control via the additionof treatment equipmentto waste streams at the end of the production
process) rather than prevention. Yet, end-of-pipe control becomes an increasingly expensive
means of meeting environmental standardsat higher reduction levels, limiting both the ability
to comply with escalating environmental requirements and the abilityto compete with foreign
producers.
The submitted manuscript has been authored by a contractor of the U.S. Government under contract No. DE-ACO5-
840121400.Accordingly, theU.S. Government retains a nonexclusive, royalty-free license to publish or reproduce the
published form of this contribution, or allow others to do so, for U.S. Government purposes.
213
214 Schramm and Schramm
Although some suggest that firms may move operations abroad to reduce costs and avoid
environmental regulation, the actual effectivenessof such a strategy is questionable. A recent
analysis by Cole et al. [l] examines competition between firms based on different industrial
organization paradigms, the mass production/scientific management (MP/SM) paradigm typ-
ical of the United States and the Japanese continuous improvement firm. The mass production/
scientific management form of organization uses specialization and hence functional division
within the firm as a means of gaining greater efficiencyand reducing costs. The Japanese con-
tinuous improvement organization, in contrast, focuses on overall systemsof delivering prod-
uct astherelevantscopeforanalysisandimprovement.Costreductions are achieved by
improving process, product, and overall delivery performance rather than greater specialization
in activities. Often continuous improvement firm improvements and their benefits are in the
interrelationshipof activities within the firm, rather than falling withinthe scope of individual
departments. Theseopportunities are likely to be deemphasizedor obscured by the functionally
segmented analysis indicated by a scientific management approach.
In contrpsting these two approaches, Cole et al. [l] predict a widening gap between MP/
SM and continuous improvement firm performance and point to a need to go beyond a narrow
cost minimization and functional specialization approach to compete successfully.In terms of
relocation, these findings suggest thatif a change in focus is not made, a one-time reduction in
costs from moving operations overseas may prove insufficient for an MP/SM firm to maintain
competitiveness. The Cole et al. findings imply that in order to compete, firms must develop
the abilityto continuously increase value provided to customers by improving all facetsof their
operations.
This chapter considers one aspect of operations, environmental management,where some
U.S. firms may be developing such an ability. Recently, various firms have initiated environ-
mental management programs thatgo beyond mere reaction to regulatory dictates, treating en-
vironmentally responsible corporate policies as not only economically beneficial but essential
to corporate survival in a changing legal and social environment. Pollution prevention and
waste minimization efforts are integral parts of these proactive environmental management
programs.Pollutionpreventionusesproductreformulation,processmodification,chemical
substitution, and equipment redesign to eliminate the generation of pollution at its source.
Where it is not possible to completely eliminate waste streams, waste minimization uses these
techniques as well as recovery systems, waste recycling, and reuse to reduce the amount of
waste generated.
Thischapterconsiders (1) the changesthat haveledsome firms toreevaluate their
environmental management goals, (2) the basic elements and outcomes of proactive environ-
mentalmanagementprograms,and (3) theimplications of theseprogramsforindustrial
competitiveness.
II. CHANGINGCIRCUMSTANCES
This section considers changes that have influenced the business environment over the past 20
years. These changes include societal views on environmental issues, governmental responses
to publicenvironmentalconcern (i.e., regulation), theavailabilityof data on pollution-
generating activities, and the level of global competition.
Although public opinion on the subject of the environment isdiverse, it is not inaccurate
to suggest that the level and nature of public interest on environmental matters have changed.
Generally, Americans have become less tolerant of pollution from all sources, particularly
from industrial sources. In a democracy, industry, like government, ultimately operates with
the consent of the people. The importance of retaining public confidence has been demon-
AApproach
Proactive to Environmental
Management 215
strated as industries failing to adequately consider public sentiment have had their right to op-
erate questioned. The chemical industry in North America experienced this. Surveys in the late
1980s indicated profound public distaste for the chemical industry[2]. Many industry leaders
concede that the industry’s failure to meaningfully address public opinion contributed signifi-
cantly to the passage of the Comprehensive Environmental Response, Compensation and Lia-
bility Act (CERCLA) in 1980.
This experience hasbeen repeated in other countries as well. In Canada, a public opinion
poll in 1986 indicated that 48% of Canadians felt that the risks from the chemical industry’s
activities in Canada outweighed the benefits. In Japan, pollution abatement is viewed as a
moral obligation.Governmentholds an antibusiness attituderegardingpollution,although
government in Japanis not inimical toward business on other accounts [3]. In western Europe,
“green” parties, once considered fringe groups, have developed into a significant political
force. Nor is growing environmental concern just a featureof industrialized countries. A recent
GallupInternationalInstitutesurvey [4] foundthatmajoritiesinbothdevelopedandless
developedcountriesgaveahigherpriority to increasedenvironmentalprotectionthan to
economicgrowth.Respondentsalsoindicatedawillingnessto pay higherpricesforsuch
protection.
Governmentshaveresponded to publicdemandforenvironmentalsafeguardswith
regulation.’ While environmental regulation in the United States has often meant increased
operatingcostsanduncertainty, ithas also provided an improvedenvironmentalinforma-
tion base.
Under the early U.S. environmental laws [the National Environmental Policy Act (1969),
the Clean Air Act (1970), the 1977 amendments to the Clean Air Act, the Federal Water Pol-
lution ControlAct (1972), and the 1977 amendmentsto the Federal Water Pollution Control Act
that, among other things, changed that act’s name to the Clean Water Act], industry could
readily and reliably estimate the costs associated with meeting environmental requirements,
allowing decision making to proceed in a familiar manner. While the requirements of increas-
ingly stringent environmental regulation led to rising costs for end-of-pipe treatment, these cost
increases were small in comparison to the costs that resulted from the of passage
CERCLA (the
Superfund act) in 1980. CERCLA and SARA (the 1986 Superfund Amendments and Reautho-
rization Act) changed the economicsof U.S. environmental regulation and industry’s view of
environmental responsibility and liability. Under CERCLA, the government imposed retroac-
tive strict liability for actions that were legal (and in some cases common practice) at the time
they occurred. Strict liability imposes legal responsibility for injuries even though the liable
parties were not negligent and did not intend to cause injury. Courts have also held that land-
owners keeping potentially dangerous substances on their land that are certain to cause injury
‘Command mechanisms whichdominate environmental regulation inthe United States [5], mandate that all polluters
achieve some specified standard of control on releases. The United States is not alone in its emphasis on command
mechanisms; numerous other countries, including Japan [3,6], France, Germany, and The Netherlands [7],rely pri-
marily on command mechanisms to achieve pollution control objectives.
Many economists view command mechanisms as inefficient and wasteful of society’s resources because they require
all emitters to achievethe same controlstandard regardless of cost to the individual firm or the cost per unit of pollution
reduction. In contrast, market mechanisms suchas taxes, subsidies, and tradable permits provide economic incentives
for desired behaviorsrather than mandating them. Economists generally prefer market mechanisms. However, the sharp
contrast frequently made between command mechanisms and market mechanisms in economic discussions may be
somewhat misleading because command mechanisms encompass a broad range of techniques, someof which are, like
market mechanisms, fairly sophisticated and cost-sensitive[7].Market mechanisms, while theoretically more efficient
than command mechanisms, represent an unknown. Governments havelittle experience with market techniques, and,
unlike command mechanisms, market mechanisms lack a recordclearly demonstrating their effectiveness [7].
216
Schramm and Schramm
to others or to others’ property if released, must make good the damages resulting from the
escape of such substances.
The potential environmental liabilities and uncertainty faced hy industry increased with
CERCLA. While it was understood in 1980 that CERCLA’s imposed liability represented a
substantial cost, its true magnitude was unclear. Time has clarified the cost; investigating and
cleaning up old waste sites has proved so expensive that involvement in a Superfund site as a
“potentially responsible party” may represent a liability sufficient to threaten the existence of
many firms. Cropper and Oates [7] argue that the imposition of strict liability places an ex-
pected value on pollutingactivities. The expected valuewould be the discounted costof a po-
tential future cleanup or compensation effort multiplied by the probability (<1.0) that the
action would be conducted. Such an estimate may be incalculable within reasonable limits of
certainty.* What can be ascertained, however, is that the potential liability may be extremely
large.
In addition toan implicit expected value assessment of liabilities in response to CERCLA,
other factors, particularly uncertainty,appear to be important. Very largeliabilitieslimit
management’s abilityto plan because of significantly increased uncertainty in its decision pro-
cess. Firms frequently cannot accurately determine the probability of their involvement with
CERCLA litigation, and it is difficult to effectively allocate resources when potential liabilities
(recognized or unrecognized) may exist that could dwarf investment plans. Uncertainty nega-
tively affects decision making because decision tools, such as cost-benefit analysis, cease to
provide reliable information when necessary inputs (e.g., costs and cash flows) cannot be es-
timated within reasonable confidence limit^.^
The retroactive natureof liability imposition under CERCLA is particularly significant be-
cause it suggests that compliance withcurrent laws and regulations is not adequate protection
against future retroactive laws [8]. Thus, firms do not know what standards their current ac-
tions may be held to in the future. The difficultyof managing this kind of uncertainty suggests
that the potential for liability should be avoided. Some firms have determined that this can be
done by minimizing releases of potentially offensive materials into the environment regardless
of current regulatory requirements.
The information available on industrial pollution in the United States has improved sig-
nificantly in the past two decades. Regulation, particularly SARA Title 111, has been respon-
sible for much of the improvement in data. This is because the statute requires the collection
of information onthe volume of materials that industrialfacilities release into the environment
or ship off-site. While the legislation does not require any pollution control activity on the part
of industry, it sheds light on releases for two important groups: the public and boards of di-
rectors of firms. Public access to information has led to increased public pressure to curtail
%e expected valuecalculation would require estimates of (1) the future release or emissions standard, (2) the prob-
ability that the firm would violate the unknown future standard, (3) the probability that the violation of the standard
would be recognized. (4) the probability that the firm would be held responsible for the waste of others that may be
commingled with that of the fii, (5) the future cleanup standard, and (6) the cost of meeting the cleanup standard.
%is type of uncertainty differs from normalrisk. Risk as addressed in insurance actuarial tables is associated with a
reasonably well defined probabilitydistribution. While uncertainty exists regarding an individual event’s probability of
occurrence under normal risk, sufficient information exists to limit uncertainty regarding the overall probability dis-
tribution. This, in effect, allows the quantification of risk (via a probability) andenables managers to make reasoned
provision for occurrences. However, significant uncertainty regarding an entire probability distribution is moredifficult
to address. This uncertainty may occur because the information availableto define a probability distribution may be
inadequate or unreliable. In the case of CERCLA or future CERCLA-like laws, uncertainty regarding the probability
distribution for CERCLA site involvement limitsthe ability of fums to estimate their involvement risk and therefore
to anticipate and plan for potential liabilities.
toAApproach
nvironmental
Management
Proactive 217
releases. Equally important, however, is the fact that data now exists that fully disclose the
magnitude of releases to the leaders of firms. Boards have begun to realize not only that current
practices may be setting firms up for future liabilities, but also that substantial quantities of
valuable resources are, in effect, being thrownaway.
These environmental constraints come at a time of increasing international competition. In
addition to demands for greater environmental protection, the public also demands greater
choice and quality in the products offered. Thus, industry must meet the challenge posed by
public environmental expectations in the context of other public demandsand growing inter-
national competition.
111. PROACTIVEENVIRONMENTALMANAGEMENT
Firms that have responded to the changed circumstances described above by implementing pro-
active environmental management programs are moving from a focus on problem management
to a focus on problem elimination. These firms have set goals to eliminate both the environ-
mental problem and associated costs.
F m s have demonstrated that proactive efforts to eliminate pollution and reduce waste
generation do not necessarily represent added costsand may enhance earnings and efficiency.
Problems, in effect, become opportunities to gain further insight into operations and
to suggest
process improvements. Experiences of these firms offer insights concerning the specific re-
quirements of successful environmental management efforts. This section describes the basic
features of environmental management programs that successfully respondto both new envi-
ronmental and competitive challenges. The essence of the approach will be familiar to those
acquainted with pollution prevention and waste minimization. These “guidelines” are pro-
vided by the experience of proactive firms. The implications of these proactive programsare
discussed in later sections. The suggested guidelines include
Treat the task seriously.
Invest the time needed to learn processes in intricate detail.
Set and clearly communicate goalshargets, and measure progress quantitatively.
Empower people to uncover and fix problems.
These guidelines are not revolutionary. Many would state “We do this now” and question
whether such guidelines offer much insight. As with many undertakings, success in environ-
mental management appears to be a matter of degree. It is likely that no firm applies (or ig-
nores) these guidelines in its operations100% of the time. Rewards will likely be proportional
to the consistent applicationof sincere effort. Successful programs will be those that obtain
and
sustain a strong commitment from the broadest spectrumof employees, particularly manage-
ment. In other words, successful programs will involve a significant cultural change. The re-
mainder of this section considers the guidelines listed above in more detail.
A. Treat the Task Seriously

Success in the elimination of pollution depends on the effective efforts of all employees. If
environmental issuesare viewed as solely the responsibility of an environmental department or
if input to production process modifications are provided solely by process engineers, the
needed commitment from other departmentsmay not be achieved. Further, if the firm fails to
maximize its use of available information, it may miss important insights. To a large extent, the
degree to which individuals within the firm accept the oftask eliminating pollution will depend
onthe“signals”delivered by uppermanagement.Topmanagementmust be absolutely
committed in word and deed and must be prepared to invest time andthe firm’s resources in the
effort. It is the responsibility of management to (1) increase the environmental awareness of
the firm’s personnel,(2) demonstrate the firm’s commitment, and (3) move the activitiesof the
firm from discussion to analysis and action.
Increasing awarenessof the problem means communicating with personnel frequently and
describing a clear “vision” of the course the firm intends to follow. Minnesota Mining and
Manufacturing (3M) states that the corporation’s ultimate environmental goal is to reduce
emissions to as close to zero as possible. With regard to corporately owned and operated fa-
cilities, Martin Marietta has told its employees, “We are going to get out of the business of
[generating]hazardouswaste.” The ChemicalManufacturersAssociation(CMA)hasan-
nounced that with regard to the reduction of emissions, “Improvement will be continuous,
there will be no cut-off in sight where companies can say we finished.” CMA notes that this
effort is intended to be“a fundamental changein the way the chemical industry will do busi-
ness” and has asked the publicto check on their progress. Theseare simple, vivid statements
of intent. What they share is a commitment to move beyond regulatory requirements. This
moves the focusof activity from oneof reacting to regulatory change to proactively addressing
the source of pollution problems within the firm and eventually allowing the firm to regain
control of its environmental agenda.
Awareness is not a one-way street, however. Officials with responsibility for environmental
management of several firms stress the importance of “putting light on problems” and indicate
that this requires a willingness on the part of personnel to bring problems forward. Awareness
of potential process modifications must, of necessity, move from the bottom up within the firm.
For many employees, participation in a proactive environmental management program will in-
volve a work activity, the contributionof their ideas, that isnew to them. Because the activity
is new, workers maysee it as a risk, and it is upto management to provide an environment that
ensures that this contribution is possible. This demands a willingness to listen and management
that stresses problem analysisand the search for solutions rather than blame.If problem anal-
ysis is directed at finding out who is responsible rather than what process changes are needed
to ensure that problems (including human error) do not recur, bottom-up communication is
undermined.Some firms haveestablished“hotlines” or ombudsmansystems to provide
paths for this information when employees do not feel they can communicate through their
supervisors.
The firm’s commitment to an environmental vision must be demonstrated by the active
involvement of top management, the commitment of appropriate levels of resources, and other
signals. A number of firms have taken opportunitiesto indicate that the issueof pollution re-
duction transcends economic considerations. For example, 3”s top management decided that
credits earned for “excess” emission reductions (beyond regulatory requirements) that are not
needed for future 3M expansion would not be sold, as allowed by existing legislation, but do-
nated back to regulatory agencies. Obtaining credits provides thefirm with greater flexibility
in meeting future production needs. The donation of excess credits sends a strong signal to
employees and others concerning the firm’s commitment.
At times, this commitmentmay appear to challenge short-term profit maximization goals.
In Florida, Martin Marietta Corporation decided to terminate a printed circuit line’s daily
100,OOO-gal discharge to a private utility. Although discharge to a local water body probably
would have been permissible, the company chose to eliminate most of the effluent through a
closed-loop system using ion-exchange columns. The change not only eliminated the effluent
concern but also improved process stability, significantly reducing wastage previously associ-
ated with the line. While savings as a resultof lowered wastage covered installation costs of the
closed loop system within18 months, the potential for the high level of process stability even-
AApproach
Proactive to Environmental
Management 219
tually achieved was notfully appreciated at first. Consequently, the short-term financial benefit
was not initially recognized.
It is this demonstration of a clear goal and the firm’s commitment that enables manage-
ment and employees to focus their energies onaction. Time spent discussingthe relative merits
of environmental statutes or regulations is time, energy, and focus that are not applied to the
analysis of operational processes. Finally, the active participation of employees is encouraged
by the knowledge that past employee input has been considered seriously and has to change.
led
Firms have used a variety of approaches to communicate this messageto employees, including
posting descriptions of successful process changes along production linesor near the worksta-
tions of the responsible individuals, printing and circulating such successdescriptions among
workers, or formally recognizing individuals involvedin successful changes.
B. Learn the Process

The word “process” here is very broadly defined. It incorporates all of a firm’s activities,
including management systems, product development, and means of dealing with customers
and suppliersin addition to whatare typically considered process engineeringactivities. Learn-
ing the firm’s processes means becoming intimately familiar with all phases of operations, be-
ginning with those process phases that involve targeted substances. This learning must cross all
phases of firm operations. For example, the solution tothe costly disposalof expired chemicals
may be better communication between users and purchasers anda change in purchasing pro-
cedures(e.g.,buyingchemicals in smaller quantities). Assessingprocessesnecessitates a
process-by-process inventory and cataloging of procedures, inputs, products, and wastes and
the development of a quantitative process baseline. Developingthe quantitative process inven-
tory requires a significant upfront “investment,” primarily in the form of time. The CMA
made the development of “quantitative inventories” the heart of its Code on Pollution Pre-
vention, and it is anticipated that this will be the most difficult part of implementing the code
for many firms [9]. The developmentof the process inventoryinitiates the firm’s learning pro-
cess and is essential to pollution preventiodwaste minimization efforts. Time invested in the
development of the inventory, however, is not an investment in the environment alone, since
this information baseis fundamental to sound management and to process improvement efforts
regardless of the specific goal.
C. Set Goals and Targets and Measure Progress Quantitatively

Deadlines are effective motivators. History providesa myriad of examples, large and small,of
seemingly impossible tasks accomplishedin limited time frames because a dedicated group of
people were given a clearly defined goal, adequate resources, anda deadline. Goals for envi-
ronmental performance have been put forth voluntarily and publicly by numerous firms. In
mid-1988, 3M stated that, using 1987 as a baseline, it intended to cut all hazardous and non-
hazardous releases to the air, water, and land by 90% and reduce the generation of waste by
50% by the year 2000. Martin Marietta committed itself to reducing emissions of 17 targeted
toxic chemicalsby 50% by 1992 and 75% by 1995. (Martin Marietta met its 1992 goal in 1990
and anticipates beating the 1995 target as well.) Corporate officials of various firms indicate
that such targets are essential as activity drivers and reminders of commitment.
Measuring progresstoward a deadline is valuable not only because itserves as a reminder
of the deadline but also because quantitative measurement provides feedback onthe direction
future activities should take and aids in the definition of priorities. Tom Peters, a well-known
management consultant, has noted simply that what gets measured, gets-done. Quantitative
measurements support analytic thinking about relationships among problems and other factors.
Quantitative measurement is also the root of statistical process control and total quality man-
agement. By examining the specific circumstances in which a problem emerges, insight can be
gained into possibilities for change. In some cases, just measuring the problem is enough to
precipitate change by giving employees feedback on operations. By clearly identifying the
source and magnitude of undesirable effects, all involved have the opportunity to consider and
recommend possible improvements.
D. Empower People to Fix Problems

Empowering employees involves both communication and support. Communication includes
defining the firm’s goals, as previously discussed, and communicating detailed objectives and
process performance information. Information regarding processes is important to both the un-
covering of potential areas of improvement and the development of solutions. Empowerment
requires that this process-related information be available to all those affected by the problem
or by the potential solution. This information sharing is vital if those who have direct insight
into the processes being evaluated (such as line personnel and process engineers) are to give
informed consideration to problem assessments and proposed solutions.
Since it is extremely rare that one individual has all the information relevant to the eval-
uation of a situation and because solutions do not always fall neatly within departmental areas
of responsibility, pooled efforts are required. Seeking the input of others and collectively as-
sessing information and information needs supports employee efforts by limiting information
gaps, oversights, miscommunications, and wasted time. Additionally, communication and in-
put from the full spectrum of those affected is required to prevent situations in which different
groups addressing related problems work at cross-purposes. As change that has not been prop-
erly considered may be disruptive, firms equip employees for proactive change by supporting
the development of a discipline of thoroughness, preparation , coordination , and inclusion.
Firms have also attempted to support employees by establishing clear procedures for raising
suggestions and by training workers in analytic tools and methods, such as statistical process
control, for uncovering and examining problem sources.
IV. Results and Implications of Proactive Environmental Management

for Firm Competitiveness
The experience of proactive firms indicates that significant reductions in the generation or re-
lease of wastes are not only possible but may be achieved within limited periods of time. With
its voluntary Pollution Prevention Pays program, 3M cut its hazardous waste generation by
nearly 50% between 1980 and 1990. The member companies of the CMA reduced total releases
(air, water, land, and underground injection) by 35% between 1987 and the end of 1990. In a
period of 3 years, Martin Marietta Corporation cut hazardous waste generation by 80% and cut
releases of both ozone-depleting and toxic chemicals by 65%. In fact, in the first year of its
hazardous waste reduction program, Martin Marietta cut hazardous waste generation by 47%.
Numbers such as these suggest that substantive reductions are not dependent upon the devel-
opment and implementation of complex new technologies. It is unlikely that such technologies
could have been developed and implemented in one year. These results further suggest that the
payback period on these efforts is brief, a suggestion confirmed by an EPA study of 28 firms
that found that 54% of the waste reduction efforts undertaken paid back the initial investment
in less than one year [lo].
While the solutions used to achieve these results were often innovative and imaginative,
they frequently represented modest improvements in the way things were done, and surpris-
A Proactive Approach to Environmental Management 221
ingly few were high tech. This suggests that long before high tech solutions can be developed,
less technical solutions (e.g. , operational changes) are developed that are simpler, cheaper, and
more readily implemented. It appears to many in industry with responsibility for environmental
management that state-of-the-arttechnological capabilities are simply not a major limiting fac-
tor in determining the success of efforts to reduce waste generation. Further, although outside
consultants may offer insights, the experience of firms seems to indicate that the identification
and solution of most pollution problems are situation-specific and are therefore best developed
internally by those with the most direct and detailed knowledge of the situation. The message
appears to be “Have faith in your people.”
The economic results, like the environmental results, of proactive environmental manage-
ment have been impressive. Dow Chemical’s Louisiana Division reduced waste production by
250 million pounds and saved $5.2 million between 1984 and 1990. During the period 1975-
1989, 3M Corporation not only cut its pollution per unit of production in half, but by its own
accounting realized cumulative cost savings of $500 million. Cost savings occurred in the form
of cost reductions in meeting environmental and worker safety objectives and reduced opera-
tional costs associated with more efficient resource use. For example, in Cottage Grove, Min-
nesota, 3M discharged an 8% ammonium sulfate solution into the facility’s wastewater
treatment facility. Regulations required a reduction in the ammonia content of effluent. The
company installed a system that removed ammonium sulfate from the waste stream before di-
lution in the wastewater treatment facility made recovery impractical. The compression evap-
oration equipment that was installed strips ammonia until a 40% solution, which is marketable
as fertilizer, is achieved. The $1.5 million removal system eliminated the need for $1 million
worth of downstream control equipment and produced annual fertilizer sales of $150,000.
Positive economic results have been achieved by smaller firms as well. In 1986, Cleo-
Wrap, a producer of gift wrapping paper in Memphis, Tennessee, completed a conversion from
solvent-based inks to water-based inks. The conversion reduced waste disposal costs by
$35,000 annually, resulted in lower fire insurance premiums, and eliminated the need for un-
derground storage tanks (USTs) for solvents. The elimination of USTs allowed the firm to avoid
involvement with federal UST regulations.
Additionally, firms may recognize increased revenues as a result of product improvements
and the development of new market niches. For example, when Martin Marietta decided to
remove chromium from various products produced for the steel industry, it was predicted that
revenues would decline as a result of the action. Revenues did decline initially, until the steel
industry recognized that products that met their specification without chromium content were
available. Sales and revenues then rebounded and surpassed previous levels.
Numerous corporate officials with responsibility for environmental management suggest
that their firms would have been foolish not to make environmentally motivated process
changes for purely economic reasons. However, the need for and benefits of change were not
recognized until environmental concerns necessitated a search for process improvements and
brought the opportunities to top management’s attention. This raises the question, which we
consider later, as to why such large potential economic benefits went unrecognized for so long.
The goal of merely controlling pollution is being questioned as firms address liability is-
sues; recognize that pollution control, at best, transfers contaminants from one medium to an-
other; and evaluate the waste of valuable resources under current practices. This is spurring
many firms to move beyond a focus on regulatory compliance by establishing internal goals
with the intent of exceeding regulatory requirements. In this way, firms may lift many regula-
tory requirements on operations and enhance their flexibility in planning and decision making.
Efforts under way at 3M are explained this way: “Conventional control only constrains the
[pollution] problem temporarily; it does not eliminate the problem.’’ With the objective of
222
Schramm and Schramm
eliminating the pollution problem, 3”s “ultimate goal is to reduce emissions to as close to
zero as possible.” In accordance with this goal, efforts have been initiated that “will take 3M
from a position of compliance with government regulations to being substantially under the
limitations established by the regulations.” DuPont Corporation, too, has stated that the “ul-
timate goal is zero pollution in all activities” [ll]. DuPont’s chief executive officer, EdgarS.
Wollard, Jr., stated.
The environmental challengeis not one of responding to the next regulatory proposal.Nor
is it making the environmentalists see things our way. Nor is it educating the public to
appreciate the benefitsof our products and thus tolerate
to their environmental impacts and
those of the processes usedto make them. Our continued existence asa leading manufac-
turer requires that we excel in environmental performance and that we enjoy the nonob-
jection-indeed the support-of the people andgovernmentsin societies where we
operate around the world. I’m calling fora corporate environmentalism, which I define as
an attitude and a performance commitmentthat places corporate environmental steward-
ship fully in line with public desires and expectations.
In fact, entire industries have adoptedthis approach. The CMAinitiated their Responsible Care
program in 1988, in part due to a recognition of the need to address the public’s perception of
the industry. In this program, member firms commit themselves to “continually improve per-
formance in the areas of health, safety, and environmental quality,” to do a better job of elic-
iting and respondingto public concerns about products and operations, and to make available
to the public detailed performance measurements forthe purpose of judging industry progress.
The actions that constitute proactive environmental management programs have much in
common with the efforts of certain Japanese firms to improve product quality and process
efficiency. The Japanese practices have been referred to as a “continuous improvement” ap-
proach to production. Similarities between proactive environmental management and contin-
uous improvement involve establishing and committing to goals, integrating both improvement
efforts and normaloperations across functional divisions,and continually analyzingoperations
for appropriate modifications. Given the documented role of continuous improvement in im-
proving the qualityof Japanese productsand the efficiencyof Japanese industry, itshould, per-
haps, not be surprising that proactive environmental management has yielded benefits in areas
of product quality and process efficiency as well as in achieving environmental goals. Theex-
perience of proactive environmental management indicatesthat improvements in process and
resource use efficiency andin product quality that accompany proactive efforts change the eco-
nomics of environmental management. Achieving environmental goals does not necessarily
represent an additional cost and need not, in all cases, reduce othercorporate investments. This
is significant because the opposite concept, that environmental management necessarily rep-
resents an added cost, has long been assumed by the management of many firms.
With regard to international competition, Piasecki and Asmus [l21 note that many Euro-
pean firms combine economic motives and environmental goals through an emphasis on three
principles: conserve energy, save materials, and reduce waste. In fact, some European man-
agers “see waste reduction as a comprehensive strategy to cut production costs, spur innova-
tion and promoteinternational competitiveness” [lo]. There is some precedence for thisview.
Japan realized major benefits from actions its industry took in response to the oil price shocks
and environmental legislation of the 1970s.
In the early 1970s, the Japanese parliament passed antipollution legislationthat is among
the strictest in the world. At the same time, Japan imported 99.8% ofits oil [6]. The oilprice
increasesandinvestmentsforpollutioncontrol of the 1970srepresentedmassivecostsfor
Japanese industry that threatened the profitability of firms and, indeed, their very existence.
oactive
roach A to Environmental
Management 223
Japanese industry was forced to seriously address both energyuse and environmental quality,
and the response of industry to these demands is credited with playing a significant role in
inducing the rapid progress of Japan’s industrial technology [13]. These efficiency and tech-
nological gains positioned the Japanese to capitalize on changing market demands.As a result,
Japan realized direct gains in competitiveness from their responseto energy and environmental
constraints. For example, Japanese standards for NO, emissions from automobiles, when ini-
tially established, were generally considered “unmeetable.” Nonetheless,in a matter of years,
several automobile manufacturers had developed the technology to meetthe standards [3]. Ja-
pan’s domestic efforts to reduce air pollution gave ita competitive edge in the world automo-
bile market [14]. This and the fuel efficiency of Japanese cars, which improved as a result
of the energy constraint at home, contributed to Japan’s successful entry into the U.S. auto
market.
V. OBSTACLES TO ADOPTING A PROACTIVE APPROACH

Traditional management approaches and corporate cultures can present substantial obstacles to
finding and implementing changes to existing methods. An emphasis on short-term financial
indicators to the detriment of more fundamental measures of operational excellence, a culture
of blame, and a rigid segmentation along functional or hierarchical lines can easily obscure
opportunities to advance corporate performance.
Short-term financial indicators by themselves are inadequate to provide insight into the
opportunities for improvingfirm operations, and a focus on these indicatorsto the exclusion of
other performance measures is one possible reason thatthe potential economic benefits of some
environmentally related process changes went unrecognized for years and in some cases de-
cades. Yet the meaningful utilization of other performance measures requires an understanding
by top management of the importance of operational improvement to the long-term financial
stability and competitiveness of the firm.
A focus on blame,rather than understanding how and why problems arise, precludes dis-
covering inherent flaws in procedures. Firms need to determine, regardless of individual cul-
pability, what in the management system allows problems to occur. Root causes are a matter of
system characteristics that allow problems to develop and individuals to makeerrors. Evalua-
tion that assigns an individual responsibility for
a problem may provide a sense of having solved
the problem while, in fact, the root cause remains undetermined and the flawed system un-
changed.
A lack of shared responsibility and cooperation resulting from organizational barriers be-
tween levels and stages of firm activities stands in the way of improving operations. Process
success fromthe standpoint of overall system effectivenessmay be quite low even with super-
lative performance on the basis of individual departmental criteria, if those criteria fail to
reflect overall system success. For example, implementing solutions to problems that are un-
covered requires flexibility in the use of operational funds. If financial management systems
place excessive restrictions on the application (or redirection) of funding, the motivation to
implement improvementsmay falter. This may be a problem in any organization, but it is par-
ticularly problematic in government organizations. Environmental considerations are more ef-
fectively dealt with when integrated into every activity of the firm. A functionally restricted
approach leaves environmental improvementas an activity apart from normal operations and
gives no incentive forothers to take responsibilityor initiative in finding opportunities to elim-
inate problems before they begin.
Overcoming these culturalbarriers depends on theattitudes and commitment demonstrated
by top management within a firm. Efforts by others in the firm will not be sustained if cor-
porate actions appearto contradict, downplay,or otherwise fail to support the task. The lead-
ership needed to overcome these obstacles requires genuine commitment and vision by man-
agement in order to guide a rethinking of firm practices at the most fundamental levels.
VI. CONCLUSION
In addressing environmentalobjectives, industry has historically focused on end-of-pipe treat-
ment and compliance with governmentally imposed pollution standards. Changesin corporate
legal responsibilitiesas a result of environmental legislation(particularly CERCLA) and evolv-
ing social views toward environmental issues worldwide have led many firms to question the
premises on which they previously based their environmental management programs. A new
premise-that environmentally responsible corporate policies are notmerely economically
beneficial but essential to corporate survival in a changing legal and social environment-is
emerging. As a result, these firms have focused not on regulatory compliance but onthe goal
of eliminating waste generation and pollution resulting from their operations. The results of
these proactive environmental management programs suggest that internalizing responsibility
for the reduction of pollution and establishing stringent voluntary targets for reductions en-
courages actions that broadenthe environmental protection optionsinvestigated, enhance en-
vironmentalmanagementeffectiveness,reducecompliance costs, andlimit the uncertainty
firms face in the environmental arena.
Proactive environmental management programsstrive to use the skills and knowledge of
all employeesby increasing employee awareness viaclearly defined environmental goals, an-
alyzing all firm activities quantitatively, setting and measuring progress toward targets based
on overall goals, and equipping employeesto uncover and solve problems.
A growing body of evidence suggests not only that this proactive approach to environmen-
tal management improves environmental performance, butalso that the continuous process re-
view employed improves understanding of operations, thereby contributing to more efficient
resource use, reduced costs, and improved product quality. Thus, proactive environmental in-
itiatives appear to have beneficial spin-off effects that improve a firm’s competitive capabili-
ties.Thesenonenvironmentalbenefitsseemtoresultfrom characteristics of a proactive
environmental approachthat are similar to the Japanese continuous improvement methodology
for improving product quality and industrial efficiency.
REFERENCES
1. Cole, W. E., Mogab, J. W., and Sanders, R. D., The continuous improvement fwm: implications for
economicanalysis,internationalcompetition, and technology transfer,WorkingPaper No.269,
Univ. Tennessee, May 1992.
2. Coombes, P,Responsible c m : a journey of profound cultural change, Chem. Week, July 17, 1991,
p. 5 .
3. hud’homme, R., Appraisal of environmental policies in Japan, inEconomic Growth and Resources,
Vol. 5 , Problems Related to Japan (S. Tsuru, e d . ) , St. Martin’s Press, New York, 1978, pp. 193-
208.
4. Dunlap, R. E.,Gallup, G. H., Jr., and Gallup, A. M., The Healzh ofthe Planet Survey, George H.
Gallup International Institute, Princeton, N.J., July, 1992.
5. Butler, W. A., Incentives for conservation, inEcology, Economics, Ethics:The Broken Circle (F. H.
Bormann and S. R. Kellert, eds.), Yale Univ. Press, New Haven, Conn., 1 9 9 1 , pp. 180-195.
6. Barrett, B. F. D., and Therivel, R., Environmental Policy and Impact Assessment in Japan, Rout-
ledge, New York, 1991.
7. Cropper, M. L., and Oates, W. E., Environmental economics: a survey, J . Econ. Lit., 30(2),June
1992, pp. 675-740.
A Proactive Approach toEnvironmental Management 225
8. Freeze, R. A., and Cherry, J. A., What has gone wrong?, Groundwater, 27(4) (1989).
9. Rotman, D.,Pushingpollutionprevention, Chem. Week. July 17, 1991, p. 14.
10. Hirshhorn, J. S., Cutting production of hazardous waste, Technol. Rev., 91, 52-61 (1988).
11.Kirkpatrick, D.,Environmentalism:thenewcrusade. Fortune, Feb. 12, 1990, pp. 44-55.
12. Piasecki, B., and Asmus, F!, In Search of Environmental Excellence: Moving Beyond Blame, Simon
& SchusterlTouchstone, New York, 1 9 9 0 .
13. Watanabe, C., Santoso, I., and Widayanti, T.,The Inducing Paver of Japanese Technological In-
novation. Pinter, London, 1991.
14. The Economist, The endless road a survey of the car industry, Oct. 17-23, 1992.
10
Health Hazards Associated with
Pollution Control and Waste
Minimization
Patick D.Owens
Tosco Rejlning Company
Martinez, California
I. INTRODUCTION
This chapter focuses onthe need for engineering controlsto reduce the risk of adverse health
effects due to occupational exposures at hazardous waste treatment, storage, and disposal fa-
cilities. From a management perspective, the best opportunity for preventing adverse health
effects lies with engineers who can recognize the potential risks while designing processes for
waste minimization. Oneof the first steps toward reducing riskis the awarenessof the etiology
of the adverse health effect. In some cases, once an engineer becomes aware of a potential
problem, the solution to reducing the risk is apparent. Therefore this chapter begins with a
discussion of identification and prevention of health hazards. Examplesare presented of work-
related hazards found in general industry and in several emerging hazardous waste treatment
technologies.
II. HEALTHHAZARDRECOGNITION
In any remediation, pollution control, or waste minimization activity there exists the need to
recognize and prevent occupational disease. When designing for chemical process pollution
control and waste minimization, the engineer must consider the human element. Those design-
ing processes for hazardous waste handling should consider the potential exposures of person-
nel operating the process. If engineers knowof the potential adverse health effects of the
hazardous materials and other agents, then the design can incorporate methods to reduce these
effects on workers and nearby residents. In many cases, the design stage is the critical time to
incorporate safety measures. During the design stage of a Superfund remediation project,the
designer is responsibleforunderstanding andcomplyingwiththeboundaries of29 CFR
1910.120 and for describing the reasons for the boundaries’ locations [l]. In addition, retro-
fitting a process is costly and time-consuming. Two examples of costly mistakes are the im-
provement of local exhaust ventilation in a chemical lab to reduce worker exposureto volatile
227
228 Owens
organics each time the exposure limit decreases and the purchase of a less expensive, noisier
motor that then requires a motor intake silencerto reduce the sound pressure level.
In somecases, the etiology of a disease is attributed to a known agent. If a process includes
that agent, the design goal should be to reduce all exposures to the agent. By identifying the
specific agents present at a site and including ventilation, material substitution, or isolation,
the designer may prevent the possibility of occupational disease.
The recognitionof occupational diseaseand the steps leading to it is the key element in the
prevention of the disease. Many occupational diseases are attributed to specific etiology and
therefore are relatively easyto identify. Physical agents suchas electron beam sources thatlead
to mutations are easily identifiable. Other hazardsarise from known exposures to identified air
contaminants. For instance, eye and respiratory tract irritation arise from acute exposure to
hydrogen sulfide in the petroleum industry. Asbestosis or lung cancer can result from yearsof
handling asbestos insulation. Other work-related adverse health effects have multiple causes or
unknown causes. For instance, increased renal cancerdeaths in the petroleum and steel indus-
tries have not been related to a specific agent [2].
The fields of epidemiology and occupational medicine provide guidance in determining
specific causes of disease. However, when dealing with hazardous material and emerging tech-
nology, there is a need to recognize potential sourcesof exposures at a specific site. Once the
potential sources of exposure and disease are identified, prevention is the next step toward a
safer workplace. However, identifying the potential dangers for hazardous waste workers is
difficult because hazardous waste streams vary from site to site and may vary from day to day
at any one site.
Of utmost importancein recognizing occupationaldisease is the identification of all agents
present in the workplace that, alone or with other materials, are capable of causing adverse
health effects. Agents are divided into two broad categories: physical and chemical. Common
agents include noise, solvents, heavy metals, and temperature extremes. The list of harmful
agents also includes ionizing radiation, infectious agents, and musculoskeletal stressors. At a
typical hazardous wastesite a single physical agent, such as vibration, may not pose a signif-
icant risk; however, in combination withother stressors it may have an additive or synergistic
effect. For instance, workers requiredto wear personal protective equipmentmay be more sus-
ceptible to heat illnesses, rashes, and allergies.
For each physical task, answer the following questions: How close, how long, how often,
and under what conditions? For each task or job, examine the workers’ interaction with their
equipment. Jobs that typically lead to physical ailments include those that require repetitive
motions, awkward positions, prolonged lack of movement, and/or exposure to extreme tem-
peratures. The combinationof low temperature and repetitive motion have led torepetitive mo-
tion syndrome, for example.
A. Identification
Identification of potential health hazardsa learned
is skill, and proficiency in it can be attained
by evaluating work practices. Many adverse health effects are due to acute exposure to con-
taminants,especiallyconcentratedchemicalagents.Whenever a concentratedchemical is
present, there isa potential for harmful exposure. It is importantbe toespecially cautiouswith
chemicals that require periodic replacement because of evaporation. Even light solvent evap-
oration may result in personnel exposure and adverse health effects.
Solid material lost in processes involving cutting, grinding, drilling, or pulverizing may
also cause adverse health effects. For instance, invisible carbide steel grinding fines may result
in overexposure to agents that produce pulmonary sensitization and cancer. One way to check
Control
zards Health
Pollution and 229
for airborne dusts is to observe surfaces for accumulated dust;however, this only signifies that
a dust source is present, not the degree of hazard. Also, any chemical that visibly state,
changes
for example, from a liquidto a solid, may be an exposure point. Even if the material does not
visibly change, heating a solid can liberate fumes. Off-gassing of new carpets, particleboard,
and plywood has been implicated as the source of formaldehyde in indoor air quality com-
plaints. Stirred, heated, or agitated liquidsmay generate mists, fumes,or fogs that are invisible
to the naked eye. These and other processes are keyto identifying potential exposure sources.
B. Prevention
Prevention of occupational disease should beone of the engineer’s objectives when designing
a hazardous waste handling facility. The purpose of handling the hazardous waste in the first
place is to reduce the riskof harm to humans. Therefore, it isof utmost importanceto protect
those workers who typically work closely with the material. The design of these advancing
technologies should intentionally and actively incorporate a concern for human health and
safety. Asking facility operators for their input on new processes may go a long way toward
maintaining a happy and healthy work force. In addition, the EPA “strongly endorses an open
communication policy in which all health and safety inquiries receive a prompt, professional
response”[l]. Workers and facility operators are more likely to adopt a new process when their
ideas are incorporated into the design. Some people are skeptical of new processes because of
experiences associated with past “wonder products” such as asbestos. Workers may adopt a
new facility if they can examine the proposed design for hidden risks. And these risks, if any
are found, should be addressed by the engineer.
Newly legislated and anticipated occupational regulations pose challenges to the engineer
who is designing a facility that should operate for several years. new
A amendment soon to be
law or an amendment to an existing regulation may instate or lower an exposure limit and
thereby require retrofitting of existing processes or relocation of site boundariesand zones of
contamination.
C. OccupationalRegulationsandRecommendations
The Occupational Safety and Health Administration (OSHA) regulates occupational hazards.
In doing so, OSHA defines exposure limits for substances, monitoring requirements, control
methods, andmany other items. Engineers shouldbe aware of changing exposure limitsas well
as control methods for hazardous environments. As an example of the former, consider the re-
cent changes for the OSHA 8-hr Permissible Exposure Limit (PEL) for benzene, knowna car-
cinogen. Several years ago, OSHA lowered its 10 parts per million (pprn) limit to l ppm.
Presently, OSHA is considering a 0.1 ppm limit, which represents a significant drop from the
original exposure limit. OSHA also requires specific control methods for workers exposedto
one-half the exposure limit, and the first choice lies with engineering measures. Ventilation,
isolation, substitution, etc., mustbe the first line of defense employed by the engineto reduce
exposure. However, an engineer who designs a complete ventilation system to reduce exposure
from 50 ppm to 10 ppm could be wasting time and money if the exposure limit drops later.
Therefore, to plan properly, engineers need to stay current with OSHA regulatory require-
ments, International Agency for Research on Cancer (IARC) classifications, toxicologic data,
and epidemiologic studiesto determine to reduce the PEL. Undoubtedly, the safest engineering
designs will reduce all carcinogenic exposures to as low as reasonably achievable.
The Occupational Health and Safety Administration (OSHA), which guarantees the right
to a safe and healthful workplace, mandates that the first step taken to minimize occupational
exposure be “engineering protective measures.” A caretidly engineered facility may provide a
230 Owens
low-risk workplace that leads to the prevention of occupational disease. On such case study in
the proper designof a hazardous waste processing unit involved metals in a caustic stream[3].
In this design, ventilation successfully reduced worker exposure to hazardous waste.
1. Hazwoper
In addition, OSHA requires safety and health activities for hazardous waste operations, in-
cluding treatment, storage,and disposal facilities, uncontrolled waste sites, and also any emer-
gency responses for hazardous materials. The regulations cover employee protection during
initial site characterization, air monitoring for employees, precautions for material handling,
training, and emergency response capabilities [l]. For instance, the employer must write a site-
specific healthand safety plan;however, a general plan may be used for all but the site-specific
activities if the owner has multiple locations. Site-specific activities include analyzing tasks
and warning workers of both the known and potential hazards presentat that site. This training
requirement includes contractors. The final design should include (1) an estimateof increased
hazards (over background),(2) degree of hazard based on the contamination,(3) standards for
protection of workers and the public, (4) “safe” contaminant concentrations and levels mea-
sured at the site, and ( 5 ) emergency responseand evacuation plans. Also, the employer should
provide an emergency response plan with written procedures for responding to on- and off-site
accidents.
Some of the specific requirements that can be included in facility plans are eyewash and
shower equipment, spill and overflow control, storage location for hazardous substances, and
specific processes for treatment and handling of hazardous substances. Facilities in which em-
ployees handle eye corrosives, irritants,or toxins absorbable through the skin must be provided
with eyewash and shower equipment. The eyewash station must be located where an affected
employee can get to it within 10 s e c . In addition, if an employee needs both the eyewashand
shower simultaneously, the station mustbe designed so that the employee can use both simul-
taneously. The American National Standards Institute (ANSI)Standard 2358.1-1981 provides
detailed information on eyewash station design and placement.
Zoning remediation sites provides a clear indication of the locations of hazards. And, de-
pending on the toxins present, zoning defines the level and type of personal protective equip
ment. Also, it helps reduce the spread of contaminants into support zones where workerseat,
smoke, or drink. The contaminant reduction zone should be far enough fromthe source to re-
duce exposure potential to decontamination workers. The contaminant reduction zone may en-
compass several hot zones provided that the workers follow the decontamination procedures for
each agent [4]. Of course, workers exiting a hot zone must remove protective clothing in an
orderly fashion to prevent hand or face contact, and the used clothing should be bagged and
labeled to warn other personnel of the contentsof the bags.
The Superfund Remedial Design (RD) and Remedial Action (RA) Guidance Document
provides assistance to privateparties who are designing remediation measures. Currently, the
document is being revised to include a health and safety chapter. The pertinent items to address
at any remediation site include identifying potential worker exposures, making agreements
with community emergency responders, and defining roles and responsibilities of all the in-
volved personnel. The central theme is the identification of hazards via task analysis. One key
design feature of a safer site is the regulatory site-specific health and safety plan, which in-
cludesmeteorologicalmonitoring,downwindandperimeterairmonitoring,personnelair
monitoring, dust suppression, zoning, decontamination areas, and specific health and safety
controls.
Some of the regulations that pertain to hazardous material handling are confusing. For
instance, two separate regulations applyto site remediation; these areOSHA‘s General Indus-
Health Hazards and Pollution Control 231
try Standard (Part 1910) and Construction Standard(Part 1926). Both regulations apply during
remediation projects; however, they cover similar points. When deciding which regulation ap-
plies, use the more protective standard. As another example,EPA fugitive emission standards
presently require abatement of emissions from equipment that emits10,OOO parts of hydrocar-
bon per million parts of air (ppm). In contrast, the Occupational Safety and Health Adminis-
tration (OSHA) regulates the workplace exposure to benzene at 1 ppm, andCalOSHAhas
proposed a limit of 0.1 ppm. In some industries, workers required to abate the EPA “air tox-
ics” emissions may be overexposed to benzene. In this case, the environmental and occupa-
tional acceptable concentrations differby four orders of magnitude.
2. ExposureLimits
While OSHA Permissible Exposure Limits (PELS) carry the weight of law,the American Con-
ference of Governmental Industrial Hygienists (ACGIH) Threshold Limit Values (TLVs) do
not. A panel of scientists, physicians, and engineers who have worked in industry or who have
knowledge of industrial processes develop the TLVs. OSHA has adopted many of the TLVs in
the past, and OSHA’s 1910.120 regulation specifically defersto the use of the TLV when it is
stricter than the PEL [5]. There are certain contaminants for which the PEL is more stringent
than the TLV,andOSHAusually regulates these Contaminants as carcinogens. Hexavalent
chromium compounds, formaldehyde, and benzene are a few of these chemicals.The best man-
agement practice consists of designing processes that attempt to reduce exposures to carcino-
gensto as low as achievable. The National Institute for OccupationalSafetyandHealth
(NIOSH) also publishes recommended occupational exposure limits called RELs. addition, In
the American Industrial Hygiene Association (AIHA) publishes a list of exposure limits called
Workplace Environmental Exposure Levels (WEELs). Theselimits, developed and published
by professionals in the field of industrial hygiene, do not carry the weight of law; however,
similar to the TLVs, the WEELs cover some contaminants not addressed by OSHA. For in-
stance, methyl tert-butyl ether (MTBE), one of the “clean gasoline” additives, has a WEEL
but no PEL.
When handling, concentrating, or treating a variety of solvents, one must be aware of cer-
tain potentiating health hazards. For instance, toluene and some chlorinated hydrocarbons act
synergistically to induce liver disease. In these cases, extreme caution must be taken in com-
paring exposure monitoring results for each compoundto its respective occupational exposure
limit. For agents acting on the same target organ with similar modes of action, a weighted
average of the exposure limitsfor both compounds usually adequately representsthe degree of
health hazard present.
In addition to engineering control methods, OSHA requires special control of areas where
known exposures to carcinogenic or regulated materials exceedthe exposure limits. Suchareas
require posting of contaminant-specific warning signs and control of the personnel working in
the area. The design of a work area should include clearly marked entrances and exits and
locate personnel and equipment decontamination stations at exits from “hot” zones. In addi-
tion, areas not subject to remediation should beisolated, thus preventing exposure to workers
outside the hot or contaminated zone. This may not always be possible, especially with air-
borne contaminants, but there are other methods for controlling these contaminants. Fixed-
point air-monitoring stations positioned at the edge of the hot zone or site perimeter with
alarms set at appropriate levels have been used successfully at hazardous waste sites [6]. The
latest technology for vapor or gas continuous monitoring is open-path Fourier-transform in-
frared spectrometry,which may be used as a short-term or hourly concentration-averaging de-
vice. When workers handle a chemical with an established PEL, OSHA requires personal air
monitoring data to define each potentially exposed worker’s exposure concentration. If no site-
232 Owens
specific data are obtained, an employer may be liable when specifying what level of personal
protective equipment workers mustwear.
When deciding how to design a waste treatment process, one must consider the toxicity of
the material. If the material is regulated as a carcinogen by OSHA, then specific regulations
apply. These require engineering controlsto reduce exposuresto as low as reasonably achiev-
able. Although OSHA may not classify an agent as carcinogenic, other regulatory agencies,
such as the International Agency for Research on Cancer (IARC), publish lists of suspected,
probable, or possible carcinogens. If IARC identifies the agent as a potential or probable hu-
man carcinogen, the wise engineer takes steps to reduce exposures before OSHA promulgates
regulations requiring engineering controls.
A contaminant’s toxicityand physical and chemical characteristics determine how workers
and engineers handleit to reduce possible exposure.If at all possible, engineers should design
facilities requiring no additional chemical treatment. Engineers designing chemical treatment
processes should consider using the most economical material with the highest occupational
exposure limit. Often, the higher the exposure limit, the less toxicthe chemical. The engineer
must also consider the route of intake by the chemical. If the route is inhalation, using a less
volatile chemical may reduce exposure. Many exposure limit concentrations are so low that
overexposure may occur in unexpected cases. For instance, less than 0.1% lead in paint has
been shown to overexpose welders, cutters, or grinders to lead fumes and dust. Other contam-
inants may be organic compounds, pesticides,or minerals. Anothercase involved heating poly-
ethylene floor covering, which liberated enough formaldehyde to approach the recently reduced
exposure limit. The contaminants frequently found on hazardous waste sites include benzene,
arsenic, asbestos, beryllium, cadmium, carbon tetrachloride, chloroform, chromates, cobalt,
ethylene dibromide, formaldehyde, methylene chloride, B-naphthalene, nickel, vinyl chloride,
and vinyl bromide.
3. HazardCommunication
OSHA’s Hazard Communication Standard (HAZCOM) requires a written program to describe
and identify all hazardous chemicals in the workplace except Resource Conservationand Re-
covery Act listed waste. The facility must have a listof all the hazardous chemicals used in the
workplace. There mustbe training methods for handling all these chemicals and suggested pro-
tective measures for possible exposure areas. In addition, all containers leaving the workplace
must be labeled with the chemical identity, appropriate hazard warnings, and the name of the
responsible party, Installing computers that have hazard material warning information stored i
a database is one method of providing information about material stored in vessels or tanks.
Material safety data sheets (MSDSs) for purchased chemicals must be kept in a readily acces-
sible location for each worker.
Engineers who subcontract work on a site should identify all contamination on the site and
inform workers of potential exposure. This may require taking samples soil, water, and/or
of the
air long before any work occurs. Hazardous material warning sheets or other written informa-
tion on the site-specific contamination canbe distributed to the workers or supervisors. In ad-
dition, an emergency evacuation plan mustbe developed and discussed with the subcontractor.
111. HEALTH HAZARDS ASSOCIATED WITH GENERAL INDUSTRY

A. ChemicalAgents
Chemical agents suchas solvents or hydrocarbons may have multiple effects on many different
body systems. Solvents are ubiquitous at hazardous waste sites; therefore, there is a good
chance that workers handling hazardous waste will be exposed to one or more solvents. For
Control
zards Health
Pollution and 233
many of these agents, the adverse effect is seen relatively soon, so the cause of the effect is
identifiable; with some carcinogenic agents that may cause cancer years later, the link between
the agentand the disease is less clear. When workers handle mixtures of solvents, the etiology
of the disease may be difficult to determine. In some cases, epidemiologic studies provide in-
formation on the etiology of the disease.
1. Solvents
Organic chemicals can cause many different adverse health effects. Solvents or hydrocarbons
present at a site may cause specific symptoms suchas dizziness, eczema, and chloracne. One
may see respiratory tract irritation from inhalation,or skin irritation from skin contact. There-
fore, the routeof exposure determines,to some extent, the chemical’s effect and site of action.
Skin diseases canbe reduced by designing equipment that reduces skin contact. Designs should
eliminate the need for manual contact with material and avoid equipment that unnecessarily
heats, agitates, or stirs a material. However, if engineering precautions such as local exhaust
ventilation are implemented, workers should be adequately protected.
For inhalation hazards such as air sparging of contaminated soil, engineering solutions
may include ventilation of the off-gases. When engineering control methods fail to reduce ex-
posures to below the OSHA PEL, workers must wear personal protective equipment. OSHA
requires the use of properly fitted respirators only when an engineering solution is being de-
veloped or if all other engineeringor administrative controls fail. In addition to inhalation haz-
ards, diseases occurwhen workers ingest hydrocarbons, metals, and other agents. Likely times
include breaks when workers eat, drink, or smoke. Engineers should design facilities with
break rooms or areas that are separated from the workplace by a washing station and some
means of preventing dust, fumes, or mist from being carried by convection currents into the
break area. Besides the organic agents posing ingestion hazards, some metallic agents can pose
ingestion or skin contact hazards; examples are silver, arsenic, beryllium, cadmium, chromium,
mercury, nickel, lead, selenium, tin, and thallium. In addition, insecticides, herbicides, and
pesticides pose health hazards from food contamination.
Workers handling incompatible substances have risks in addition to the potential toxicity.
Incompatible substances should be stored far enough apart to eliminate the hazardof accidental
mixing. Incompatible substances are those that, when mixed, react violently or evolve toxic
vapors or gases, or in combination become hazardousby reason of toxicity, oxidizing power,
flammability, explosiveness, or other properties. These chemicals should be stored in chemi-
cally compatible containers, and the location chosen to prevent accidental damage to the con-
tainer, for instance, avoiding high-temperature areas. Improper storage can to the
leadevolution
of toxic gases to which employees can be exposed when they open the container.
Some emerging hazardous waste treatment processes such as reverse osmosis may poten-
tially concentrate the hazardous material. Concentrated hazardous material poses health risks,
’ and if improperly handled there is an increased risk of overexposure to the workers. In general,
themoreconcentratedthematerial,thesmallerthequantitynecessaryforoverexposure.Fil-
tering waste streams generates another problem. One potential exposure point occurs when
workers replace contaminated filters. In addition, if the filters are air-dried, there is a greater
risk of particulate exposure once the collected material dries. Also, workers’ potential expo-
sures include the volatile chemicals offgassing from an overloaded filter. For that matter, any
particulate matter, with the exceptionof reactive metals, when kept damp with water, should
pose little inhalation risk. Where feasible, all solid hazardous material should be kept damp.
When mixing substances that may splatter, splash, spray, boil over,or produce heat, shielding
is the first control priority for worker protection. If pressurized air or steam is used,as in sparg-
ing, engineering controls must be used to prevent excess airor steam thatmay induce a violent
234 Owens
reaction. When the engineer lays out the controlsfor a process, he must locate them so that the
employee will not be exposed to or come into contact with a hazardous substance. If the sub-
stance is a liquid, care must be taken to ensure that no employee will be exposed to liquid
accidentally released from gaugesor other measuring instruments thatmay be under pressure.
2. Allergens
A variety of airborne agents resultin occupational asthma. These include plant matter, animal
products, and organic chemicals. The chemicals thought to produce an immune-type asthmatic
response that may be presenting hazardous waste include formaldehyde, urea, and ethylenedi-
amine [ 7 ] . Chemicals known to be respiratory tract irritants and that cause or contribute to
asthma include ammonia, chlorine, sulfur dioxide, and hydrochloric acid.
Some individualsmay develop an allergic dermatitis response to a chemical after being in
contact with it or another chemical once. The initial exposure may be by an route-skin ab-
sorption, ingestion, or inhalation-as long as the chemical is absorbed in sufficient quantity.
After the initial contact, the individual is said to be “sensitized” to the chemical. Thereafter,
the chemically allergic individual experiences an adverse effectafter a brief exposure to a lower
concentration than would normally result in an adverse effect. The sensitization reaction may
occur at extremely low doses; however, a dose-response curve applies-a certain concentration
of chemical must be present to cause a reaction. A number of chemicals can cause sensitization
by external contact; these include formaldehyde, mercury(metallic, ammoniated, and bichlo-
ride), cobalt chloride, ethylenediamine hydrochloride, epoxy amine hardener, and alcohol [7].
3. IonizingRadiation
Ionizing radiation at a remediation site may be a significant health hazard owing to its poor
warning properties and nonspecificity of target organ. Radioactive waste on abatement sites
must be located andidentified, and all unknown materials discovered at a site must be surveyed
for radioactivity. Then the engineer should draw a plot plan that identifies all radioactive
sources by zones indicating the degree of hazard. Some hazardous waste sites that may have
radioactive materials presentare those with wastes from hospitals and dental offices, petroleum
production pipe scale, or certain types of petroleum distillation scale and sludge, nuclear test
sites, nuclear power generators, and some types of instrument manufacturers [S]. Instruments
that haveemployedradioactivesourcesincludetelevision sets, smoke detectors, electron-
microscopes, and luminous painted dials. The survey meters most commonly used are scintil-
lation counters and Geiger-Muller counters, both of which detect beta and gamma rays, and
alpha counters for alphaparticles.
Airborne alpha particle emitters pose inhalation and ingestion hazardsbut less of an ex-
ternal (i.e., skin) hazard. Beta rays, X-rays, and gamma rays may cause internal injury from
external exposure becauseof their penetratingpower. The actual health effects due to radiation
exposure depend on the quality factor,i.e., penetrating and linear energy transfer,of the source.
Different sources, for example, betaor alpha emitters, have different quality factors and hence
different degrees of health hazard for a given route of exposure. The dose equivalentof radi-
ation, or the absorbed dose multiplied by the quality factor and other modifying factors, ex-
presses theirradiation that directly causesthe adverse health effects[8]. When prioritizing risk
from radiation exposure to design protective measures, the dose equivalent shouldbe used be-
cause it expresses the absorbed dose on a common scale.
Shielding radiation sources from workers is one way to reduce or eliminate exposure.
However, the type of radiation must be known because alpha and particles beta interact with the
shield differently. Beta particles that strike other atoms, have a portion of their energy con-
verted into X-rays, which are more penetrating [8]. A shield for high-energy beta emitters
zards Health 235
should be of medium density, i.e., water, plastic, or aluminum, to reduce the production of
X-rays. It is possible for an engineer to design a shield specifically for that emitter’s energy and
to successfully prevent most radiation exposure. On other the hand, gamma rays have no charge
and therefore pass easily through matter, being stopped onlyby chance encounters with elec-
trons. Gamma ray shielding calls for dense material such as lead or leaded glass. However,
some portion of a large source of gamma photons will penetrate shielding, and the key to
shielding is to reduce the concentration penetrating toan acceptable level. On the other hand,
alpha particles usually do not require shielding becauseof their short penetrating powerin any
material. However, inhaled or ingested alphaparticles pose a high risk of cancer. Ifengineering
controls fail to protect workers from inhaling alpha particles, workers must wear respirators
equippedwithhigh-efficiency particulate (HEPA) cartridges whoseefficiency for 0.3-pm
aerodynamic diameter particles is 99.97%. Ionizing radiation at high dose rates has caused
cancer, pulmonaryfibrosis, and pneumonitis[g]. Low dose rates may lead to adverseeffects on
cell reproduction, andcells that undergo mitosis frequently, suchas bone marrow cells, sperm
cells, and oocytes, are more susceptible to adverse effects than long-lived cells. One indicator
of radiation exposure at moderate dose rates, i.e., 25 rem (radiation equivalent, man) is the
frequency of chromosome aberrations in the lymphocytes of human peripheral blood. Acute
effects may be observed at absorbed doses as low as 50 rad (radiation absorbed dose) if expo-
sures occur rapidly, for example, at several rad per hour. Qpically, by the time the adverse
health effects occur, it is too late for medical intervention.
4. Dusts,Mists, andFumes
Vibration of any dry material will generate some dust. The quantity of dust generated depends
on how dry the material is and on how much force is applied in vibrating, cutting, or sanding
the material. Invisible particles may penetrate deep into the lungto the alveoli andmay remain
there for a considerable length of time. The majority of these particles are less than 5 pm in
aerodynamic diameter. Fumes are solid particles having particle diameters of less than 1 pm,
and they may remain airborne, and hence in the worker’s breathing zone, for hours. These
fumes may increase in concentration in the breathing zone throughout theday unless there is
adequate dilution ventilation.
The potential health hazard posed by dusts or mists depends not only on the mass con-
centration but also on the particle size. Because not all dust clouds contain the same size par-
ticles, there are twoindices for dustconcentrations,total and respirable. The total dust
concentration is the mass of dust collected on a filter divided by the volume of air sampled.
However, the respirable dust index represents the concentration of dust that can penetrate
through the nose and trachea to the alveoli. This index is the fraction of the total respirable
particles that pass through an aerodynamic size-selective sampler.For a thorough analysis of
the hazard potentialof a specific dust source, the engineer measures the size distribution using
a size-selective sampler,which collects particles in specific size ranges and therefore allowsthe
industrial hygienist to determine the percentage of the total dust that is respirable and other
peramaters. Given two identical dust concentrations, the greater potential health hazard lies
with the concentration consistingof a larger quantity of smaller aerodynamic diameters.
The health hazardmay be greater if the dust containscrystalline silica, metals, or organics
that have absorbed ontothe dust. For instance, charcoalused to absorb organics posesa greater
risk than clean activated charcoal. Also, one must be careful when handling dusts that may
contain low percentages of heavy metals. There existsa risk of workers taking the metal-laden
dust home with them, thereby exposing children and other adults the to hazard. Good personal
hygiene, including after-work showering and the use of disposable coveralls, should reduce the
risk of taking toxins home.
236 Owens
There are two forms of silica, crystalline and amorphous silica, and they differ in their
toxicity. Amorphous silicais similar to the sand on beaches, in cement, and in ordinary soil and
has a relatively low toxicity. Crystalline silica has a different molecular structure and is more
toxic via inhalation. Crystalline silica may be formed by heating amorphous silicates such as
kawool wool. Silica that has been heated above 1400"for a considerable length of time forms
crystalline silica in varying percentages. However, thereis some evidence that heating to higher
temperatures produces amorphoussilica, which is much less toxic than crystalline silica [lo].
Crystalline silica causes chronicsilicosis, a disease that usually occurs inthe upper lobesof the
lungs from long-term exposure to low concentrations. Short-term, extremely high concentra-
tions from worksuch as sand blasting have caused acute silicosis. Unlike typical silicosis,
which develops into measurable health effects years later, acute silicosis may be diagnosed
within 6 months to 2 years after exposure. The adverse health effectsare similar for acute and
chronic silicosis. When handling a mixture of crystalline silica and amorphoussilica, one must
adjust the exposure limit to account for the proportion of crystalline silica in the dust. The
greater the percentage of crystalline silica, the lower the concentration thatmay cause adverse
health effects, and therefore the lower the exposure limit.
Crystalline silica is not usually found in most typical earthen materials such as diatoma-
ceous earth. However, when diatomaceous earth is heated to remove organic material such as
absorbed hydrocarbons, crystalline silica forms. It is considered fibrogenic and may lead to
silicosis. Furnaces lined with fire brick made of silica have the potential for crystalline silica
exposures. The same is true ofany refractory lining material in kilns or thermal oxidation
chambers. When the temperature of refractory ceramicfiber insulation rises, such as in an in-
cinerator, furnace, or heat exchanger, some percentage of the insulation converts from amor-
phous to crystalline silica. Thus, when workers mustenter equipment that was heated to above
about 1400" for any length of time, they must take precautions to reduce their exposure to dust.
This can be done by wetting, isolating, or ventilating the material.
In addition to dust from silica, workers must avoid exposure to wood dusts, especially
wood treated with fungicides or bactericides. Ordinary wood dust has been associated with
asthma in some susceptible workers. These woods include oak, mahogany, California redwood,
andWestern red cedar [9]. Inhaled wood impregnatedwithfungicides or otherorganics
may pose a health hazard greater than the hazard for wood alone. The wood dust acts as the
carrier for the organic chemical, whichmay remain in the lungs fora long period of time. As
the chemical leaches from the wood pores, the lung absorbs it, and it then enters the blood.
Any abrading of wood may release particles small enoughto penetrate to the alveoli and remain
there.
When designing crushing processes, one must always consider the combustible hazard po-
tential and the associated control measures requiredby OSHA. If the concentration of a flam-
mable or combustible liquid or powder has the potential to reach 25% of its lower explosive
limit, then specific control measures are designed into the process. First, there must be no
source of ignition, and the potential for static charges must be eliminated by bonding and
grounding all equipment. This includes all machines, air hoses, cleaning systems, and air noz-
zles. In addition, equipment expected to contain an explosive concentrationmust be designed
to explode away from personnel performing normal duties. This same equipment should be ven-
tilated by a permanently installed groundedvacuum cleaning system.
5 . Catalysts
The destruction of organics by catalysts poses potential health hazards due to the catalysts or
dust liberated duringcatalyst transport. Nickel, cobalt, chromium, and vanadium catalystsmay
be oxidized, thus releasing gasesor fumes that may cause a variety of responses including res-
ontrol
rds Health
Pollution and 237
piratory diseaseand skin sensitization.The toxicity of metals from catalyst dust depends on the
dust’s lipid solubility and therate of reaction of the toxicant in the body. Metal compounds that
are lipid-soluble are more readily absorbed into the body to cause internal reactions [9]. How-
ever, catalysts dusts that are not lipid-soluble may also lead to adverse health effects. For in-
stance, a high concentration of nickel dust results in a skin reaction that looks like chronic
eczema, i.e., redness, itching, and scaling. fipically, only the Ioading and unloading of cat-
alyst from sealed reactors poses an inhalation and dermal exposure risk to catalyst dust.A vac-
uum truck transfer from the reactor reduces the inhalation risk. In addition, the workers should
be protected from inhalation and dermal contactby the use of supplied-air respiratory equip-
ment and full body suits.
6. Metals
Although thereare metals inmany hazardous wastestreams, the potential for exposureto haz-
ardous concentrations varies depending on the matrix. Metals may be bound in an inorganic
matrix and pose little riskor exist as a fume in the oxidized state with the potential for carci-
nogenicity. For a specific metal, the more soluble it is in the body, the greater the toxicity. A
metal is soluble in the human body only if it is in a specific oxidation state or bound to an
organic molecule. When the element is bound to an alphatic hydrocarbon or nonpolar hydro-
carbon, such as tetraethyllead, the potential for skin absorption is greater than if the element
exists alone or is bound in a polar molecule. In some instances, its oxidationstate determines
to a great extent an element’s toxicity in the body. For instance, hexavalent chromium is a
known carcinogen, but the trivalent and divalent states cause no cancer[9].
There are a few known potential exposure points for metal intoxication, and inhalation of
metal oxides poses a health risk. Ingestion of high enough concentrations of a metal to cause
an effect, although rare,may occur at sites with poor washing facilities. This is especially true
for metals that tend to bioaccumulate, such as lead. Whenever lead-contaminated waste con-
tacts the skin, the potential for ingestion exposure exists. Burning any material containing met-
alsleads to theformation of metaloxides,whicharerespirablebecause of theirsmall
aerodynamic diameter. Incinerationof metal-containing waste may generate nonhazardousfly
ash, which canbe recycled; however, care should be taken when handling the feedstream. The
to the incineratorand the vent openingsare two
site of transfer of the waste from the tank trucks
potential, albeit usually insignificant, exposure points.
B. Physical Agents
1. Noise
In almost all industrial facilities, noise is a common agent. However, engineers can reduce
noise exposure easilyif they address itin the design stage.The engineering design stage is the
crucial timeto plan for a quiet process unit. The noisy process unit usually contains sources of
noise that could havebeen much more easily fixed before construction than after.In designing
fluidflow,especiallyturbulentflow,vibratingpipes are quieted by (1) designing gradual
bends, (2) placing control valves as far as possible from bends, (3) using pipe with gradual
expansions and contractions, and (4) using oversized pipingto reduce fluid turbulence[ll]. A
simple means of quieting an electric motor to is install silencers on the motor’sair intake and
exhaust. Motorsare highly directional noise sources, and in some cases an operator’s exposure
is reduced by simply pointing the cooling-air intake toward an unpopulated area. Steam-driven
motors exhaust steam in bursts that produce pulsed noise. A steam silencer, similar to an ex-
haust muffler on a car, disperses the pressure wave and hence reduces the noise level. Overall,
the f i t choice in abating noise is to silence the source;however, isolation may be beneficial,
238 Owens
especially if the source generates toxic dusts, mists, fumes, or gases. If engineering controls
fail to reduce noise levels, personal protective equipment such as earplugs and muffs may be
recommended.
Vibration
2.
The potential of overexposure to excessive vibrations at hazardous waste treatmentfacilities is
rare. However, the engineer designing equipment shouldbe aware of the hazards of excessive
vibration. There are specific ranges of frequencies of vibration that induce adverse health ef-
fects. Depending on the frequency and source, the effects may be whole-body or segmental,
e.g., affecting only the hands. As a rule of thumb, the smaller the body part, the higher the
frequency needed to produce an effect. For instance, allof the body organs tend to resonatein
the range of 2-100 Hz; however, the torso resonates predominantly in the lower frequencies.
The human eye resonatesat 60-90 Hz,and the head tends toward this higher frequency range.
Excessive exposure of the eye to vibratibns in the 60-90-H~ range is associated with vision
disorders [2]. Whole-body vibration exposure may cause digestion problems and changes in
nerve conduction and bonestructure. In addition, segmental, i.e., hand and foot, exposure to
low frequencies of vibration has led to tenosynovitis, bone cysts, and Raynaud’s phenomenon,
i.e., vibration white finger [12].
Engineering control measuresare the first line of defense against excessive vibration ex-
posure, and administrative controls are second. Equipping heavy machinery with seats that ride
on a cushion of air or water helps dampen the motor vibration. Operators of heavy tractor trail-
ers hope that these and other engineering solutions will reduce back, neck, and shoulder dis-
orders associated with the trade. The use of hand tools, such as pneumatic hammers, that
vibrate in the 40-300-Hzrange may lead to Raynaud’s phenomenon. It is a reversible disease
in the early stages, but continued exposure can leadto permanent hand disability. In addition,
simultaneous exposure to cold can enhance the progression of the disease. Engineering mea-
sures to cancel or dampen the source of the vibration are the most appropriate. Personal pro-
tective equipment suchas antivibration gloves have not been shown to be effective in all cases.
If the temperature is cool, the firststep should be to increasethe ambient working temperature.
In the new groundwater vibrorecovery process, engineers can reduce worker exposure to whole
or segmental vibration and thereby reduce the risk of adverse health effects.
3. ConfinedSpaces
The definition of a confined space takes into account the potentialfor an oxygen-deficient or
displaced atmosphere. Thusthe conventional definition includesmany areas not typically con-
sidered confined. Oxygen-deficient atmospheres may be present dueto displacement by another
gas source or by an oxidation reaction, and both of these may not be readily apparent. OSHA’s
confined space standard required employersto evaluate confined spaces for oxygen deficiency
or other hazards prior to entry of personnel. A potentially oxygen-deficient worksite is eval-
uatedwithdirect-readingoxygensensors. A confinedspaceshouldbeequippedwith
continuous-reading oxygen sensorsif there is a possibility of toxic gas releases. The monitor
should be set to alarm when the workplace oxygen concentration dropsto 19.5%. Typical ad-
verse health effects, including inattention and increased heart and ventilation rates, begin to
develop in oxygen-deprived atmospheresof 16% [9]. Symptoms progressto nausea, vomiting,
unconsciousness, and deathwhen the oxygencontent drops below 16%. Examples of confined-
space hazards foundat hazardous wastesites include vessels, scrubber towers,tanks, trenches,
sewers, drains, and building basements. Normal oxygen content ranges from 19.5 to 21%, but
in the presence of some hazardousmaterials, oxygen is displaced orits concentration reduced
by oxidation.
In addition to oxygen deficiency, confined spaces pose other health hazards. For instance,
stabilization reactions may leave a caustic material in the vessel. If soil has been ground in a
vessel, workers may be exposed to metals, silica, or fibers from the fine powder remains. Dusts
from soil vitrification processesmay create an explosive, if not oxygen-deficient, atmosphere.
Some solid materials usedas catalysts or additives in soil stabilization will explode at certain
concentrations. Hydrogen sulfide may be generated in some soil treatment processes that use
acids mixed with sulfur compounds. This toxic gas has good warning properties at first due to
its odor, but the sense of smell is diminished after prolonged exposure, at which time the con-
centration may increase enoughto lead to respiratory center paralysis.Any vessel or tank that
needs cleaning after use poses hazardsbeyond those associated with the contained material.
The safest method for preventing health hazards due to oxygen deprivation isto ventilate
the space until the oxygen content is above 19.5% and to monitor the air continuously. If work
must be done in an oxygen-deficient atmosphere, supplied air-breathing equipment operating in
the positive pressure modemust be worn. In addition, workers must wear emergency respira-
tory breathing equipment to prevent asphyxiation in the event of the failure of supplied air
equipment. Ventilation of the confined space is the key to providing a working space safe from
oxygen deprivationor other inhalation hazards, provided the ventilationrate reduces the con-
taminant concentration in the vessel to a safe level and prevents exposure at the exhaust of the
ventilation. One recommendation is to provide direct communication between workers inside
the confined spaceand attendants outside. Also, all workers should wear a harness with a line
attached so the attendant can remove a worker without entering the vessel. There have been
numerouscases of fatalitiesofrescuerswhoprematurelyenteredaconfinedspace.One
confined-spaces improvement is the use of structural support for pulleys above manholes, the
idea being that the attendant can easily remove a worker by using a block and tackle.
4. Heat Stress
Heat stress may cause illnesses ranging from behavioral disorders to heat stroke and possibly to
death [13]. Heat stress can leadto a range of reactions, and workers who are acclimatized are
more heat-tolerant. The mildest form of heat stress is transient heat fatigue, which manifests
itself as impaired mental and sensorimotor performance. Workers exposed to temperatures
above normal body temperature over several weeks develop a tolerance to the heat referred to
as heat acclimatization. This increases the heat exposure a worker can tolerate before experi-
encing disorders. A few days without heat exposure can substantially reduce the degree of ac-
climatization, but even after weeks without heat exposure, some heat tolerance remains[13].
Skin reactions to heat include rashes, i.e., “prickly heat,”and anhidrotic heat exhaustion,
which is a rare disease. Rashesmay occur more frequently in humid environments or when the
skin is constantly damp, as when chemical protective clothing is worn. Workers wearing per-
sonal protective clothing that does not allow passage of moisture are more susceptible to all
forms of heat stress than workers wearing water-penetrable clothing. Heat cramps and heat
exhaustion aretwo reversible illnesses that result from excessiveofloss body moisture and min-
erals. When the body failsto regulate its temperature, heat strokeor heat syncope may occur.
Heat syncope, or fainting while standing, may occur in physically fit individuals who are not
acclimatized because blood flows away from the brain toward the extremities to cool thebody.
Symptoms of heat stroke include hot dry skin and an elevated core body temperature, which
may cause loss of consciousness leadingto coma.
Effective engineering means of reducing these effects include shielding, cooling the sur-
rounding air, increasing the workspace air velocity, dehumidifying the surrounding air, and wet-
ting the skin surface. Engineering a cooler environment, which lessens the evaporative sweat
loss, is one solution to reduce these adverse effects. Provided atmospheric humidity is rela-
240 Owens
tively low and air temperature is less than skin temperature, increasing air velocity provides
increased evaporative cooling. In environments in which radiant heat loadingis a contributing
factor, such as the area adjacent to a furnace, shielding consisting of reflective material may
significantly reduce heat stress. Radiant heating arises from objects that are hotter than skin
temperature. Shielding designed to reflect light provides the most efficient protection from ra-
diant heat. One exampleof a material that provides radiant heat protectionis aluminized Kev-
tar. In humid environments, dehumidifiers reduce ambient moisture content and effectively
increase the body’s evaporative sweat rate, thus providing cooling.
When engineering controls fail to provide a safe environment, administrative controls,
such as task rotation or mandatory rest periods, are the second means of hazard control. If
administrative controls failor cannot be implemented, the last resort is the use of personal pro-
tective equipment. This includes coolvests, vortex coolers, icepacks,andotherdevices.
Workers wearing level A,B, or C chemical protective equipment frequently also wear personal
protective equipment such as cool vests, vortex coolers, and ice packs.
IV. HEALTH HAZARDS ASSOCIATED WITH EMERGING TECHNOLOGY

In this emerging field, new technologies may cause occupational diseases that may not have
readily identifiable causes. In addition, hazardous waste contains toxins from many different
industries simultaneously; therefore worker exposure can include exposure to toxins from mul-
tiple sources. And the waste stream that workers handle often varies from day to day, making
it difficult to identify the toxic agent(s). Besides the usual chemical hazards, since emerging
technologies use engineering froma variety of industries, workers need to be protected from
the various physical agents discussed in the preceding section. For instance, the use of vibrat-
ing tools to liquefy soils for remediation may lead to Raynaud’s syndrome and is in contact with
the worker [12,14]. However, a simplemodification-raising or loweringthedesignfre-
quency-can significantly reduce the risk of adverse worker health reactions.
A. Trenching
Trenching at remediation sites poses hazards in addition to the potential oxygen deprivation.
The major concernis a cave-in, but other concerns include uncovering contamination,electric
lines, gas lines, etc. OSHA regulates trench design in Title 29 CFR 1926 Subpart P [15]. The
conditions likely to lead toa cave-in include loose soil, previously excavated soil, moist soils,
vibrating equipment placed close to the trench, and trench sloping inappropriate for the soil
tYpen
B. AirStripping
Air stripping of groundwater may expose workers to hydrocarbons when work is carried out in
the vicinity of the effluent. There are several potential exposure points, including sampling
points, leakage from lines, monitoring wells, the insides of vessels during maintenance, and
effluent vents. The design of sparging wells should include assurances that the extraction well
pressure will always be less than that of the injected air well. If the extraction line includesa
dilution port, a check valve should be added to prevent vapor release when the blower cycles
on and off. Air emissions from the extraction well pose inhalation hazards that should be con-
trolled by engineering means. If activated charcoal is the absorbent used, one should consider
the exposure of the workers to carbon dust saturatedwith hydrocarbons. Respirable dust thatis
saturated with hydrocarbons may be more hazardous than carbon dust. In addition, the worker
is potentially exposed when disconnecting the inlet hose tothe absorbent container. Exposure
risk should be reduced by installing a block valve on the upstream side of the inlet flange.
Measurements of the effluent should be obtained to determine whether carbon breakthrough
has occurred. If the vapors are released directly to the air, measurements should be taken to
ensure that the concentrations are well below occupational exposure limits.
Also, fittings at pumps, valves, and flanges should be monitored for leaking hydrocarbon
streams because theseleaks may become a source of operator exposure. Volatile hydrocarbon
process units that include valves, flanges, and pumps must be maintained to reduce emissions
of what the EPA calls “air toxics” The EPA refers to these emissions fromidentifiable sources
as “fugitive emissions” and limits the concentration emitted to 10,OOO parts of contaminant per
million parts of air. However, the occupational exposure limit for some toxic air contaminants
is 1 ppm. The EPA requires certain pumps and seals to be installed for specific process streams
to reduce emissions. These and other measures should reduce operator exposure to fugitive
emissions.
Engineers should be aware of the new pump systems designed to reduce process stream
losses through the pump seals. Also, selection of appropriate flange gasket material may re-
duce operator exposure because a gasket that slowly dissolvesmay leak product. Engineers de-
signing new processes should consider the possible presence of chemicals that were in limited
use until recently, such as methyl tert-butyl ether (MTBE). For instance, MTBE swells Viton
gaskets, which may lead to leakage and failure at flange seals.
Designing towers, vessels, and drums with large manholes reduces worker exposure by
providing better ventilation. Maintenance may consist of welding, chemical washing, and/or
packing replacement. OSHA requires confined space ventilation to provide an atmosphere
free of toxic gases and fumes and to supply sufficient oxygen. The typical method for provid-
ing a large volume of air is by general dilution ventilation. An air-stripping tower should
have many manholes, and, if possible, they should be spaced evenly throughout its length to
offer ventilation options. The ideal ventilation is local exhaust or supply ventilation for each
worker, but this usually requires ductworkentering the manholes. The manhole should be large
enough that the worker can make an emergency escape while the ductwork is inthe manhole.
Ventilation supplied todry a tower after chemical washing requireslarge volumes of air to be
drawn through the tower. As long as all the air is flowing in the same direction, for example,
top to bottom, the tower should dry quickly. The larger the volume of air, the faster the tower
will dry, and once it is dry the maintenance workers can begin work inside. When the air
flows from the ground up, the air laden with chemical cleaner exhausts higher above ground
and, ideally, away from personnel. However, if the tower contains puddles of cleaner at the
bottom, bottom-to-top air flow may spread the cleaner throughout the tower, thus increasing
drying time.
When designing the sample points, it is important to provide more than adequate local
exhaust ventilation to eliminate operator exposure. This is a good idea if carcinogens are
present, because their exposure limits are gradually being reduced to “as low as feasible.”
Therefore, the design of sample pointsin processes should be based onthe toxicity of the spe-
cific chemical(s). For instance, samples of highly flammable chemicals must have ventilation
provided by nonsparking means, and sampling points for acutely hazardous chemicals should
have closed-loop line purging and valves that spring closed upon release.
C.PhotolyticDegradation
Photolytic degradation uses sunlight or artificial sources of ultraviolet (UV) light to initiate
photochemical reactions in hazardous waste [16]. These reactions occur faster when the process
uses shorter wavelengths or more energetic light. One concern when using high-energy light is
242 Owens
the possibility of eye exposure and subsequent injury. Sunlight contains a variety ofwave-
lengths of light, some of which may cause biological damageif viewed for extended periodsor
if concentrated. Focused sunlight may form energy concentrations of up to 10 MW/m2.
If the viewing angle is less than l", naked sunlight can cause photochemical blue light
injury. Photochemical blue light injuryto the retinaof the eye is primarily the result
of exposure
to wavelengths of 400-550 nm. One proposed method of detoxifying hazardous waste is to
concentrate sunlight into a narrow beam. There are two potential health problems associated
with concentrating the sunlight on Earth: (1) the increase in the effective vewing angle,which
potentially increases the absorbed irradiance; and (2) the greater intensity associated with in-
creasing concentration. For photochemical blue light injury, the lowest irradiance known to
cause injury is 1 X MW/m2. A retinal burn may result if the sun is magnified so the view-
ing angle subtended by the sun is 4" or greater. For instance, viewing the sun through a bin-
ocular or other magnifying lensmay cause permanent damage to the retina. Viewing a source
of magnitude greater than 0.01 MW/m2 overa viewing angleof 4" has caused retinalbums, and
a viewing angle of only 5 minutes (5") with a source greater than 1 MW/m2 leadsto the same
effect. Thus, the engineer should consider adding eye-protective mechanisms to systems that
use magnified UV sources. Besides the thermal injury that canresult, skin exposuremay cause
bums andlead to skincancer. Protective equipmentcouldincludepolycarbonateeyewear,
which absorbs more than 99% of the incident UV light and most of the infrared. Complete
enclosure of the concentrated sourceis an option, and a fail-open switch should prevent acci-
dental exposure when the enclosure is opened.
D. UltravioletOxidation
Ultraviolet (UV) oxidation is gaining popularity for its ability to destabilize organicsand cat-
alyze oxidation [17]. However, equipment must be carefully designed to reduce the riskof ac-
cidentaleye or skinexposureto UV. Sources usedby photosensitiveindividuals or in
conjunctionwithphotosensitizingagentsproduceadversehealtheffects.Basal cell and
squamous cell skin cancers result from long-term exposure toUV theportion of sunlight. How-
ever, they can also be caused by exposure to specificportions of the UV spectrum produced by
a UV lamp. Mercury vapor discharge lamps usedas UV sources are associated with increased
risks.
The wavelength of the light emitted is directly related to the potential for adverse health
effects. Radiation having wavelengths near 270 nm have a greater hazard potential; therefore
these exposures should be limited as much as possible. As the wavelength increases, the av-
erage daily exposure limitto skin or eyes increases;e.g., with an increase from300 to 320 nm,
the limit increases by a factor of about 2. The 8-hr time-weighted average exposure for wave-
lengths around245 nm, the primary emission froma mercury vapor discharge lamp, should be
limited to about 0.002 J/cm2. When designing treatment technologies, one should be cautious
when the sourceemits more than this. If the exposure periodis half as long, the exposure limit
is approximately 2 times as great. Therefore, if the exposure lasts for only1 sec, the exposure
limit would be about 3000 times that for the 8-hr exposure.
One lamp undergoingtests to detoxify organic wasteis a type of mercury vapor lamp with
spectral emissions at 254 nm, which can be a significant health concern if handled unsafely.
This wavelength has a relatively high spectral effectiveness, and if changed to a lower wave-
length, i.e., below 180 nm, or to a higher wavelength, i.e., above 315 nm, would pose less of
an eyeor skin hazard. If at all possible, the source shouldbe sealed to eliminate all chancesof
radiation being emitted exceptin the directionof the waste stream. Thereis always therisk that
a maintenance worker will open the cover of a UV source. For all UV sources, regardless of
zards
Control Health
Pollution and 243
strength, the cover should be equipped with off the power to the
a fail-open switch that will turn
lamp when the cover is opened.
The relation between an acceptable exposure leveland the exposure period is linear until
the exposure period is less than 0.1 sec. OSHA requires that machinery producing UV radia-
tion, either direct or reflected, be shieldedto protect employees’ eyes. This is because a worker
may accidentally look directly intothe source of radiation for more than 0.1 sec. Where such
shielding is not practicable, employees must be given goggles that prevent radiation injury to
the eyes.
E.
Stabilization
A common treatment practice among hazardous waste disposal facilities is the stabilization of
contaminated soil or sludge. The process involves mixing the waste with some type of solid
matrix, typically cementor kiln dust. However, this mixing occurs in open pitsor bins, both of
which are open to the atmosphere. In somecases, the workers mixingthe dust doso with heavy
equipment such as backhoes. These generate dust concentrations that could overexpose the
workers. The waste could contain metals, asbestos, and solvents. Worker exposure can be re-
duced by mixing the waste in a closed or ventilated container such asa cement mixer. An ad-
ditional concern is the stabilization reaction by-products such as heat.
V. CONCLUSION
This chapter addressed some of the health hazards associated with emerging technologiesfor
hazardous waste minimization.Much of the information focused on hazards inherent to general
industries, because many health issues pertainto both production and treatment facilities. Haz-
ardous waste handling facilities and sites pose unique health hazards, some of which were fo-
cused on with examples. Engineering and design solutions are the best methods to reduce
worker exposure, and some examples of specific solutions were included. In designing pro-
cesses for hazardous material handling, engineers must incorporate ways to reduce occupa-
tional health hazards. With knowledge of the health hazards associated with processes and
sites
and a concern for the human element, engineers can significantly reduce the risk of adverse
health effects for hazardous material workers.
ACKNOWLEDGMENTS
I am grateful to Paul Borenstein for providingcase studies and to Cathy Aaron for editing.
REFERENCES
1. EPA, Health and Safety Roles and Responsibilities at Remedial Sites, U.S. EPA, Office of Solid
Waste and Emergency Response, 9285.142. July 1 9 9 1 .
2. Levy, B. S. (ed.), Occupational Health: Recognizing and Preventing Work-Related Disease. Little,
Brown, New York, 1988.
3. Oransky,J. J., et al., Implementation of industrial hygiene engineering principles to reduce em-
ployee exposure at ahazardouswasteprocessingunit,PresentedatAlHAConference.Boston,
Mass.,1992.
4. Andrews, L. F? (ed.), Worker Protection During Hazardous Waste Remediation, Van Nostrand Re-
inhold. New York, 1990.
5. ACGIH, Threshold Limit Values for Chemical Substancesand Physical Agents and Biological Ex-
posure Indices with Intended Changes for 1991-1992, American Conference of Governmental In-
dustrial Hygienists, Cincinnati, Ohio, 1991-1992.
244 Owens
6. Mickunas, D. B., The use of remote optical sensing for fenceline monitoring during cleanup op-
erations at uncontrolled hazardous waste sites, Presented at AIHA Conference, Boston, 1992.
7. American Industrial Hygiene Biohazards Committee, Biohazards Reference Manual, American In-
dustrial Hygiene Association, Akron, Ohio, 1986.
8. Shapiro, J., Radiation Protection:A Guidefor Scientists and P hysicians, Harvard Univ. Press, Cam-
bridge, Mass., 1990.
9. Cassarett, C. D., and Doull, J. (eds.), Toxicology:The Basic Science of Poisons, Macmillan, New
York,1986.
10. Young, J., Health-related aspects of the heating of refractory ceramic fibre,Mechanisms
in in Fibre
Carcinogenisis. Plenum, New York, 1991.
11. U.S. Department of Labor, Noise Control:A Guidefor Workersand Employers, OSHA 3048, 1980.
12. Chaffin, D.B., Occupational Biomechanics, Wiley,NewYork,1991,p. 449.
13. U.S. Dept. of Health Services, The Industrial Environment: Its Evaluation and Control, Washing-
ton,D.C.,1973.
14. Reddi, L. N., Integrated vibrorecovery process (IVP) for remediation of NAPL-contaminated sites,
HMCRI Proc. R&D92 Natl. Research and Development Conf. on the Control of Hazardous Mate-
rials, San Francisco, 1992, pp. 305-309.
15. U.S.OSHA,ExcavatingandTrenchingOperations,Pub.No.2226,U.S. Govt. Printing Ofice,
Washington,D.C.,1975.
16.Sutton, M. M., Solar-photochemicaldestructionofhazardousorganicchemicalwastes,HMCRI
Proc. R&D92 Natl. Research and Development Conf. on the Control of Hazardous Materials, San
Francisco,1992,pp.122-126.
17. Camp, D. W., Effect of lampcoating mineral deposits on oxidation of groundwater contaminants,
HMCRI Proc. R&D92 Natl. Research and Development Conf. on the Control of Hazardous Mate-
rials, San Francisco, 1992, pp.111-116.
Part I1
METHODOLOGIES
OF WASTE
CONTROL
11
Techniques for Controlling Solid and
Liquid Wastes
Hsai-Yang Fang
k h i g h University
Bethlehem, Pennsylvania
Jeffrey C . Evans
Bucknell Universiw
Lewisburg. Pennsylvania
1. INTRODUCTION
Wastes canbe grouped intosolid and liquid forms.The majority of solid wasteis urban refuse.
This refuse will decompose with time and generate gases and liquid waste, generally referred
as leachate. According to the U.S.EPA [l] about 90% of wastes (which includes industrial
hazardous wastes) are in liquid form. Therefore, control of solid and liquid wastes requires
special emphasis on the control of liquid wastes.
The understanding of the interaction between pore fluids and clay behavior requires knowl-
edge of environmental aspects of geotechnical engineering. Itis essential to the engineering use
of naturally occurring materials for the containment of hazardous and toxic wastes. Without
this knowledge of clay behavior in responseto hazardous wastes, engineering systemsdesign,
such as remedial action programs, can have no sound basis on which to project the long-term
behavior of that system [2].
Solid and liquid waste control facilities are complex systems [3], requiring interdiscipli-
nary knowledge fromgeotechnical, hydrogeological, and environmentalfields to analyze, de-
sign, and construct waste containment systems. Conventional passive hydraulic barriers are
frequentlyadapted asbarriers forwastecontainment; however, special considerations are
needed in dealing with these barriers. In this chapter, discussion will focus on the following
points:
1. Characteristics ofurban refbse including decomposition processes

2. Basic considerations for analysis and design of control systems
3. Techniques of wastecontrol
4. Precautions and protections on these controlling facilities
247
248 Fang and Evans
II. CHARACTERISTICS OF URBAN REFUSE

A. General Discussion
There are several ways to dispose of municipal refuse, including incineration and landfilling or,
where the nature of the waste permits, by reuse as a substitute construction material. Land-
filling is presently the most expedientsimple way to manage refuse. Historically,the refuse was
referred to as garbage and the landfill was known as the dump.
Waste disposal material consists of anything that cannot be further used or recycled eco-
nomically. As a result, its composition varies from country to country and from community to
community as well as from season to season. The density varies from 50 to 400 lb/ft3 depend-
ing on the amount of metal and debris. Table 1 gives the average composition of solid waste
based onU.S.national survey results and the cities of New York, New York andOsaka, Japan.
In general, refuse can be divided into two categories: degradable and relatively nonde-
gradable. Among refusematerials, some are hazardous and/or toxic and some are not. Depend-
ing on environmental conditions in the landfill, the wastes are found in each of the states of
matter-solid, liquid, and gaseous forms. Many wastes, when mixed with other wastes or ma-
terials at a facility, can produceeffects that are harmful to human health andthe environment,
such as heat, pressure, fire, explosion, violent reaction, dust, mist, and gas. Generators of
waste materials are required to determine whether the waste is a hazardous wastein one of two
ways:
1. They are either waste and spent materials that are hazardous by definition and contained
in specific lists (such as U.S. EPA lists), or
2. They exhibit one of four hazardous characteristics-ignitability, reactivity, corrosiveness,
or toxicity.
B. Basic Considerations for Analysis and Design of Landfill Facilities

Municipal refuse or any other industrial waste dumpedinto a landfill site requires that proper
precautions be taken. Technical aspects such as hydrogeological, geohydrological, climatolog-
ical, and geotechnical must be examined. However, from the geotechnical engineering view-
point, the ability of control facilities to mitigate contaminant migration is most important and
includes the following considerations:
Table 1 Comparison of Composition of Urban Refuse

~~
New York City U.S. (national) Osaka, Japan

Spe (1968) (1973) (1980)
Paper 58.8 51.6 37.1

Food wastes 13.2 9.2 19.3
Metal 7.6 10.2 5.5
9.9
Glass 8.6 12.3
Wood 2.5 3.0 2.5
2.7
Textiles 0.8 4.0
1.9
Rubber,leather 0.8
Plastic 15.2 0.8 1.4
Garden wastes 10.1 - 2.5
Source: Data from Remson et al. [4]. Sowers [S], and Yarnamura [6].
Controlling Solid and Liquid Wastes 249
1. Control of any polluted water (leachate or contaminated runoff) in the landfill to prevent
it from seeping into the groundwater aquifer
2. Control of the top of the landfill so no additional water (i.e., rainwater, surface water) or
vectors (i.e., burrowing animals, flies) disturb the landfill materials
3. Environmental pressures (loads) and their effect on stability
4. Hydraulic conductivity and mass transport phenomena
C. Processes of Decomposition of Refuse in Landfills

Landfilled material will gradually change in form and will exhibit different engineering and
physical properties as a result of various environmental factors. Witmer and coworkers[7,8]
reported the garbage decomposition process for a 10-year period as reflected on a particle size
distribution curve. The aging process from fresh trash to aged trash along with the environ-
mental and mechanical factors are illustrated in Figure 1.
1. MechanicalProcesses
Mechanical processes do not directly contributeto the decomposition process. Compression of
landfill materials due to the weight of the overlying landfill materials (self weight) may result
in significant settlement in a landfill area. Additional settlement results from additional loads
such as surcharge loading from landfill cover materials, snow, and downward percolating rain-
water. Since the refuse is nonhomogeneous and contains organic matter, the settlement in the
landfill areas is also nonuniformly distributed. Becauseof this differential settlement, the top
seal (the landfill cover) is subject to cracking.
H
Mechanical Environmental Factors
Loads
Hazardous wastes
Surcharge Toxic wastes
Compaction Polluted pore fluids
Rainwater
Snow, etc. Acid rain
Freezing-thawing
Wet-dry
b
Mechanical Process
Physico-chemical
Process
Chemical Process
I G Pe ro om ci ec sr so b i o l o g i c a l
1
t
I Time
~~
Factor
~ ~~~~~~~
I
Figure 1 Aging process (geomorphic)stages between fresh and aging garbage.
250 Fang and Evans
2. ChemicalandPhysicochemicalProcesses
Leaching and ion-exchange reactions may significantly affect soil properties. Such soil prop-
erty changes occur when rainwateror drainage processesremove some soluble clay minerals in
the clay liners or around the landfill site by leaching. During this leaching, mineral elements
suchascalcium,magnesium,nitrogen,potassium,andphosphorus may be removed.The
leaching process in turn reducesthe cementation of the soil matrix and/or changes the ion con-
centration withinthe soil-water-electrolyte system andmay result in significant changesin the
properties of soil.
3. BiologicalDecompositionProcess
During the biological decomposition processin the landfill, the temperature increases. At el-
evated temperatures, sulfate concentrations increase. The problems result from the reduction of
sulfates to hydrogen sulfide (H,S). Hydrogen sulfide is the cause of corrosion of various un-
derground structural members. In sanitary landfill areas, the refuse is nonhomogeneous and
contains a large amount of organic matter, generating biological changes causedby decompo-
sition for many years. There are five stages relatedto the biological activityin the landfill [9].
Figure 2 shows a schematic diagram illustrating the cumulative settlement due to decomposi-
tion of organic matter versus time.
D. Contaminated Water and Pressures Produced in the Landfill Site

1. m s of Contaminants
Leachate produced in a landfill site generally results from the interaction
of infiltrating liquids
with the landfilled material and from the liquids contained within the landfill material at the
time of disposal. The properties of leachate change from communityto community as well as
from seasonto season. The parameters and their range of concentrations are shown on Table2.
Time
Figure 2 Schematic diagram illustrating cumulative settlement of waste due to decomposition of or-
ganic matter versustime. Decomposition stages:(1) aerobic, (2) anaerobic (nonmethanogenic), (3) anaer-
obic (methanogenic), (4) anaerobic decline, (5) return to anaerobic growth. (After Wardwell et al. [g].)
Table 2 Range of Composition of Leachate from Municipal

Solid Waste
Component Range
PH 3.7-8.5
Hardness, CaC03 200-7600
Alkalinity, CaCO, 720-9500
Ca 240-2400
Mg 64-410
Na 85-3800
K 28- 1700
Fe 0.15-1640
Ferrous ion 8-9
Chloride 50-2400
Sulfate 20-750
Phosphate 0.5-130
Organic N 3.0-490
NH4 nitrogen 0.3-480
BOD 22,ooO-30,ooO
COD 800-50,ooO
Zn 0.02-130
Ni 0.15-0.9
Suspended solids 13-27,ooO
BOD, biological oxygen demand; COD, chemical oxygen demand.
For purposes of examining the effect of leachate on the landfill liner system components, lea-
chate can be grouped into inorganic and organic pore fluids.
Aqueous inorganic fluids are those in which water is the solvent and the solute is mostly
inorganic. Aqueous organicfluids are those in which water is the solvent and solutesare pre-
dominantly organic.The organic part covers organic wastes and organic fluids. Organic wastes
are those in which an organic fluid is the solvent and the solutes are other organic chemicals
dissolved in the organic solvent. Organicfluids can be classified as organic acids and organic
bases. Organic acids include those organicfluids that react with bases and include proton do-
nors; and organic bases include any organic fluid capable of accepting a proton to become an
ionized cation [IO].
2.Acidity at the Linear Interface

Pore fluids produced from landfillsare generally acidic. The acidic leachate seeps through from
the landfill site into the liner; regardless of the type of liner used, the polluted fluid will interact
with soil at various stages. All soils contain H+ ions in their aqueous phases since wateritself
is dissociated into H + and OH- ions. Higher H+ concentrations are due to exchangeable H+
ions on the soil particles and/or the presence of mineral or organic acids such as H2S04 from
oxidation of pyrites and other organic acidsfrom the decompositionof vegetation. Soilacidity
varies with the season [ll].
Soil acidity and acidic pore fluid affects many geostructural members. For examples, they
lead to corrosion of metals and other construction materials. On the other hand, acidity may
have a desirable impact such as the catalytic effect on certain reactions employed in soil sta-
bilization [121.
Evans 252 and Fang
Table 3 Hydraulic Conductivity and Mass Transport Phenomena in Fine-Grained Clay

Liner Material
Mechanical energy field
Hydraulic conductivity due to mechanical (hydrostatic) potential
Multimedia energy fields
Energy conductivity (environmental)
(a) Hydration energy due to the hydration energy of ions, related to the heat of wetting
(b) Osmotic energy due to the osmotic energy of ions either held in a kind of Donnan equilibrium
on the solid particle surfaces or free in the aqueous solution
(c) Capillary potential due to the surface tension of water and the size and geometry of the
soil pores
(d)Electricpotential;electroosmosis;electrokineticphenomena
(e)Thermalpotential;thermoosmosis.thermalelectriceffect
(f) Magneticpotential;electromagneticforce
(g)Vaporpressurepotential
~~
Source: Based on Fang [14].
3. Stresses fromLandfills
The stresses or pressures developed with the soil-water system are caused mainly by changes
in the overlying stress conditions. There are at least three types of pressures to be considered,
including external loads such as surcharge weight from landfill, lateral earth pressures, and
loads due to construction activities around the landfill area [13].
4. Conductivity Phenomena in Landfills and Liner Systems

Flow through fine-grained liner material is at low velocity, unsteady, nonuniform, and some-
times discontinuous and contains contaminants insolid or gas forms. There are at least eight
possible causes (potentials) of flow from one place to another. These are summarized in Table
3. In most cases, the potentials (and thus the flow) are small in magnitude. However, the ac-
cumulation of these small amounts canbe significant, affecting the performance of waste con-
trol systems. In addition to factors shown on Table3, bacteria, chemical corrosion, and erosion
may contribute to barrier leakage as previously indicated. Case studies indicate that liners or
barrier walls may leak because of these factors, which are not commonly considered in trans-
port calculations.
E. Effect of Pore Fluid on Liner Behavior

Pore fluid effects on liner behavior havebeen discussed in various publicationsin recent years.
Many of these studies considered construction impacts, settlement effects, and pore fluid-
hydraulic conductivity interactions. In the following sections, selected additional factors such
as changes insoil cracking patterns, swelling, shrinking, and volumeas well as changes in soil
particle distribution.due to pollution are discussed.
1. Soil Cracking
Soil cracks are frequently observed in natural and constructedearthen structures such as clay
liners, Cracks can be a result of an internal energy imbalance in the soil mass caused by non-
uniform stress distribution from compaction energyduring construction. These cracks, usually
small and considered insignificant,may be the initiation point for progressive erosion and pre-
0 20 40 60 80 100
3
ElapsedTime, (x10 minutee)
Figure 3 Effect of pore fluid on permeability of sand-bentonite mixture.
mature failures. Cracking patterns developed in the presence of various fluids are significantly
different between noncontaminated (water) and contaminated pore fluids [E]. Contaminated
inorganic pore fluids (such as those studied with a pH < 2 or pH > 11) produce significant
cracking. Certain organic pore fluids such as aniline (C,H,NH,), acetic acid (C,H,O,), and
carbon tetrachloride (CCI,) show greater influence on cracking than others.
2. Particle Size Distribution

Effects of pH value on soil-water structures indicate that the higher the pH value, the smaller
the effective grain size and the greater the uniformity coefficient as determined using standard
procedures for particle size distribution (ASTM D422-72). The effect of changes in porefluid
chemistry on the measured grainsize distribution may result in wincorrect assessment offilter
requirements since the filter design criteria are based solely on grain size distribution.
3. HydraulicConductivity
The effects of pore fluid on hydraulic conductivity are of considerable interest to geotechnical
engineers concerned with the construction of hazardous and toxic material control systems.
Several technical symposia encompassing this topic, both national andinternational, have been
organized in recent years. Hydraulic conductivity is generally correlated with void ratio of the
soil and properties of the pore fluid (such as pH value anddielectric constant). The porefluids
can include organic and inorganic acids along with landfill leachate. Significant variability in
hydraulic conductivity and changes in hydraulic conductivity have been measured by various
researchers using various types of pore fluids, such as those shown in Figures 3-5. Various
explanations are presented by many of the investigators as reported by Evans [2].
254 Fang and Evans
Brown S a r n i a S o i l f r o m Canada
Void Ratio - 1.0
10"
10-5p d , n e , Propanol
"Acetone
tn-6 0- .'Methanol
I I I I I I I I I I I
0 20 40 60 80 l00
D i e l e c t r i c Constant
Figure 4 Effect of dielectric constant on hydraulic conductivity of Brown-Sarnia soil from Canada,
void ratio 1.0. (After Fkrnandez and Quigley [16].)
' l
t
Water Leachate
CO
I m
1
I
I I I I I 1
W 0.000 23
0
r) T i m e (x~OGmlnutes)
Figure 5 Log permeability versus time for clay liner material. (After Fang and Evans [17].)
111. BASIC CONSIDERATIONS FOR DESIGN OF WASTE

CONTROL SYSTEMS
Waste disposalfacilities can be grouped intothree catagories as shown in Table4. Facilities can
be classified as past disposal/waste management sites, active waste management facility sites,
and future landfillsites. A systematic approach to the controlof wastes requires the engineerto
fully assess both the site and subsurface conditions and evaluate the applicability of contain-
ment alternatives. Basic requirements for controllingthe wastes are given by Fang et al. [19].
There are four steps involved, the steps being closely interrelated.
A. CollectHistoricalData
Data collection often begins witha review of existing information including historical site data
as well as geotechnical, geological and hydrological, and geohydrological data. For past dis-
posal sites, it is necessary to obtain as much information as possible on the types of waste
disposed, the timetable of waste disposal, and the previous disposal practices-drum, solid
waste, or lagoons.
Aerial photos have been found to be quite useful in reconstruction of the site development
history. Historic drainageways,landfilling practices, haul roads, and liquidimpoundments
all show up quite well on photos. Information regarding the subsurface conditions can be ob-
tained from past records and borings, from the site construction history, and from geological
information.
B.PerformInitialSiteAssessment
It is necessary to assess, by gathering site-specific data, the existing site conditions including
geological conditions, groundwater conditions, and contamination distribution. Insitu investi-
gations are required at this stage. The use of geophysical instrumentsprior to test boringor the
monitoring of well installations can provide valuable insight into the subsurface conditions. De-
tails regarding subsurface investigations are discussed by Lowe and Zaccheo [20].
C. Perform Detailed Quantification of Site Conditions

It is typically necessary to quantify site conditions including the direction, volume, and ve-
locity of groundwater flow;the interaction of groundwater with surface water; thedistribution
Table 4 WasteDisposalFacility Classification

y Facility
es names
description
category
I disposal
Past site none
abandoned
toLittle
inactive
retired
midnight dump
uncontrolled site
orphaned
I1 disposal
Active secure landfill Some
sanitary landfill
I11 disposal
Future waste treatment Well controlled
complex
recycling facility
Source: Evans and Fang [H].
256 Fang and Evans
of contamination in the groundwater system; and the contaminant loading.The degree of so-
phistication of this quantification phase may vary froma simple conceptualmodel to a complex
computer model. For example, the recently developed GEOTOX knowledge-based expert sys-
tem can be used for this purpose [21,22].
D. Develop the Containmentrrreatment Program

The development of the containment and/or treatmentportion of the program is where the ap-
plication of environmental geotechnology receivesthe major emphasis. In many cases, inves-
tigations described in the first three steps (above) are primarily geohydrologic investigations.
Geotechnical properties of soil may not normally be includedin the routine investigation. It is
desirable to have geotechnical engineering input during the site investigation phase to avoid
future data gaps. Thus, testing should include tests for both physicochemical and engineering
properties. [23-251. Waste control systems to be considered at this stage are described in the
following section.
IV. WASTE CONTROL SYSTEM COMPONENTS

Solid and liquid waste control systems can consist
of a wide rangeof components. For purposes
of discussion these components canbe classified in two general categories: active and passive
[W.
A. ActiveComponents
Active components of a containment system are those that require ongoing energy input. Ex-
amples of active components include disposal wells, pumping wells, and treatment plants. Dis-
posal wells include injection wells; pumping wells include pumping create
to a pumping ridge;
and treatment processes include activated carbon specialty processes.
B. PassiveComponents
Passive componentsof a containment system are those that do not require ongoing energy in-
put. m i c a 1 examples of passive components include drain tile collection systems, barrier
walls, liners, and covers. While an active system requires ongoing energy input, the passive
components typically require maintenance. For example, itis necessary to keep vegetationtap-
roots from penetrating a clay cap. (Treehegetation effects on liner stabilityare discussed fur-
ther in Section VI.)
C. Passive Waste Control Systems

Passive components canbe further divided into three major subsystems.
1.Vertical barrier walls, such as soil-bentonite cutoff walls, cement-bentonite walls, com-
posite vertical cutoff systems, and vibrating-beam cutoff walls
2. Top seals (cap or cover barrier layers) such as natural clay caps, bentonite admixed caps,
and polymeric membrane caps
3. Bottom seals (liner barrier layers) such as natural clay liners, bentonite clay liners, and
polymeric membrane liners
The structures of these systems are illustrated in Figures 10 and 11, and a brief discussion of
each system follows.
V. ENGINEERING STRUCTURE OF WASTE CONTROL

SYSTEM COMPONENTS
A. Barrier Walls
The control of contaminant migration from existing disposal sites or impoundments may ne-
cessitate a vertical subsurfacebarrier to horizontal groundwater flow.Barriers commonly con-
structed include soil-bentonite slurry trench cutoff walls and cement-bentonite slurry trench
cutoff walls. Vibrating beam cutoff walls, grout curtains, sheet piling, and composite walls are
also used. For vertical barrier walls to be effective, they are generally keyed into an imper-
meablestratum of naturalmaterialsbeneaththesite,althoughthisisnotrequiredin
all cases.
1. Soil-BentoniteSlurryTrenchCutoffWall
Design and construction methods for soil-bentonite slurry trench cutoff walls are well docu-
mented [18,26,27]. As shown in Figure6, a trench is excavated below the ground surface using
the slurryof bentonite and water to maintain trench stability. The bentonite-water slurry exerts
a hydrostatic pressure, and a thin filter cake of bentonite forms on the walls of the trench to
maintain trench stability in much the same way as drilling fluid maintains borehole stability.
Figure 7 is a photograph of an actual installation.
The bentonite-water slurry is designedby the
geotechnical engineerto have proper density, viscosity, and filtrate loss properties, which allow
lm (3')
WATER
TABLE \
+
-
t
. . .
SOIL-BENTONITE
... BACK F ILL
BENTONITE-WATER ...
AOUl FER SLURRY . . .... 1.2 % BENTONITE
( 5 % TYPICAL) . '. .' . . . .
' [TYPICAL)
F I L T E RC A K E
Irnul.5m
77777
/AOUlCLUDE /
IAOUITARD ,
DURING EXCAVATION E X C A V A T IAOFNT E R
Figure 6 Schematic drawing of section of slurry trench excavation and backfill.

258 Fang and Evans
Figure 7 The excavation of a slurry trench.
for the formation of a filter cake along the walls of the trench and for sufficient fluid pressure
to result in a computed factor of safety greater than 1 for trench stability [2,28,29].
Trench depths can generally reach about 10 m using conventional backhoes. To achieve
greater depths (up to about 17 m), a modified dipper stick is required and can be provided by
specialty slurry wall contractors. To go deeper than 17 m usually requires the use of a clam-
shell, and an extended backhoe capable of excavating 22 m has been developed [30].
m i c a 1 cross sections of a slurry wall during excavation andafter backfilling are shown in
Figure 8. Upon the completion of excavation under the head of bentonite-water slurry, the
trench is backfilled with a mixture of soil and bentonite (addedby way of the bentonite-water
slurry). The mixture of soil and bentonite-water slurry typically has a consistency similar to
that of high slump concrete. Soil-bentonite slurry trench cutoff walls can generally developa
hydraulic conductivity of 1 X 10” c d s e c or less. For the design of a soil-bentonite slurry
wall for waste containment, studies are required beyond those typically required for conven-
tional dewatering applications. Chemical analysis of samples of on-site materials considered as
potential backfill materials may be required. Leachate compatibility tests must be conducted
using the site liquid as a permeant.
2. Cement-Bentonite Slurry TrenchCutoffWalls
An alternative to a soil-bentonite cutoff wall is a cement-bentonite cutoff wall. The trench is
excavated ina manner similar to soil-bentonite walls as described above, usinga slurry to main-
taintrenchstability.However,cementisadded to the slurry. Thecement-bentonite-water
slurry is left in the trench and allowedto harden. A strength equivalentto that of stiff clay can
be obtained after a period of about a month. Design considerations include the cement and
bentonite content andtype and their relationship to the strengthand permeability of the backfill
1251.
The overall permeability of cement-bentonite cutoff walls (typically about 1 X lO-‘cml
sec) is generally higher thanthat of soil-bentonite walls. Laboratory testing of a cement-ben-
tonite mix for a plastic diaphragm wall is discussed by Gill and Christopher [31].
I n 1
I
INTO CLAY
Y
BACKFILL
PLACED
HERE
-
C LAYER
B E N T O N I T E SLURRY
Aquiclude Aquitard
(Impervious Zone)
3. CompositeVerticalCutoff Barrier Systems

A concept for constructing a composite vertical impermeable barrier to prevent the migration
of contaminated groundwateror leachate from a hazardous waste site or waste disposal area is
described by Druback and Arlotta [32]. The composite system is a hybrid cutoff wall con-
structed with high-density polyethylene (HDPE), and sand backfill and is installed using the
slurry trench construction method. When properly installed, a low-permeability composite ver-
tical barrier results that has unique engineering properties, including improved chemical re-
sistance, leak detection, and groundwater migration control.
A full-scale construction test project of the system was performedat an existing sanitary
landfill in New Jersey to demonstrate the overall fabrication and construction procedures. De-
tailed procedures on this system, including design, construction, and performance data, are
provided by Druback and Arlotta in their 1985 paper [32].
4. Vibrating-BeamWalls
Vertical barriers to horizontal groundwater flow have been designed and constructed using the
vibrating-beam injection method as shown in Figure 9. This technique uses a vibratory-type
pile driver to cause the penetration of a beam of specified dimensions to the design depth.
Slurry is added through injection nozzles as the beam penetrates the subsurface soils andas the
beam is withdrawn.
The slurry used with the vibrating-beam technique is generally either cement-bentonite or
bituminous grout. Mix design considerations for cement-bentonite were discussed above. Bi-
tuminous grouts are prepared as a homogeneous blend of asphalt emulsions, sand, portland
cement, and water. Fly ash may also be included. It is reported that this bituminous grout can
resist strong acids and high saline content wastes.The use of thin slurry cutoff walls installed
by the vibrating-beam method is discussed by Leonards et al. [33] and McLay [34].
B. Top Seals (Cap or Cover Barrier Layers)

Top seals (i.e., surface seals, caps, covers), as shown in Figure 10, function to control surface
water so as to minimize infiltration, maximize runoff, prevent direct contact (suchas by bur-
rowing animals, whichmay dig into the landfill areas), and thereby reduce leachate production
260 Fang and Evans
MIX I NC P L A N T
SLURRY PUMP
V i b r a t i n g Bean S l u r r y
SLURRY INJECTlNC
NOZZLES AT BEAM
P e r v i o u s Zone
p e r v i o u s 20
1 1 1 1 1 1 1 1 1 I I I I IIIIII
Figure 9 Schematicdrawing of avibrating-beam slurry wall. (1) Topseal; (2) landfillmaterial;

(3)bottom seal.
I m p e r v i o u s Zone @A.’
Figure 10 Qpical cross section of a solid waste landfill witha native clay top seal. (1) Surface ero-
sion; ( 2 ) nonuniform settlement; (3) bottom erosion.
Solid Controlling and Liquid Wastes 261
and/or contaminant transport potential. Several types of materials can be used for the top seal
barrier layer, including compacted natural clay, bentonite clay, and synthetic membrane. Each
of these is discussed briefly in the following.
1. CompactedNaturalClayCaps
The most cost-effective top sealbarrier layer usually isone of compacted native clay material
from locally available sources. If suitable native claysare not available, imported materialsor
synthetic membranes mustbe used. In general, clays are thought to last longer than synthetic
materials, and, where feasible, clay caps rather than synthetic caps may be chosen. However,
to avoid the “bathtub effect” (more water entering the facility than can drain out), the use of
a synthetic membrane cap is required whenever the bottom liner is also a synthetic membrane
W].
Selection of clay materials for clay caps is based on the compacted hydraulic conductivity
of available materialas discussed by Johnson et al. [27]. As shown in Figure 10, the thickness
of the clay cap is typically0.6-0.8 m. The following are some of the factorsto be considered
in the design of a clay barrier layer.
The top several inchesof clay cannot beas well compacted as the remainder of the thick-
ness owing to the lack of confinement. Further, it may be difficult, in the long term, to
maintain the clay density in the top few inches
due to potential desiccation cracking,wet-
dry cycles, and freeze-thaw cycles.
The bottomof the claycap barrier layer may become somewhat intermixed with subgrade
material during construction. Therefore,the effective thicknessof a nominal 0.6-m cap is
likely to be less than 0.6 m.
The compaction procedures for the clay barrier layers are, in many ways, similar to those
followed for standard compacted fills as discussed by Hilf [36].
Protection of the claybarrier layer from degradation due to erosion by surface water run-
off, cracking due to drying, rutting from moving vehicles, and penetration by tree roots
and other vegetation mustbe provided. Some of these factors willbe further discussed in
Section 4 below.
Bentonite Clay Caps
Where local natural clay is not available in sufficient quantity or at an acceptable quality or
price, processed clay is a common alternative. Processed clay is typically bentonite from so-
dium montmorillonitic clay deposits. Bentonite clay is a strongly hydrophilic colloidal clay that
swells (expands) in water. The construction of a processed claycap requires the applicationof
the bentonite in powdered or granular form at a controlled rate (e.g., about 2 lb/ft2) followed
by adequate mixing with the in-place soilto a predetermined loose thickness. The mixture of
soil and bentonite is then compacted. The main advantages of this method are the low cost
coupled with relatively low hydraulic conductivity. The disadvantages are (1) it is difficult to
obtain uniform application and blending and (2) bentonite clay swelling is very sensitivepore
to
fluid chemistry. Thus if contaminated water permeates the bentonite clay barrier layer, signif-
icant increases in the hydraulic conductivitymay occur.
3. SyntheticMembraneCaps
Synthetic membranes (Figure11) can be used as the barrier layer in covers for waste contain-
ment [37,38]. The principal advantages of geosynthetics are their low hydraulic conductivity
and their ability to deform and remain intact. Thus geosynthetics can often accommodate the
large total and differential settlements that may occur in the landfill beneath the cover layer.
262 Fang and Evans
Polymeric Membrane Seal

Vegetated
ion
WASTE
(Garbage)
LBottom Seal
Figure 11 vpical cross section of a waste control system with a polymeric membrane seal. (1) Sur-
face erosion; (2) nonuniform settlement; (3) bottom erosion.
Membranes are available in a wide range of materials from numerous manufacturers. Addi-
tional information regarding geosynthetic materials is provided later in this chapter.
4. OtherSurfaceControls
In addition to surface sealing with
barrier layers, surface water diversion andcollection systems
can provide short- and long-term measures to isolate waste disposal sites from surface water
inputs. Techniques used to control flooding and off-site erosion transport of cover and surface
seal materials include dikes andberms, interceptor ditches, diversion dikes and berms, terraces
and benches, sheets and downpipes, levees, seepage ditches, and sedimentation basins and
ponds [39].
In summary, surface seals provide multiple functionsin the overall liquid and solid waste
containment control system.Their main function has been discussed as the control of infiltra-
tion by minimizing water infiltration and/or maximizing surface runoff.
C. Bottom Seals (Liners)

In newwaste containmentfacilities, it is usually necessaryto provide a liner system beneath the
waste disposalarea. The major functionof a liner is to prevent leachate or waste from migrat-
ing downward and entering the groundwater flow regime. The barrier layer for liner systems
can consist of nativeclays, prucessed clays, or geosynthetic membranesas previously discussed
for covers. It is importantto note that under the presentU.S.regulations, the use of a synthetic
membrane liner is considered the best technology to “prevent” migration of wastes, whereas
a clay liner will “minimize” migration of wastes.
1. CompactedNativeClayLiners
The compatibility between the compacted natural clays and the waste is an important design
consideration for the use of natural clays as liners. It is important to ascertain the volume
change and permeabilitycharacteristics of the proposed clay linermaterial. The bulk transport
of liquid waste throughcracks as discussed in Section I1 must be precluded. Bulk transport of
liquid through clay liners could occur due to differential settlement of the foundation basema-
tes Controlling
Liquid Solid and 263
terials. Compacted natural clay liners are often used as the final barrier layer in a liner system
composed of multiple leachate collection and geosyntheticbarrier layers. In this configuration
the capacity of natural clays to sorb contaminants is acknowledged.
2. Bentonite Clay Liners
Design and construction considerations for the use of processed clay for liners must include
waste-linercompatibility as well as the considerations previouslydiscussed. The volume
change characteristics of the processed clay are especially important. Generally, a bentonitic
processed clay is mixed with the subgrade material to form the low-permeability liner. The
impedance to groundwater flow is primarily due to the processed clays, especially when the
matrix soilis relatively free of natural fines. Hence,if the processed clayshrinks upon exposure
to the waste or leachate, large increases in hydraulic conductivity can occur. The hydrationof
a processed clay liner with uncontaminated water prior to waste disposalis recommended [M].
Triaxial permeability tests using the actual proposed clay subgradematerial, groundwater, and
leachate should be conducted as part of the design studies.
3. GeosyntheticMembraneLiners
As with other liner types, waste compatibility is a major design consideration. However, the
permeability of a polymeric liner canalso increase dueto liner stretching. Thus, total and dif-
ferential foundation settlement can impact the liner design. Close construction control is es-
sential to the overall system performance. The “permeability” of an installed membrane liner
system is generally a function of bulk transport through seams, joints, tears, holes, and pin-
holes. The long-term durability of geomembranes is discussed by Koerner et al. [41]. Studies
include ultraviolet radiation and chemical degradation as well as swelling, oxidation, and tem-
perature. In addition, predictive methods for the evaluation of long-term durability are pro-
posed and discussed.
D. Double-CompositeLinerSystem
A double-composite liner system proposed by Daniel and Koerner [42] is based on the com-
bination of clay and geotextile structures. This system is the minimum standard of care to
which future landfills should be held. It requires careful design, testing, and construction. As
shown in Figure 12, the double-composite liner system consists of four major parts:
Leachate collection systems (layers 1, 2, and 3)
Primary liners (layers 4, 5 , and 6 )
Leak detection system (layer 7)
Secondary liners (layers 8 and 9)
These major parts form nine layers. A tenth layer, the soil or rock subgrade, completes the
double-composite liner system.
1. Leachate Collection System
The leachate collection system is the uppermost segment, as shown in Figure 12. The system
is composed of a highly permeable granular material on the base of the disposal unit and a
high-transmissivity geocomposite materialfor side slopes, provided timely cover andadequate
protection are provided.
Layer I :Filters (Soil or Geotextile). A filter (soil or geotextile) to separate the lowest portion
of select waste or initial operations layer of soil from the leachate collection and drainage me-
dium is essential. If suspended particles from the leachate travel into the drainage system, it
264 Fang and Evans
Individual components
A
Cover
f
geotextile)
Filter
or
(soil
/ Waste
/ //
/ (geocomposite) Drain
or other)
Protector (geotextile
Barrier (geomembrane)
Leachate collection system

Primary composite liner
Leak detection system
Secondary composite liner
Jbgradf3
Figure 12 Double-composite liner system. (After Daniel and Koerner [42].)
may clog. To minimize this problem, it is suggested that(1) filters be used only when they are
truly needed and that (2) high-permeability filters be employed.
A geotextile filter is part of the geocomposite drainage layer along side slopes. Geotextiles
are sensitive to ultraviolet light degradation if left exposed and therefore require protectionto
avoid this failure mode.
Layer 2: Drain (Gravel for Base, Geocomposite for Side Slopes). The leachate collection
layer requires high in-plane transmissivity and pores sized to resist plugging. In this way the
hydraulic head on the underlying barrier layer can be minimized.
Layer 3: Protector (Geotextife or Other). This layer prevents materials in the drainage layer
from puncturingthe primary geomembrane liner.Protectors are usually thick, needle-punched,
nonwoven geotextiles.
2. Primary CompositeLiner
Layer 4: Barrier (Geomembrune). This component of the primary liner can be made from
polymeric materials, includingpolyvinyl chloride (PVC), chlorinated polyethylene (CPE),
chlorosulfonated polyethylene (CSPE), ethylene interpolymer alloy (EIA), high-density poly-
ethylene (HDPE), and verylow density polyethylene (VLDPE).At present, HDPE geosynthet-
ics offer the most versatility with respect to contaminant resistance and overall engineering
properties such as strength and permeability.
Layer 5: Barriers (GeosyntheticCfayLiner). For the soil component of the primary liner, the
geosynthetic clay liner (GCL) is recommended. GCLs, previously called prefabricated clay
blankets or referred to by other terms, are factory-manufactureddry bentonite clay layers sand-
wiched between geotextiles or attached to a geomembrane. This barrier offers low hydraulic
conductivity along with adsorption capacity and reduces the rate of contaminant transport, par-
ticularly transport due to diffusion.
Layer 6 Separator (Geotextifeor Other). To avoid migration of clay particles from the GCL
into the underlying geonet, adequate separation is needed. Best results in experimental tests
have been obtained with (1) nonwoven, needle-punched geotextile with small apparent open-
ings; (2) nonwoven, heat-bonded geotextile; and (3) geomembranes.
3. LeakDetectionSystem
This leak detection system is the third major part of the system. It is also known as the sec-
ondary leachate collection system. It identifies leakage from the primary lining system and
enables it to be collected and removed. Its design is similar to that of the primary leachate
collection system.
Layer 7 Drain (Geonef). A geonet is preferable to granular materials for the leak detection
layer because itis much easier to place onside slopes and canbe placed with lightweight equip-
ment, and because granular materials can puncture the underlying geomembrane. Geonets also
offer fasterdetection of leaks thanmost granular materials. Hazardous waste facilities typically
must detect leaks within 24 hr, and often a geonet is the only material than can do this.
4. SecondaryCompositeLiner
m e r 8: Barriers (Geornembrane). Technical requirements for the secondary geomembrane
liner are generally the same as for the primary layer (layer5), so the same type and thickness
of material is usually used.
Layer 9 Barriers (Cornpacred Soil Liner). A compacted soilliner can be constructed without
risk of damaging any underlying liner system components.
5 . Subgrade (Soil or Rock)(Layer 10)
For large-scale facilities, a complete subsurface soil investigationis necessary. The large areal
extent of landfills resultsin a significant depthof stress influence. The strength and compress-
ibility of the underlying soils must be fully investigated to ensure foundation stability.To cor-
rect any disturbance due to construction, the site should be proofrolled after final grading.
VI. MAINTAINING PERFORMANCE OF WASTE CONTROL SYSTEMS

A. GeneralDiscussion
It is necessary to ensure that the waste control system willcontinue to operate as designedfor
many years. The landfilled waste may remain toxic for many hundreds of years. As engineers
we have frequently been gearedto a design life of 40 or 50 years whereas the landfills we are
presently buildingwill be here for generations to come. It is therefore necessaryto design and
construct waste control systems that acknowledge future uncertainties and properly account for
long-term impacts on the system performance.
B. ChemicalAttackonLiners
Long-term durability evaluations for liners of both clay and geosynthetic membranes require
studies of the impact of chemicals on the engineering properties of the liners. The change in
hydraulic conductivityof clay barriers due to changes in pore fluid chemistry must be studied
if the liner is to successfully perform over the long term. The “compatibility” of geosynthetics
with the landfill leachate must be evaluated. In allof these studies it is necessary to accelerate
time in order to complete the testing within a reasonable time period. For hydraulic conduc-
tivity testing, this acceleration of time is accomplished through the use of high hydraulic gra-
dients. In other studies, more concentrated forms of the contaminants are used. In anycase, our
ability to predict barrier performance for long time periods is limited as we do not have per-
formance data to verify our models.
266 Fang and Evans
Figure 13 Mechanisms of soil-root-pore fluid (leachate) interaction at landfill area. (1) hre fluid
(leachate) in landfillseepsoutthroughroothairsbysuctionforce. (2) Pore fluid (leachate) in landfill
seeps out between root and soil by capillary action. (3) Cross section of liner.
C. Vegetative Root Attack on Liners

Landfill sites are generally planted with vegetation to enhance evapotranspiration and for the
purpose of beautification of unattractive landfill sites. Further, without regular maintenance,
woody vegetationwill begin to appear. Trees and vegetation also have a detrimental side effect.
l k o important phenomena related to how tree roots attack liners are discussed below.
1. Tree roots lookingfor nutrition (food) and water will grow deeper intothe subsurface of the
landfill area. Roots can and will penetrate barrier layers.
2. Pore fluid (leachate) in landfill can migrate through and along roots and root hairs.
Roots penetrate the subsurface to acquire food and water, and landfill sites readily provide
these necessities for growing trees and other vegetation. The penetrating force producedby tree
roots is strong enough to penetrate clay liners or synthetic membranes. For example, bamboo
roots can penetrate into a 6-in. thick concrete wall. Many roadways, pavements, and drainage
facilities have been damaged by roots of common trees that grow around landfill areas.
Some typesof vegetation (such as squashes) spread theirroots laterally and widely in the
near-surface (less than 1 ft in depth) zone. Some roots systems are coarse and open, whereas
others consist of masses of fine fibrous roots. The abilityof roots to obtain nutrient substances
also varies greatly. Even though we cannot explain wholly the quantity of nutrients produced in
the landfill environment that is utilized by roots, the forces within the plants and aroundtheir
feeding roots may also have a controlling influence.
Plants also require immense quantities of water, practically all of which is absorbed from
the soil through their root systems. Special plant features that providefor absorption includethe
tips of roots and innumerable root hairs.A mechanism by which pore fluid (leachate) in land-
fills may migrate out through the root system is illustrated schematically in Figure 13. This
phenomenon of moisture migration within the root hair and between root hair and soilis due to
suction force and capillaryaction. Plant species differ not only in their water requirements but
also in their adaptation to water conditions. Some plants are so constituted that they can tol-
erate an abundance of soil water, whereasothers can endure limited moisture. Since our present
regulations requirethat a landfill site be maintained for a period of 30 years after closure, it is
necessary to determine the impact of vegetation on the waste control system forthe reminder
of the landfill life while the contained contaminants are still toxic.
D. Other Factors
Construction quality assurance (CQA)is required to correctly transfer the design as contained
in reports and drawings into the real systems as constructed in the field. Careless or incom-
petent construction can defeat the best design.
VII. SUMMARYANDCONCLUSIONS
Almost 90% of hazardous wastes are in liquid form. An understanding of the effect of pore
fluids on liner behavior is essential to the design of various components of waste control fa-
cilities. Without a good understanding of the liner-pore fluid interaction, there is no sound
basis on which to project the long-term behavior of these systems;
Passive techniques presented in this chapter can and have been used to mitigate contam-
inant migration. Consideration must be givento the identification of all contaminant pathways
and selection of the most appropriate control technique. Each technique then must be evaluated
as to its effectiveness, and the design and construction must incorporate all site-specific and
technique-specific considerations.
Contaminants will eventually migrate into the environment, despite our best efforts. With
this premise, our control systems must reduce the rate of migration to an imperceptible rate or
to a rate at which our environment can assimilate the contaminants without damage.
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Solid Controlling Wastes 269
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12
Solidification and Stabilization
Techniques for Waste Control
A. Samer Ezeldin and George I? Korfiatis

Stevens Institute of Technology
Hoboken, New Jersey
1. INTRODUCTION
Industrial activities inthe United States and other developed countries generate large volumes
of by-product waste. These by-products mustbe disposed of in a safe manner in order to avoid
adverse impacts on the environmentand public health. In recent years, solidification and sta-
bilization techniques have emerged as viable alternatives for safe waste disposal. Currently a
large number of research organizations and professional companies are engaged in waste sta-
bilization and solidification processes.
The terms stabilization and solidification have been traditionally used interchangeably.
The fact is, they are two separate processes. Stabilization refers to a chemical fixation tech-
nique used to render a waste less toxic or less harmful to the surrounding environment. In
general, stabilization reduces the hazard potential of the waste. Examples of stabilization tech-
niques include ion exchange of heavy metals in the aluminosilicate matrix of a cementitious
stabilization agent and sorption of heavy metals on fly ash in aqueous systems. Solidification
is used to transform the waste into a stable and durable matrix that is more compatible for
storage, landfill, or reuse. Solidification can be accomplished with or without chemical fixa-
tion. This process creates barriers between waste components and the environment by either
reducing permeability of the waste or reducing the effective surface area available for diffusion,
or both.
II. NONCHEMICALSOLIDIFICATIONTECHNIQUES
Nonchemical solidification includes dewatering, mixing with absorbents, and vegetative sta-
bilization.
Dewatering is the removal of water by thermal drying, filtration, or centrifugation. The
dried waste is usually either left in place or transported to a suitable landfill location.
271
272 Ezeldin and Koflatis
In the process of mixing with absorbents, the purposeis to absorb the water phase of the
waste using agents with high absorptive capacity. The most commonlyabsorptiveused material
is soil. Becauseof the absence of chemical reactions betweenthe waste and the absorbent, the
absorbed water can be pressurized from the waste-absorbent system. This process is usually
followed by chemical solidification, which solidifies the waste-absorbent matrix. In order not
to oversaturate the absorbent (resulting in a larger quantity of waste to be disposed of), the
addition of absorbent must be carefully controlled.
Vegetative stabilizationinvolves growing plants whose roots stabilizethe soil. This method
has been used for decades in the erosion control of unconsolidated soil systems. This process
can be applied for waste stabilization provided that the waste constituentsare compatible with
the vegetative growthand that the long-termuse of the landdoes not include productionof food
crops or fodder.
111. CHEMICAL SOLIDIFICATION AND STABILIZATION PROCESSES

Chemical solidification and stabilization processes are used to treat industrial and hazardous
wastes. These processes represent alternatives to Ocean disposal or conventional landfilling.
Most of these processes originatedin the field of radioactive waste control and management.
Chemical solidification and stabilization refer to waste treatment that results in the combined
effect of
1. Improvement of physical properties (mechanical stabilization)

2. Encapsulation of pollutants (immobilization by fixation)
3. Reduction of solubility and mobility of the toxic substances (immobilization by isolation)
Mechanical stabilization reduces the bulk mobility of the waste and makes it durable and
dimensionally stable, The final product should be capableof resisting deterioration caused by
mechanical or environmental stresses. The extent of mechanical stabilization is evaluated by
conducting strength and durability tests. Immobilization by fixation minimizes the local mo-
bility of individual contaminant components. Leaching tests are conducted to determine the
effectiveness of fixation. Immobilizationby isolation limits the risk of the contaminants reach-
ing the boundaries of the deposited massby providing protection againstinternal contaminant
transport (avoiding internal and external cracking) and by restricting internal transport path-
ways (low permeability).
There are many solidificationand stabilizationtechniques used inthe industry for different
types of waste materials.Each of these techniquesis usually recommended for use with specific
waste constituents. Hence, process selection involves weighing advantages and disadvantages
for each particular project. Generally, stabilizatiodsolidificationtechniques can be divided
into the following seven major categories:
1. Cement-basedtechniques
2. Pozzolanictechniques(silicate-basedtechniques)
3. Thermoplastic techniques (including the incorporation of bitumen, paraffin, and polyeth-
ylene)
4. Sorbenttechniques
5 . Organicpolymertechniques
6 . Encapsulationtechniques(jacketing)
7. Vitrification
Solidification and Stabilization Techniques 273
A. Cement-BasedTechniques
Portland cement is obtained by heating limestone and clay or other silicate mixtures at high
temperatures. The resulting clinker is ground to a highly uniformpowder.fine Anhydrous port-
landcementconsistsmainly of C3S,C2S,C3A,and C,AF, whereC = CaO, S = SiOz,
A = A1203, and F = Fez03. In ordinary portland cements, the respective amounts rangebe-
tween 35 and 65%, 10 and 40%, 4 and 15%, and 5 and 15%. Table l presents selected char-
acteristics of these materials. Addition of water to portland cement initiates the cementation
process. Needle-like crystals of calcium sulfoaluminate hydrate (ettringite)start forming within
a few minutesof cement hydration. After a period of time, the ettringite eventually transforms
to the monosulfate hydrate. A few hours after initiation of the cementation process, large pris-
matic crystals of calcium hydroxide (CH) and very small crystals of calcium silicate hydrates
(C-S-H) beginto fill the empty spaces previously occupied by water and the dissolving cement
particles. There are three major components of the hydrated cement paste.
Calcium silicate hydrate forms about 60% of the solids volume and is the most important
component. It is composed of layer structures with a very high surface area (about 500
m2/g). Its strength is attributed mainly to van der Waals physical adhesion forces.
Calcium hydroxide constitutes about 25% of the solids volume. It is formed of large crystals
with low surface area. Its limited van der Waals forces and its higher solubility compared
to C-S-H make the concrete reactive to acidic solutions.
Calcium sulfoaluminate forms about 15% of the solids volume. It plays a minor role in the
cementitious structure properties. Due to the presence of the monosulfate hydrate, con-
crete chemical durabilityto sulfate attack is usually of concern.
Most hazardous wastes can be incorporated in a waste-cement system. The suspended pol-
lutants would be incorporated into the final hardened concrete. During the solidification pro-
cess, the concrete formation binds and strengthens the mass, coats and incorporates some
Table 1 Principal Compounds of Portland Cement and Their Characteristics

Ca0.Al2O3FezO3
Ca0.AIz03
fJ-CaO.SiOz
CaO.SiOz
Abbreviated formula c3s C3A C4AF
Common name Alite - Ferrite phase, Fss
Principal impurities MgO.AI2037 SO2, MgO, SiO2. MgO
b 0 3 alkalies
Common crystalline Monoclinic Cubic, Orthorhombic
form orthorhombic
Avg. amount present 50 (35-65) 8 (0-15) 8 (5-15)
(%) (range) in ordi-
nary cement
Rate of reaction with Medium Fast Medium
water
Contribution to
strength
Early age Good Good Good
Ultimate Good Medium Medium
Typical heat of hydra- 120 (medium) 320 (high) 100 (medium)
tion (calk)
274 Ezeldin and KoMatis
contaminant moleculesin the siliceous solids, and blocks pathways between pores. Due to the
elevated pH of cement mixtures (in the range of 9-11), most multivalent cations are converted
into insoluble hydroxides or carbonates. Thus, this process is highly effective for waste com-
ponents with high levels of toxic metals. However,the presenceof certain inorganic compounds
and organic componentsin the waste can create an interference mechanism, delaying the set-
ting and curing of the final product. Biczok[l] presented twolists of industrial wastesthat are
harmless or are deemed to be aggressive to cementitious products. The list of wastes that can
be tolerated includes
Brines containing basesbut not sulfates
Potassium permanganate, occurring at fermenting and purification installations
Sodium carbonate and potassium carbonate
Bases, provided that their concentrations are not excessively high
Oxalic acid occurring at tanneries
Mineral oils and petroleum products (benzene, kerosene, cut-back oil, naphtha, paraffin, tar) as
long as they contain no acids that can continue to remain in the products after chemical
treatment
The list of wastes considered aggressiveto cementitious products includes
Water containing gypsum
Ammonia salts
Hydrochloric, nitric, acetic, and sulfuric acids
Chlorine and bromine
All sulfur and magnesium salts
Salts of strong acids
'High sulfate content in the waste can be tolerated by using Vpe I1 or Vpe V portland
cement rather than the typically used "Qpe I cement. There is reasonable correlation between
sulfate resistance of cement and its tricalcium aluminate (C3A)content. Hence, use of 1s.pe I1
cement (C3A is limited to8%) or "Qpe V cement (C3A is limited 5%) to can providea moderate
or good sulfate resistance, respectively. Additives havebeen developed to overcome the effects
of several of the other interfering agents. Some of these additives
are clay, vermiculite, soluble
silicates, and some proprietary products.
The advantage of cement-based techniques is the use of low-cost materials and common
commercial concrete processing equipment with no need for specially skilled operators. The
main disadvantage isthat most of the wastesare not chemically bonded. Hence, once subjected
to acidic leaching, resolubilization of the metal hydroxides and carbonates becomes a major
concern.
B. Pozzolanic Techniques
Pozzolanictechniquesinvolvemixing a siliceous (pozzolanic) material with other alkaline
earths such as lime or gypsum in the presence of water to produce a concrete-like mass. This
technique generally involves pozzolanic reactions between SiO,, A1203, F%03, and available
calcium in lime. The results of these reactions are very stable and strong calcium silicates and
aluminates that can be considered the equivalent of portland cement in initiating the cemen-
tation process. The most common pozzolanic materials used in stabilizatiodsolidificationof
wastes are fly ash, ground blast-furnaceslag, and cement kiln dust. The use of these materials,
themselvesconsideredby-products of little commercialvalue, to stabilindsolidify another
waste may offer economic advantages. The vulnerability of the final product to acidic leaching
is the major disadvantage of this technique. Combined cement-pozzolanic processes can be
used to give a better and more economical final waste containment.
C. ThermoplasticTechniques
In thermoplastic processes, the waste is dried, heated, and then dispersed through a heated
plastic system. Bitumen is themost common matrix material. However, paraffin and polyeth-
ylene have alsobeen employed. The final mixture is then cooled and is usually embedded in a
containment system. Organic chemicals that could react with the plastic matrix, leading to
physical deterioration, cannot be disposed of with this technique. The process employs spe-
cialized equipment, is energy-intensive, and requires trained operators. The elevated temper-
atures of the process limit the typesof materials that canbe incorporated into the matrix (e.g.,
citrates). Typically, the associated leach rates are low. Also, the binders tend to perform well
in resisting water and microbial attack.
D. SorbentTechniques
The sorbent techniques involve the use of certain clay minerals characterized with high specific
surfaces to fix and immobilize hydrocarbon molecules. This immobilization usually takes place
on the outer and inner surfacesof clay particles. Typical clay minerals used in this technique
include sodium montmorilloniteand vermiculite.
E. OrganicPolymerTechniques
Originally, organic polymer techniques were introduced to solidify and/or stabilize radiological
wastes to allow for transportation. The urea-formaldehyde (UF)system is considered the most
frequently employed organic polymer solidification technique. However, this system has been,
criticized becauseof its high cost, water loss during reaction, and environmental concerns with
formaldehyde. Generally, in this technique, the wet or dry waste is mixed with a prepolymer
in a waste secondary containment system. After the two components have been thoroughly
mixed, a catalyst is introduced into the mixture. This process forms a mass that traps the waste.
Any water associated with the waste should be disposed of after polymerization. After curing,
the polymerized mass becomes highly impermeable. The product is characterized by a slow
leaching rate even when crushed owing to its hydrophobic nature.
F. EncapsulationTechniques
In this type of technique, wastes that have been compactedor bonded togetherare encapsulated
in a coating of inert materials. These coating materials are chemically stable, with good re-
sistance to biodegradation and adhesionto enclosed wastes. High-density polyethylene (HDP)
and polybutadiene have been used to encapsulate wastes.The process is energy-intensive and
1 requires
skilled
labor.
G. Vitrification
Vitrification is a thermal treatment process that uses high temperatures
to melt waste material.
The melted waste is then fused in glass or another form of synthetic mineral. Organic con-
are in-
taminants are volatilized during the melting process, while the inorganic contaminants
276 Ezeldin and Kolfiatis
L
corporated intothe impermeable matrixof the final product. Glass andsynthetic silicates offer
a safe means of waste disposal because they are very slowly leached by water. The process
mandates highly skilled labor and is extremely energy-intensive.
Vitrification requires an electric source to produce high temperatures (1500-2OOO"C)to
melt the waste material. Electrodes made of molybdenum or graphite are commonly used for
this purpose. An electric current is then applied to the electrodes and travels throughthe waste
material. Typically a 12,500-V three-phase current is used. The melted waste becomes more
conductive, and the current causes the melt to continue downward and outward. Heat willei-
ther destroythe organics or cause volatilization. A gas collection and treatment systemis usu-
ally required to address the problem of emissions. Because of melting, the pore spaces are
eliminated, resulting in a volume reduction of about 20-40% depending on the porosity ofthe
treated waste. The melted material cools to a glassy microcrystalline material commonly re-
ferred to as a monolith. The glassy product, which has a random crystalline structure, will
fracture colloidally instead of along planes. The end product has an estimated life expectancy
of 10,OOO to 20 million years.
IV. SPECIFICATIONS FOR SOLIDIFIEDISTABILIZED WASTES

The final form of stabilized/solidified waste mustbe stable, environmentally compatible, and,
if possible, of commercial value. A great deal of consideration should be given to waste and
process compatibility to avoid detrimental effectsof the final product suchas heat generation,
release of toxic materials, and loss of strength. Table 2, from Martin and Johnson [2], sum-
marizes compatibility considerations of selected waste categories. The most important char-
acteristics of the stabilizedkolidified waste that must be evaluated and found acceptable are
the following.
Leachability. Leaching tests are designed to determine the maximum concentration level of
contaminants that water can remove from the hardened waste. The most used leaching test
is the EPAToxicity Contaminant Leachate Procedure (TCLP). It requires grinding the
waste to ensure maximum surface contact area with an acidic extractionfluid. The ratio of
waste to extraction fluid is set to achieve a saturated solution. The contaminant concen-
tration is obtained and compared against the toxicity characteristics set by the EPA (see
Table 3).
Free-liquid conrenr. Current EPA regulations allow no free water in the waste final form.
h-permeability. The treated waste should have relatively low permeability (typical accept-
able permeabilityrangesfrom to 10"' cdsec). Higherpermeability wouldresultin
increased leaching of contaminants.
Biodegradation. Biological activity is undesirable and should be avoided as it can produce
acids that could dissolve and leach pollutants from the waste. Tests suchas ASTM G-21
and G-22 are used to determine the ability of wastes to withstand biological attack.
Strength. The unconfined compressive strength of the hardened waste depends on its final
use. Usually, only 20 psi is required for burial. However, if the solid waste is to be used
for other purposes, for example, as a construction material, greater strength may be re-
quired (up to 4OOO psi). ASTM C-39 is usually employed to evaluate the compressive
strength of cementitious stabilizedkolidified wastes.
Durabiliq. If it willbeexposedtofreeze-thawandwet-dry cycles, stabilized/solidified
waste should be tested for durability. For moderate exposure,ASTM D-560(freeze-thaw
durability) and ASTM D-554 (wet-dry durability) are used. However, for harsh exposure,
ASTM C-666 is recommended.
Table 2 Compatibility of Waste Categories with Solidification/Stabilk.ationTechniques
~~ ~ - ~
Treatment type
Waste component Cement-based Lime-based Thermoplastic Organic polymer (UF) Surface encapsulation
Organics
Organic solvents May impede setting; May impede setting; Organics may vaporize May retard setting of Must first be absorbed
and oils may escape as vapor may escape as vapor on heating P O l Y ~ ~ on solid matrix
Solid organics Good;often increase Good; often increases Possible use as binding May retard setting of Compatible; many en-
(e.g., plastic, durability durability agent polymers capsulation materials
resins, tars) are plastic
Inorganics
Acid wastes Cement will neutralize Compatible Can be neutralized be- Compatible Can be neutralized be-
acids fore incorporation fore incorporation
Oxidizers Compatible Compatible May cause matrix May cause matrix May cause deterioration
breakdown breakdown of encapsulating
materials
Sulfates May retard setting and Compatible May dehydrate and re- Compatible Compatible
cause spalling unless hydrate, causing
special cement is splitting
Ussd
Halides Easily leached from May retard setting; May dehydrate Compatible Compatible
cement; may retard most are easily
setting leached
Heavy metals Compatible Compatible Compatible Acid pH solubilizes Compatible
metal hydroxides
Radioactive Compatible Compatible Compatible Compatible Compatible
materials
Source: Martin and Johnson 121.
278 and Ezeldin Koflatis
Table 3 Toxicity Characteristics of Constituents and Regulatory Levels

Chronic
toxicity
Regulatory
EPA
number Constituent
HW number
WO4 Arsenic 7440-38-2 0.05 5.0
WO5 Barium 7440-39-3 1.o 100.0
DO18 Benzene 7 1-43-2 0.005 0.5
WO6 Cadmium 7440-43-9 0.01 1.o
DO19 Carbon tetrachloride 56-23-5 0.005 0.5
DO20 Chlordane 57-74-9 0.0003 0.03
DO21 Chlorobenzene 108-90-7 1 100.0
W22 Chloroform 67-66-3 0.06 6.0
m 7 Chromium 7440-47-3 0.05 5.0
DO23 0-Cresol 95-48-7 2 200.0
DO24 mCresol 108-39-4 2 200.0
DO25 p-Cresol 106-44-5 2 200.0
DO26 Cresol 2 200.0
DO16 2,4-D 94-75-7 0.1 10.0
DO27 1 &Dichlorobenzene 106-46-7 0.075 7.5
DO28 1 ,2-Dichloroethane 107-06-2 0.005 0.5
DO29 1,1-Dichloroethylene 75-35-4 0.007 0.7
DO30 2,CDinitrotoluene 121-14-2 0.0005 0.13
DO12 Endrin 72-20-8 0.0002 0.02
DO3 1 Heptachlor (and its hydroxide) 76-44-8 O.ooo08 0.008
DO32 Hexachlorobenzene 118-74-1 0.0002 0.13
DO33 Hexachloro-l , 3-butadiene 87-68-3 0.005 0.5
DO34 Hexachloroethane 67-7 -1 0.03 3.0
DO08 Lead 7439-92-1 0.05 5.0
DO13 Lindane 58-89-9 0.004 0.4
Do09 Mercury 7439-97-6 0.002 0.2
DO 14 Methoxychlor 72-43-5 0.1 10.0
DO35 Methyl ethyl ketone 78-93-3 2 200.0
DO36 Nitrobenzene 98-95-3 0.02 2.0
DO37 Pentachlorophenol 87-86-5 1 100.0
DO38 Pyridine 110-86-1 0.04 5.0
DO10 Selenium 7782-49-2 0.01 1 .o
DO1 1 Silver 7440-22-4 0.05 5.0
DO39 Tetrachloroethylene 127-18-4 0.007 0.7
DO 15 Toxaphene 8001-35-2 0.005 0.5
Do40 Trichloroethylene 79-01-6 0.005 0.5
DO41 2,4,5-Trichlorophenol 95-95-4 4 400
m 2 2,4,6-TrichlorophenoI 88-06-2 0.02 2.0
DO17 2,4,5-TP (Silvex) 93-72-1 0.01 1.o
Do43 Vinyl chloride 75-01-4 0.002 0.2
V. EFFECT OF ORGANIC AND INORGANIC WASTES ON

PORTLAND CEMENT
Several studies have examined the effects of typical organic waste components upon cement-
based solidification/stabilizationtechniques. Most of these studies investigate the setting and
durability of the waste product. Fewer studies have presented extensive testing thefor strength
Solidificationand Stabilization Techniques 279
Table 4 - Compatibility of Portland Cement with Organic Compounds

Portland cement
groupChemical I Types I1 and V
Alcohols and glycols Durability: decrease (destructive Durability: decrease (destructive
action occurs over a long time action occurs over a long time
period) period)
Aldehydes and ketones DIU DIU
Aliphatic and aromatic Set time: increase (lengthen or pre- Set time: increase (lengthen or pre-
hydrocarbons vent from setting) vent from setting)
Durability: no significant effect
Amides and amines DIU DAJ
Chlorinated hydrocarbons Set time: increase (lengthen or pre- Set time: increase (lengthen or pre-
vent from setting) vent from setting)
Durability: decrease (destructive Durability: decrease (destructive
period) period)
Ethers and epoxides DIU DIU
Heterocyclics DIU DIU
Nitriles DIU DIU
Organic acids and acid Set time: no significant effect Set time: no significant effect
chlorides Durability: decrease (destructive Durability: decrease (destructive
period) period)
Organometallics D/U DIU
Phenols Set time: no significant effect DIU
Durability: decrease (destructive
action occurs over a long time
period)
Organic esters DIU DN
DRI = dataunavailable.
Source: Spooner et al [3].
and leachabilityof the hardened waste product. In general, strength and leachability properties
vary withtime, waterkement ratio, and interaction with individual waste components. Spooner
et al. [3] compiled existing information about the compatibility of cement-based stabilization
and solidification techniques with different classesof organic chemicals. Table4, from Spooner
et al. [3],includes a matrix that summarizes the compatibility of Type I, Type 11, and Type V
cements with different groups representing thetypes of organic compounds most likelyto be
found in hazardous wastes.
Spooner et al. [3] also reviewed existing literature about the known effects of inorganic
compounds on stabilizatiodsolidification cement-based processes. Table 5 illustrates that in-
organics have a pronounced effect on setting time and durability of the final product.
VI. EFFECT OF ORGANIC AND INORGANIC WASTES ON

POZZOLANIC BINDERS
During the last decade, there has been increasing interest in the use of pozzolanic bindersto
stabilize/solidify wastes. Selected research projectsin which pozzolanic binders are used as a
binder for waste stabilizatiodsolidification are presented in Table 6 (Eklund [4]). This table
280 and Ezeldin Koeatis
Table 5 Compatibility of Portland Cement with Inorganic Compounds

Portland cement
group Chemical QpeI and Qpes I1 V
HeavymetalsaltsandSettime:increase(lengthen or pre- Set time: increase (lengthenor pre-
setting)from vent
complexes vent from setting)
Durability: decrease (destructive Durability: no significant effect
action begins within a short time
period)
Inorganic
acids
time:
Set
significant
no effect Set time: no significant effect
period)
Inorganic
bases
time:
Set
significant
no effect KOH and NaOH-
Durability: no significant effect Set time: no significant effect
Durability: decrease (destructive
period)
Others-
Set time: no significant effect
Inorganic salts Set time: increase (lengthen or pre- Set time: increase (lengthen or pre-
vent from setting) vent from setting)
action begins within a short time
period)
Source: Spooner et al. [3].
provides an overview of the types of inorganic and organic wastes that have been studied for
waste stabilization. These research projects indicate that the useof pozzolans is becoming
widely accepted in research studies to stabilizelsolidify both organic and inorganic wastes.
There is, however, a need for a better understanding of fundamental chemical and physicalre-
actions that controlthe pozzolans-waste interaction and better predictive models for determin-
ing short- and long-term performancecharacteristics of the hardened waste.
VII. EFFECT OF ORGANIC AND INORGANIC WASTES ON ASPHALT

AND POLYMERIC BINDERS
Spooner et al. [3] compiled existing studies (up to 1984) on the interaction of organic and in-
organic wastes with asphalt and polymeric binders. Tables 7-9 from that reference represent the
available information in matrix form. The effect on setting time and durability was found to
vary significantly depending on the chemical group and the binder type.
VIII. REUSE OF PETROLEUM-CONTAMINATED SOILS IN CONCRETE

PRODUCTION
An experimentalinvestigationdesigned to evaluatetheeffectiveness of usingpetroleum-
contaminated soils (PCS)as fine aggregate replacement in concrete was conductedat Stevens
Institute of Technology. The details of the experimental programand the resulting findingsare
solidification and Stabilization Techniques 281
Table 6 Research on Stabilization using Pozzolanic Binders

e Binder Organization
description Waste
type
Fly ash, lime Organic Acid hydrocarbon sludge, Drexel Univ.
spent clay
Class C ash, lime, and ce- Organic Solvent extraction raffinate ORNIfDOE
ment mixtures with Class
F ash
Fly ash, lime Organic Methanol, xylene, benzene, Corps of Engineers
adipic acid, oil and grease
Portland cement, fly ash, Organic Organic sludges Velsicol Chemical
calcium sulfate dihy- Corp.
drate, lime, recycled
rubber, asphaltene, adsor-
bent material
Class C fly ash, hydraulic Inorganic Radioactive waste alkaline E.I. DupontAJ.S.
blast furnace slag salt solution DOE
Portland cement, Class C Inorganic Radioactive soluble salts Pennsylvania State
and Class F fly ash waste Univ.
Class C fly ash Inorganic MO processing waste, Zn American
refining sludge, electro- Resources Corp.
plating sludge
Fly ash, portland cement Inorganic Zinc nitrate, cadmium ni- Oxford Univ.
trate, mercury chloride, Imperial College
mercury nitrate solutions
Fly ash, cement, lime, Inorganic Neutralized sludge from tita- State Univ. of New
hemihydrated calcium nium processing York
sulfate, dehydrated cal-
cium sulfate
'Qpe I cement with ClassF Inorganic Iron. steel Pennsylvania State
fly ash Univ.
Portland cement, Class C Inorganic Electroplating sludge Univ. of Missouri
fly ash
'Qpe 2 portland cement Inorganic Synthetic metal hydroxide Univ. of New
sludges Hampshire
Class C fly ash Inorganic Water-based drilling muds Univ. of Oklahoma
Class C fly ash, lime Organic and Garbage and chemical incin- Aardelite USA
inorganic erator waste, gasifica-
tion ash and slag, sewer
sludge, kiln waste,
gypsum, ash from Lo-
nox burners, fluidized-
bed ashes
Source: Eklund [4].
discussed by Ezeldin [5-71. In this section a general description of the experimental program
and highlights of results are presented.
Five PCS types with different levels of heating oil and gasoline contamination were in-
vestigated. Three PCSlsand replacementratios were incorporated. Setting times, strength, du-
rability, and leachability of benzene to water were evaluated. npe111portland cement meeting
ASTM C-l50standard specifications was used during the entire experimental program. Fine
282 and Ezeldin Kolfiatis
Table 7 Interaction of SolidificationlStabilization Binders and Organic Chemical Groups

p Chemical
Alcohols and glycols Durability: no significant effect Durability: decrease
Aldehydes and ketones Durability: decrease (destructive Durability: no significant effect
period)
Aldehydes only-Set time and
durability: no significant effect
Aliphatic and aromatic Durability: decrease (destructive Durability: no significant effect
hydrocarbons action occurs over a long time
period)
Amides and Amines DAJ DN
Chlorinated hydrocarbons D/U Durability: no significant effect
Ethers and epoxides DN Durability: no significant effect
Heterocyclic DIU Durability: no significant effect
Nitriles DN DIU
Organic acids and acid Durability: no significant effect Set time: increase (lengthen or pre-
chlorides vent from setting)
Organometallics DIU DIU
Phenols Durability: decrease (destructive D/U
period)
Organic esters DN D/U
D/U = data unavailable.
aggregate was a natural sand, and coarse aggregate consistedof 3/8-in. crushed stone.The soil
classification, moisture content, contaminant type, and contamination concentration are shown
in Table 10. Soils were sieved through a No. 4 sieve before use to discard any debris or large
unwanted particles.
A concrete control mixture with no PCS was used as reference and had a compressive
strength of 6OOO psi after 7 days. For each soiltype, three mixtures were obtainedby replacing
sand with PCS (PCS/sand ratio of lo%, 20%, and 40% by weight). Table 11 shows the mixture
proportions and designations. After mixing,the following specimens were cast: 3 X 6 in. and
4 X 8 in.cylinders for compression tests, 4 X 4 X 14 in.prismsfor flexural tests,
2 X 2 X 10 in. prisms for durability tests, and 2 X 2 X 2 in. cubes for leachability tests. All
concrete specimenswere left at room temperature for24 hr and then removed from their molds.
They were then immersed in water until testing, with the exception ofthe leachability test spec-
imens, which were left uncovered at room temperature.
The 3 X 6 in. compression cylinderswere tested in duplicate at an early age (2 days; see
Table 12). The 4 X 8 in. compression cylinders were tested in duplicateat a later age (7 days;
see Table 12). Testswereconducted in accordancewith ASTM procedureC-39.The
4 X 4 X 14 in. prisms were tested after 7 days accordingto A S T M C-78 as indicated in Table
12. The durability tests consisted of two parts: freeze-thaw testing and wet-dry testing. The
wet-dry testing was performedin accordance with ASTM D-559, while the freeze-thaw test-
ing was performed according to ASTM D-560. The leachability testwere performed in dupli-
cate on monolithic2 X 2 X 2 in. concrete cubes obtained using mixture C3 for eachof the five
soil types (see Table 11).
2
z
$
Table 8 Interaction of SolidificatiodStabilization Binders and Organic Chemical Groups 2.
0
Chemical group phenolic Urethane Urea-formaldehyde EPOXY Polyester 3
Alcohols and glycols DN Set time: decrease DN Durability: no signifi- Durability: no signifi- %
Cll
Durability: no significant effect cant effect ii
cant effect z
*
h
Aldehydes and ketones Set time: decrease Durability: decrease DN DN DN -

2.
g.
Durability: no signifi- (destructive action
occurs over a long 3
cant effect
time period) 3
Aliphatic and aromatic Durability: decrease Durability: no signifi- Set time: increase Durability: decrease 5
Durability: decrease 2.
hydrocarbons (destructive action cant effect Durability: no signifi- (destructive action (destructive action
9
E
occurs over a long cant effect occurs over a long occurs over a long rg
il
time period) time period) time period)
Low molecular
weight polymers only
Amides and amines DN Durability: decrease DN DN DN
(destructive action
begins within a short
time period)
Chlorinated Durability: decrease Durability: no signifi- set time: increase Durability: decrease Durability: decrease
hydrocarbons (destructive action cant effect (lengthen or prevent (destructive action (destructive action
occurs over a long from setting) occurs over a long occurs over a long
time period) Durability: no signifi- time period) time period)
cant effect
Ethers and epoxides DN Durability: no signifi- Durability: decrease DN DN
cant effect (destructive action
occurs over a long
time period)
Table 8 Continued
.~
Chemical group Phenolic Urethane Urea-formaldehyde EPXY Polyester

Heterocyclics DN DN D/U DN DN
Nitriles DN DN DIU DN D/U
Organic acids and DN Set time: increase Set time: no significant Durability: decrease Durability: decrease
acid chlorides (lengthen or prevent effect (destructive action (destructive action
from setting) Durability: no signifi- occurs over a long occurs over a long
Durability: no significant effect time period) time period)
cant effect
Organometallics DN DN DN D/U DIU
Phenols Set time: increase Durability: decrease DN DN DN
(lengthen or prevent (destructive action
from setting) begins within a short
Durability: no signifi- time period)
cant effect
Organic esters DN DN DN DN DIU
DRI = data unavailable.
Table 9 Interaction of Solidification/StabilizationBinders and Inorganic Chemical Groups
~
Chemical Urea-
Group Bitumen Silicate Acrylamide Phenolic Urethane formaldehyde EPOXY Polyester
Heavy metal Durability: Set time: Set time: D/U DN Durability: no DN DnJ
salts and decrease decrease increase significant
complexes (destructive (lengthen or effect
action occurs prevent from
over a long setting)
time period)
Inorganic acids Durabiiity: no Set time: Set time: Durability: no Set time: Set time: no Durability: no Durability: no
significant decrease increase significant increase significant significant significant
effect Durability: no (lengthen or effect. Nonox- (lengthen or effect effect. Nonox- effect. Nonox-
Nonoxidizing, significant prevent from idizing prevent from Durability: de- idizing idizing, ex-
except con- effect setting) setting) crease (de- cept NF
centrated ac- Durability: de- Durability: destructive
ids crease (decrease (de- action occurs
structive structive over a long
action begins action begins time period)
with in a within a short
short time time period)
period)
Table 9 Continued
Chemical Urea-
Group Bitumen Silicate Acrylamide Phenolic Urethane formaldehyde EPOXY Polyester
Inorganic bases Durability: no Set time: Set time: Durability: Durability: Set time: Durability: no Durability:
significant increase decrease decrease decrease increase significant decrease
effect (lengthen or Durability: (destructive (destruction (lengthen or effect (destructive
prevent from decrease action occurs action occurs prevent from action occurs
setting) (destructive over a long over a long setting) over a long
Durability: action occurs time period) time period) Durability: time period)
decrease over a long decrease
(destructive time period) (destruction
action begins action begins
with in a within a short
short time time period)
period)
Inorganic salts Durability: Set time: Set time: Set time: Durability: Durability: no Durability: no Durability: no
decrease decrease decrease decrease decrease significant significant significant
(destructive Durability: Durability: no (destruction effect effect effect
action occurs decrease significant action occurs
over a long (destructive effect over a long
time period) action occurs Bleaches- time period)
over a long Set time:
time period) decrease
Durability:
decrease
(destructive
action occurs
over a long
time period)
DAJ = data unavailable.
Source: Spooner et al. 131.
Solidijkation and Stabilization Techniques 287
Table 10 SoilDescription
Classification
Soil Moisture
content (a) Type of contaminant
Concentration
1 Well-graded
sand oil Heating 7.3 0.11% by weight
ay-silty 2 oil Heating 14.3 0.12% by weight
sand
Silty 3 oil Heating24.7 0.66% by weight
4 Poorly graded
sand
Gasoline 14.4 25PPm
5 clay
Silty Gasoline 19.6 1500 ppm
The initial and final setting times of concrete are commonly defined by the ASTM C403
test method. Setting times are determined from the rate of solidification curve. The solidifi-
cation curve of the control mixtureis shown in Figure 1. The recorded initial and final setting
times were about 1.5 and 6 hr, respectively. Figure 2 indicates the effect of introducing PCS
(soil '
I & 1) on the initial and final setting times of concrete. The initial setting time seems to
increase with the increase of PCS/sand replacement ratio. The final setting time is found to be
less affected by the increase in the PCSlsand replacement ratio. For instance, at a PCS/sand
replacement ratio of 40%, the initial setting time increasesby about 30% compared to the con-
trol mix, while the final setting time increasesby only 20%. A similar trend is observed for all
five soil types included in this investigation. During this experimental program, all concrete
mixtures reached their final setting time well before the specimens were removed from the
molds, that is, in less than24 hr (usually within9 hr). The effectof contaminant concentration
on setting time can be seen in Figure 3. When comparing the setting time of soil 1 (0.11%
contaminant concentration)to soil 3 (0.66% contaminant concentration), it is found that both
the initial and final setting times are consistently greater for the soil with higher contaminant
concentration. These results indicate that the inclusion of €'CS and the contaminant concen-
tration affect the setting time of concrete. However, for the soil types included in this inves-
Table 11 MixtureProportions
Cement Mix Sand/ PCSl PCSI Water/
cement"sand
Soilcement"
typecement"
(Iblyd')design
Control - - 0.50
1 1c1
1.37 800 0.15 10% 0.45
1.21
1c 2 800 0.31 20% 0.45
800 1C3 0.61 . 0.91 40% 0.45
2 0.56 . 2c1
10% 0.15
800 1.37
20% 0.31 1.21
2c2 800
0.91 800 2C3 40% 0.56
3
1.21 800 3C2 20% 0.47
0.61 0.91
3c3 800 40% 0.47
4
4c2 800 0.3
I 1.21 1 0.48 20%
0.61 0.91
4c3 800 40% 0.48
0.495 10% 5C1 0.15
800 1.37
1.21 800 5C2
40% 0.61 0.91
5c3 800
'Ratio by weight.
Note: Ratio of coarse aggregate to cement (by weight) = 1.52. Waterhinder ratio was adjusted to maintain slump
valueat 6 + l-in. slump.
288 Ezeldin and Korfiatis
Table 12 ExperimentalStrengthResults
Compressive
strength (psi)
Flexural
strength
(psi), Unit weight
desig.Mix 2 days 7 days 7 days (1bm3)
C 4950 6160 975 151.6
1c1 4950 5569 975 152.5
1c2 4950 5171 956 148.4
1C3 4450 5370 843 146.5
2 c1 3258 5728 750 143.6
2c2 2691 5171 731 141.6
2C3 2124 3262 656 137.4
3C1 3536 4379 693 144.3
3c2 2404 3941 675 142.6
3c3 2263 3503 487 138.4
4C 1 3395 4658 881 148.9
4c2 3395 4419 788 149.3
4c3 3253 4140 788 154.3
5C1 2688 4928 693 151.6
5C2 2826 4805 656 149.9
5c3 2826 38 19 637 148.6
tigation and for the contaminant concentrations used, this effect is not major; with a 0.66%
contaminant concentrationand a PCS/sand replacement ratio of M%, the initial and final set-
ting times recorded were only 50% and 30% higher, respectively.
The compressive and flexural resultsfor all five soils are given in Table 12. Figures 4-8
indicate that, irrespective of the soil type, concrete with a higher PCS/sand replacementratio
develops lower compressive and flexural strengths at both early and late stages. The presence
of contaminants seems to interfere with the water-cement binding reactions, delaying or pre-
venting the full hydration of the cement particles. The increase of PCS content (increase of
PCSlsand replacement ratio) yields to the presence of more petroleum contaminants, which
6000 -
4 4600 --_-I.. .. -....-....-..".......-. _.I_. -"-. -__- -
"
a
4000 "-.
600 -c I ............ .......................... ...".._

" "*..""......._....-.**.."..
.
.
..
..
.
..
..
.
..
..
.
..
..
.
. -
....._" ....."_. . -..."
1 I I I I I I
0 I I I
1 3 5
TIME, HOURS
Figure 1 Solidification curve of control mixture.

W 1.8- l .6
zc-
SOIL TYPE: 1
$
v) 1.4 "......".............".... ..""_.""._ "_.._ ......"" ....."-".."-" ,R
8
D 1.2 _....._........". I._."...._..
I-
c-
P
E
v) 1' 1
1
10% 20% 40%
PCS replacement percentage
Figure 2 Effect of PCS replacement percentage on setting time.
separate the cement particles from water. Hence, for the same total content of cement, less is
actually available to react with water to produce the hardened binder. This results in the con-
crete being weaker than the control. The strength reductionat each PCS/sand replacementratio
level depends on contaminant concentration, contaminant type, and soil type.The increase in
contaminant concentration hasan adverse effect onthe concrete strength.When comparing the
strength resultsof concrete containing soil1 (sandy soil with0.11% oil contamination)and soil
3 (sandy soil containing0.66% oil contamination),the results indicatethe following. While the
presence of soil 1 with a PCS/sand replacement ratio of 40% reduces the concrete compressive
strength by 10% after 2 days and 13% after 7 days, the presence of soil 3 with the same PCS/
sand replacement ratio yields concrete 54% weaker than the control after 2 days and 43%
weaker after 7 days. A strength comparison for concrete containing soil 1 (sandy with 0.11%
oil contamination) and concrete containing soil 4 (sandy with 0.003% gasoline contamination)
reflects the effect of contaminant type on strength; sandy soil contaminated with gasoline pro-
duces concreteof lower strength than concrete containing a higher concentrationof heating oil.
""
20% 40%
l-
W
01 PCS replacement percentage
INITIAL SET TIME(S1) m INITIAL SET TIME(Sl)
0 FINAL SET TIME (81) m FINAL SET TIME (a31
Figure 3. Effect of contamination concentration on setting times.
290 Ezeldin and Korjiatis
E
N 6000
G 4000
; 9000
, 2000
E m
l000
3 "
10% 20% 40%
I
PCS replacementpercentage
- EARLY STRENGTH (2DI
CONTROL (ID)
LATE STRENGTH (10)
FLEXURAL
S lzool
T I
I ' 10%
40% 20%
mLATE
STRENGTH (70) CONTROL (70)
Figure 4 Effect of K S replacement percentage on strength soil 1.
This is observed forearly and late stages. When comparingthe contaminant type effect on the
strength of concrete containingfine-particle soil, no conclusive observationswere obtained for
soil 2 (clay-silt with 0.12% oil contamination) vs. soil 5 (clay-silt with 0.15% gasoline con-
tamination). The effectof soil type onthe strength of concrete containingPCS was found to be
very important. The presence of soil with fine contaminated particles (soil 2) yields a lower
strength than concrete mixed with sandy contaminated soil (soil 1). Whereas for soil 1 an av-
erage of 13% strength reduction is observed at a PCS/sand replacementratio of 40%, the in-
clusion of soil 2 results in a strength reduction of about 45%.
The results of the wet-dry and freeze-thaw tests are presented in Table 13. The tests were
conducted on the control mixture andthe C3 mixture of all five soils. These results presentthe
percentage of weight loss fora 2 X 2 X 10 in. prism subjected to thewet-dry and freeze-thaw
cycles. In general, the percentageof loss for all tested specimens was less than 2%.No visible
cracking or surface deterioration could be observed on any of the tested specimens at the end
of the test procedure. These preliminary results indicate that up to 40% PCS/sand replacement
ratio could be used without seriously affecting the integrity of concrete members. However,
more tests are required before such a conclusion can be confirmed.
Leaching tests were conducted in duplicate for soils 1-5 using mixture C3 (20 samples)
after 24 hr for a test duration of 96 hr and after 10 days fora test duration of 24 hr. All of these
samples were nondetectable for benzene. Thedetection limit was0.01 ppm. It is apparent that
COMPRESSION
7000
R 6000
E
N 5000
G 4000
T
H 9000
, 2000
l000
g 0000
10% 208 40%
I
EARLY
STRENGTH (201 m LATE MRENQTH (ID1
CONTROL e01
-"----
FLEXURAL
S 1200
T
R 1000
""___I"" "
"
I ' 10% 20% 40%

mLATE STRENGTH ( 7 0 ) CONTROL (m)
Figure 5 Effect of PCS replacement percentage on strength soil 2.
the amount of benzene leaching from concretewas not sufficient to producea measurable re-
sponse. To increase the sensitivity of the leachingtest, it wasdecided tocreate a soil artificially
contaminated with neat benzene. Samples from soils 1 and3 were left in an oven at 105°C for
4 hr to drive off VOCs. The samples were left uncovered overnightto allow rehydration. Con-
taminant concentration of 0.5% and 3% benzene (C, in Table 14) were added by weight basis.
Samples free of contamination were used as a control. Concrete cubes were made using C3
mixture proportions. The leachability results, after 24. hr, for concrete containing artificially
contaminated soilsand for loose soilsare shown in Table 14.The loose soil results (designated
mix L) indicated that soil 3 leached about twicethe benzene at 0.5% benzene contaminationas
indicated by the benzene concentration in the water (C,,,)at the end of the test. At 3.0% ben-
zene concentration, little difference was observed between the behaviorof the two soils. Since
the soils were not in a solid matrix, mass transport in this system is relatively nonlimiting. It
is likely that the concentrations observedare more indicative of the adsorption behaviorof the
soils Thus it can be concluded that soil 1 is a stronger absorber than soil 3.A possible reason
why there was little difference at the higher concentration is that the concentration may be
approaching the solubility limit in this system. The leachate concentration, C,, for the PCS
concrete cubes ranged from0.55 to 40 ppm. The leaching increased with the increaseof con-
taminant concentration for both soil types. The cube surface leaching flux (M) varied from
0.003 to 0.217 g/(hr-m*). The fraction of benzene in the cubes that leached &) was 0.11-
1.27%. These levels are about 99% lower than the values for loose soil in the case of 0.5%
contamination, and about 95% lower for the case of 3% contamination.
292 Ezeldin and Kofiatis
S COMPRESSION
T 7000
R 8000 a ""~ ~
E 5000
N
G 4000
T aooo
H
. 2000
1000
P nnnn
S ""
mm 20% 40%
I
m EARLY STRENQIH (201 m LATE STRENGTH (ID)
CONTROL (101
FLEXURAL
S 1200
T
R 1000 _- " .
E
N
G
T
H
P
S
I lo% 20% 40%
=LATE STRENGTH ( 7 0 ) -CONTROL (70)
Figure 6 Effect of PCS replacement percentage on strength: soil 3.
COMPRESSION
7000
; 8000
E so00
N
G 4000
T sow
H 2000
6
s o
1000
io% 20% 40%
EARLY STRENGTH (201 m LATE BTRENGTH (7D)
CONTROL (701
FLEXURAL
S 1200
T
t
l000 . -. "
N 800
G
T WO
'r' 400
p 200
10% 20% 40%
mLATE STRENGTH (70) CONTROL (70)
figure 7 Effect of PCS replacement percentage on strength: soil 4.

Solidijkation and Stabilization Techniques 293
COMPRESSION
7000
R ln"n "" - ". . -
l
- EARLY 8TRENOTH (2D)
CONTROL (ID)
m LATE
8TTRENOTH (ID)
FLEXURAL
S 1200
T
R 1000 3
__ .____._ __._
5.- 800
~ II .."
: 800
H 400
p 200
10% 20% 40%
LATE STRENQTH ( 7 0 ) CONTROL (70)
Figure 8 Effect of PCS replacement percentage on strength: soil 5.
ACKNOWLEDGMENTS
We gratefully acknowledge the valuable assistance of several graduate students who contrib-
uted to the experimental studies.This investigation was supported by the Division of Science
and Research, NJDEPE, by the Hazardous Substance Management Research Center, Newark,
New Jersey, and by the PSE&G Company, Newark, New Jersey. Their contribution is grate-
fully acknowledged.
Table 13 DurabilityTestResults
Control c3
Soil
F-Ttype
W-D F-T W-D
1 0.30 0.20 0.90 0.50
2 0.30 0.20 0.70 1.10
3 0.30 0.20 - 0.70 0.30
4 0.30 0.20 1.80 0.90
5 0.30 0.20 2.00 1S O
W-D, wet-dry testing; F-T,freeze-thaw testing.
294 Ezeldin and Koflatis
Table 14 ExperimentalLeachabilityResults
Flux M
Mix
Soil C, (%,Run
w/w) C , (ppm) fL (%) [g/(hr.m*)]
1 c3 0.0 A 0.074 O.OOO4
1 c3 0.0 B 0.072 O.OOO4
3 c3 0.0 A 0.115 0.0006
3 c3 0.0 B 0.118 0.0006
3 c3 0.0 C 0.126 0.0007
3 c3 0.0 D 0.112 0.0006
1 c3 0.5 A 0.868 0.170 0.0048
1 c3 0.5 B 0.952 0.186 0.0053
3 c3 0.5 A 0.550 0.107 0.0030
3 c3 0.5 B 0.558 0.109 0.0031
1 c3 3.0 A 8.467 0.276 0.0467
1 c3 3.0 B 9.519 0.310 0.0525
3 c3 3.0 A 39.235 I .277 0.2166
3 c3 3.0 B 25.737 0.838 0.1421
3 c3 3.0 C 26.686 0.869 0.1473
1 L 0.0 A CO.01 O.oo00
1 L 0.0 B <0.01 O.oo00
3 L 0.0 A <0.01 O.oo00
3 L 0.0 B ,<0.01 O.oo00
1 L 0.5 A 101.4 26.122 0.7381
1 L 0.5 B 101.9 26.271 0.7423
3 L 0.5 A 193.0 49.083 1.3869
3 L 0.5 B 203.5 51.751 1.4623
1 L 3.0 A 562.7 24.178 4.0989
1 L 3.0 B 587.1 25.229 4.2770
3 L 3.0 A 599.7 25.425 4.3103
3 L 3.0 B 605.7 25.679 4.3535
REFERENCES
1. Biczok, I., Concrete Corrosionand Concrete Protection,Chemical Publishing Company, New York,
1967.
2. Martin, E., and Johnson, J., Jr., (eds.),Hazardous Waste Management Engineering.Reinhold, New
York,1986,pp.140-141.
3. Spooner, F! A., et al., Compatibilityof Grouts with Hazardous Wastes, EPA-600/2-84-015, Munic-
ipal Environmental Research Laboratory, U.S. Environmental Protection Agency, Cincinnati, Ohio,
1984.
4. Eklund, A. G., Survey of the useof coal ash in hazardous waste stabilization, Proceedings of Amer-
ican Coal Ash Association, 9th Int. Coal Ash Utilization Symp., Orlando, Fla., 1991, pp. 28.1-
28.20.
5. Ezeldin, A. S., Use of coal ash in productionof concrete containing Contaminated sand, Proceedings
of American Coal Ash Association, 9th Int. Coal Ash utilization Symp., Orlando, Ha., 1991, pp.
17.1-17.9.
6. Ezeldin, A. S., et al., Stabilization and solidificationof hydrocarbon contaminatedsoils in concrete,
J. Soil Contamination, 1(1), 61-79 (1992).
7. Ezeldin, A. S., Vaccari, D. A., and Mueller, R. T.,Fly Ash Concrete Containing Hydrocarbon Con-
taminated Soils, American Concrete Institute, Spec. Publ. SP 132-38, 1993, pp. 693-712.
ADDITIONAL READING
ASTM, Annual Book of ASTM Standards, Concrete and Mineral Aggregates, 1989.
Britton, C. L., NewJerseyGround-waterContaminationIndex,Sept.1974-April1984,NewJersey
Geological Survey, Open File Rep. 84-1.
Calabrese, E. J., and Kostecki, I? T.,Petroleum Contaminated Soils, Vol. 2, Lewis, Chelsea, Mich.,
1990.
Conner, J. R., Fixation and solidification of hazardous wastes, Chem. Eng., Nov. 10, 1986, pp. 79-85.
Conner. J. R., Chemical Fixation and Solidificationof Hazardous Wastes,Van Nostrand Reinhold, New
York, 1990.
Dowd, R. M.,Leaking underground storage tanks, Environ. Sci. Technol., 18(10), (1984).
Jones, L. W,, Interference Mechanisms in Waste StabilizatiodSolidificationProcesses, U.S.Army En-
gineer Waterways Experiment Station, Vicksburg, Miss., EPA/600/2-89/067, January 1 9 9 0 .
Kostecki, F! T., and Calabrese, E. J., Petrofeum Contaminated Soils, Vol. 3, Lewis, Chelsea, Mich.,
1991.
Malhotra, V. M. (ed.), Fly Ash, Silica Fume, Slag, and Other Mineral By-Products in Concrete, Amer-
ican Concrete Inst., SP-79, 1983.
Malhotra. V. M. (ed.), Fly Ash, Silica Fume, Slag, and Natural Pozzolans in Concrete,American Con-
crete Inst., SP-114, 1989, 2 volumes.
Martin, J. I?,Biehl, F. J.,andRobinson,W. T., Stabilized petroleum waste interaction with silty clay
subgrade,in PetroleumContaminatedSoils, Vol.2,(E. J. Calabreseand P. T. Kostecki,eds.),
Lewis, Chelsea, Mich., 1990, pp.177-197.
Mehta, l? K.,Concrete: Structures, Properties, and Materials, Prentice-Hall, Englewood Cliffs, N.J.,
1986.
hndergast, J., Fear of trying, Civil Eng., Proc., 61 (4). 52-55 (1991).
Suprenant, B. A., Lahrs, M. C., and Smith, R. L.,OilCrete, Civil Eng., Proc., 60(4), 61-63 (1990).
Sehgal, S. B., and Gronowicz, A., Solidifying and stabilizing waste at a hazardous landfill, Concrete
Int., Proc., 12(7), 41-44 (1%).
13
Soil Remediation with Environmentally
Processed Asphalt (EPA" )
S. M. Testa and D. L. Patton

Applied Environmental Services, Inc.
San Juan Capistrano, California
1. INTRODUCTION
A major consideration when formulating remedial action plans is the determination of what
technology will best serve the specific project needs. No two projects are exactly alike, and
each has site-specific limitations. However, three objectives must always be met if the reme-
diation project is to be successful: The remedial method must be cost-effective, time-efficient,
and environmentally sound. The production of asphalt is conventional in nature and well es-
tablished [l]. Recycling soil containing petroleum hydrocarbons and metals affected soil via
incorporation into cold-mix asphalt is a proven remedial technology [2-61. In addition, the
incorporation of affected soil into asphalt products by the process refer to as environmentally
processed asphalt (EPA'") is viewed as environmentally sound and has proved to be cost-
effective while providing the minimal amount of long-term liability in comparison with other
soil remediation options and alternatives. Affected soils, formerly classified as hazardous
waste, are incorporated with asphalt emulsion and specified grades of aggregate to produce a
range of cold-mix asphalt products that fulfill therequirements of a variety of end uses. Notable
among these uses are landfill caps andliners; tank farm dikes and containment structures; park-
ing lots, truck terminal and salvage yard pavements; road construction material; and port fa-
cility container shipping yard surfacing.
This chapter discusses the methodology, regulatory framework, and certain properties of
EPA pertaining to durability, chemical resistance, aging, biological resistance, permeability,
leachability, chemical aspects, and product use.
II. METHODOLOGY
The incorporation of affected soils to produce a commekially viable product can be accom-
plished with either of two processes: mixed-in-place for large quantities and windrowing for
smaller quantities. For large-quantity projects, mixed-in-place processing is accomplished us-
297
298 Testa and Patton
ing a portable asphalt batch plant. Providing production averaging 150 tons of cold-mix asphalt
per hour, the plant operation consists of a mechanical screening plant, transfer conveyor,elec-
tric generator (all equipment except the rolling stock is electrically powered), the asphalt plant
or pug mill, and asphalt emulsion truck (Figure 1). Materials are introduced into the process
through the screening unit, which serves to separate all deleterious materials (i.e., trash, plas-
tic, large rocks, etc.) from the soil and to size material in accordance with the design criteria.
For example, asphalt sub-base would use lV2-in. aggregate, whereas pavement may call for
%-in. or less. From the screen, the materials travel on the transfer conveyor to the batch plant’s
soil hopper. There are two hoppers on the plant unit: one for soil and the other for aggregate.
These materials are fed at a predetermined rate from each hopperby variable-speed conveyors
and adjustable feed gates. Mix design suchas 50% soil and 44% aggregate are maintained to
within 1% of total mix. The feed hoppers discharge onto the plant unit’s transfer conveyor to
the mixing chamber. The materials discharge from the conveyor into a fluffer wheel compart-
ment, where they are further mixed. Inside this compartment the asphalt spray bar applies the
required amount of emulsion. From the asphalt compartment the material discharges into the
mixing chamber. Inside this chamber are two counter rotating paddle-wheel mixers that have
adjustable rotating speeds. This providesthe proper retention time to ensure a complete blend-
ing of all materials. The product is then transferred into trucks or to a stockpile ready for ap-
plication. Theproductcan be. stockpiled formonths until needed.Forsmaller quantities,
windrowing involves coating the soil with a proprietary emulsion and mixingthe materials in
place. Product specifications are in accordance with or exceed those used by county and state
road departments to produce road-mixed asphalt.
111. REGULATORY FRAMEWORK

The regulatory frameworkof the federal environmental laws (and such states asCalifornia) do
not deem everything as “hazardous” and mandate its disposal in a Class I landfill or by in-
cineration. A review of current regulations proves quite the contrary. The letter, spirit, and
intent of current hazardous materials legislation is to promote and develop alternative tech-
nology that encourages the use, reuse, and recycling of materials rather than the archaic load,
haul, and dump remediation techniques that have produced more environmental problems than
they ever solved. Specifically, the recyclingof affected soil into EPA is, for example, carried
out in California under the following enabling legislation:
California Code of Regulations (CCR) Title 22, Section 66262.11, Hazardous Waste Deter-
mination
CCR Title 22, Section 66261.2, Definition of Waste
CCR Title 22, Section 66261.3, Definition of Hazardous Waste
CCR Title 22, Section 66261.4, Exclusions
California Health and Safety Code (CHSC) Chapter 6.5, Article 4, Section 25143.2(b), Re-
cyclable Material
Code of Federal Regulations (CFR) Title 40, Part 261, Section 2 (40 CFR 261.2), Definition
of Solid Waste
40 CFR 261,2(e), Materials that are not solid waste when recycled
The above are the main sections that deal withthe use, reuse, and recycling of materials. There
are a myriad of subsections and cross references to othersections that the reader will note upon
review of these main listed regulations. Briefly stated, to paraphrase CHSC 25143.2(b), recy-
clable material that is or will be (1) used or reused as an ingredient in an industrial process to
make a product or (2) used or reused as a safe and effectivesubstitute for commercial products
Soil with Asphalt 299
. . _ :
Figure 1 Portable asphalt batch plant processing cold-mix EPA via mixed-in-place process.
Figure 2 Grader producing cold-mix EPA via the windrowing process.

is excluded from classification as a waste. Hence, if the regulations do not classify recyclable
materials as “waste” and these materials are not regulated as “hazardous waste,” their use,
reuse, and recycling are within the letter, spirit, and intent of environmental legislation.
Thus, the objectives of EPA methodology as a soil remediation option are
To effectively reuse affected soil as an ingredient in a stable, nonhazardous cold-mix asphalt
that would be used on the property of origin as paving material
To reduce generator liability to a minimum by complying with pertinent federal and state
regulations
To reduce the costof remediation by reusing affected soil as an ingredient in cold-mixasphalt,
thereby eliminating many of the hazardous waste taxes and pretreatment and landfill dis-
posal costs
To demonstrate that the EPA method effectively stabilizesthe hazardous constituents compris-
ing affected soil
To demonstrate that EPA is a cost-effective, time-efficient, and environmentally sound reme-
diation alternative to landfill disposal of hazardous wastes
IV. DURABILITY
The best indicationthat asphalt liners andstructures have long-term durability and performance
is the existence of surviving asphaltic structures from antiquity [7]. Asphalt was in general use
in western civilizations from about 2000 B.C. to the first century A.D., when its use was su-
perseded by more economic methods of working wood,tar and pitch, andasphalt deposits were
no longer availableto existing mining technologies. Surprisingly, the ancient mixesare not that
dissimilar to modem ones. Besides the obvious uses as mortars, pavements, revetments, and
foundations, at many Mesopotamian sites asphalt liners from 0.1 mm to several centimeters
thick were commonly used in drainage, water tanks, and plumbing fixtures. Inmany of these
cases, the asphaltic structures that have escaped intentional or accidental destruction are still
adequately performing their primaryfunction. Samples taken from thesestructures often show
favorable properties, including low permeabilities, but it is uncertain how long exposureto UV
light and surface conditions have affected the asphalt relative to the general aging processes
expected in the subsurface environment.
V. CHEMICALRESISTANCE
The testing and performance assessment of asphalt has traditionally focused on its structural
performance as pavement and buildingmaterial. However, when evaluating the long-term per-
formance of asphalt liners produced with affected soilas part of the aggregate, the focus is on
their chemical performance. Becauseof the great immiscibility of petroleum products withie-
spect to the aqueous phases expected under impoundment conditions, large favorable free-
energy change exists for preventing the release of contaminants fromthe asphalt. Therefore,the
chemical behavior and performance of the petroleum contaminant should parallel the behavior
and performance ofthe asphalt itself. Detailed chemical testshave been performed on asphalt
liners for disposal sites for uranium mill tailings [8] and for land disposal of radioactive waste
[9]. These studies can be used to make a preliminary evaluation of the use of affected soil for
cold-mix EPA incorporation.
The resistance of asphalt to many reagents at atmospheric temperaturesis well documented
[7,8,10]. Prolonged contact with dilute acidic solutions can result in hardening of the asphalt
due to formation of asphaltenes. Nitric acid is very reactive with asphalt even in dilute solu-
Soil 301
tions, whereas hydrochloric acid does not affect asphalt. Asphalt reaction with sulfuric acid is
intermediate. Asphalts are generally more resistant to alkaline solutions than to acidic solu-
tions, a favorable characteristic for asphalt liners.However, alkaline solutions can react to form
salts such as sodium naphthenates that form excellent emulsifying agents. Theoretically, this
could be a problem for affected soilif contaminants were mobilized in the emulsified solution.
However, the emulsification depends on the degree of alkalinity and the diffusion and hydraulic
resistances of the asphalt, which are generally extremely low, less than 10"' cm2/sec and
c ds e c , respectively [l l]. Without further experimental verification, emulsification of an as-
phalt liner is not expectedto be important, nor is it leachableto the extent of releasing hydro-
carbonconstituents inexcessof regulatorylimits. The resistanceofasphalt to selected
chemicals under a varietyof conditions is listed by MRM Partnership [7].
VI. AGING
Of most importance to an asphalt liner are the effects of aging. Although not documented,
hardening and other aging affects might increase mobilization of the petroleum contaminants
from theEPA by supplying pathways out of the asphalt by and
causing separation of petroleum
constituents from the asphalt phases during aging. However, these effects would have to be
excessive and affect a large proportionof the asphalt to mobilize the small amount of contam-
inants in the 10% fines of the aggregate.
Physical hardeningdue to peptization, paraffin crystallization,and volatilization occursto
differentdegreesinalltypes of asphaltandisunaffected by thepresenceofpetroleum-
contaminated soil as a small part of the aggregate. Chemical hardening,however, may be im-
portant. The rate of reaction of asphalt with oxygen is very temperature-dependent and varies
with asphalt type at high temperatures, but below 50°C the reactions are independent of tem-
perature and asphalt type, are restricted to the asphalt surface, and should not be affected by
affected soil. The hardening rate is higher in the presence of light, but because of the dark
conditions of the subsurface environment, only the aging reactions that occur in the are darkof
importance to an asphalt liner. In the dark, oxygen is bound into SO groups after short aging
times and into CO groups after long aging times. Petroleum contaminants are not present in
great enough quantities to affect the rate or degree of these reactions. Experiments show that
the maximum depth of oxygen penetration is in the range of 2.5-5 mm [7], but the rate of
hardening reduces considerably with time.
VII. BIOLOGICALRESISTANCE
Microorganisms can degrade certain asphaltic components under ideal conditions [12]. Re-
search into microbial degradation of asphalt canbe summarized as follows [9,13,14]:
There is no single microorganism that will oxidize all asphaltic components.
Microbial degradation occurs onlyat the outermost surfaces.
The higher the molecular weight of the asphalt component, the more resistant it is to micro-
bial degradation.
Most soil asphalt-oxidizing microbesgrow best at pH 6-8.
Evenunderidealconditions,microbialdegradationrates do notexceedcmlday (0.7 mm
penetration per 1 0 0 years) and are usually an order of magnitudes less.
Anaerobic degradation is much slower than aerobic degradation.
Microbial attack is fastest for stream-refined bitumens, followedby air-blown and finally coal
tar pitches.
Parton 302 and Testa
Table 1 AnticipatedFieldLinerPermeabilities
Effectiveness
Assumed
field final Avg
Liner permeability. K (cm/sec)thickness, L (cm)factor, KIL (sec”)
~ ~~ ~~
7 concrete
Asphalt, x 10 7 X 10-9
2 Hypalon x 10“O 0.12 2 X 10-9
Asphalt
membrane
rubber
4 x 0.8 5 x 10-6
Catalytic air-blown membrane 7 X 10-9 0.9 8 X 10-9
Sodium bentonite 1 X 10-~ 10 8 X
Saline seal 100 8x 10 8 X 10-7
GSR-60 6X 10 6 X 10”
a (as Soil 10 X 10-5 1 x 10-6
Microbial inhibitors are ineffective over long time periods.

Environmentalfactors(e.g.,temperature,pH, state of hydrocarbons,nutrientandoxygen
concentrations) haveto be perfect for a very long time to result in any noticeable asphalt
degradation.
Overall, microbial degradation will be unimportant for all practical purposes.
VIII. PERMEABILITY
Permeability tests have been performed ona variety of liners that were first subjected to aging
is presented in Table 1. Permeability results
tests [g]. The permeability obtained for each liner
generated as part of this duty on five samplesof cold-mix EPA incorporating affected soilare
presented in Table 2. Accelerated aging testsof an asphalt liner at 20°C under oxygen partial
pressures of 0.21, 1, and 1.7 atm, with continuous exposure toan acidic leachate at 20°C under
varying oxygenpartial pressures havebeen performed [g]. Solution pH values of 2.5,2.0, and
1.5 were designated as normal, intermediate, and highly accelerated conditions, respectively.
Acidity levels were shown to havean unmeasurable effect on asphalt aging. Permeabilitywas
used as a means to measure the immediate effectivenessof the asphalt liner. The permeability
appears to be relatively unaffected under these exposure conditionsas shown in Figure 3.
IX. LEACHABILITY
A normal asphaltic concrete or cold-mix EPA paving material is somewhat acceptable as an
environmentally safe product even though there may be volatile organic compound (VOC)
Table 2 Results of Permeability Testing on Cold-Mix Environmentally Processed Asphalt

Hydraulic
Effective
Sample Sample Asphalt Bulk conductivity
permeability
sample No. diameter
length
(cm)
volume
(cm)
(mdarcy)
(cm’) (cdsec)
A-B- 1 6.02 5.05 120.58 0.135 1.42 X 10-7
A-B-2
5.06 6.81 136.94 0.013 1.37 X lo-’
A-B-5
4.98 4.87 94.86 0.034 3.58 X lo-*
A-B-7
5.06 6.42 129.10 0.096 1.01 X 10-~
A-B-10 7.52 5.05 150.62 0.142 1.50 X 10-7
Soil Remediation with Asphalt 303
U
W
a m
A INTERMEDIATE
m NORMAL
l- I
10-111
30 20 40 50 60 70 00 90
EXPOSUREPERIOD (Days)
Figure 3 Permeability of an asphaltlineratnormal,intermediate, and highlyacceleratedcondi-
tions [g].
emissions during manufacture and placement, notably in regardsto the hot-mix process. The
question of contamination is not frequently associated with asphaltic concrete even though cer-
tain halogenated volatile organics may be present in association with hot-mix bituminous prod-
ucts, notably those containing cut-back asphalt using kerosene, diesel, or other solvents in their
dilution process [6].
Asphalt concreteor cold-mix EPA may be accepted by Class I11 landfill and is commonly
crushed and used as a component for road base material.The fact that thereare few questions
about the safety of asphaltic concreteis justified by the existence of thousands of miles of paved
roadways constructed every on asphalt show
year. In addition, the performance of leachate tests
a definite lack of contaminants that might leach out under extreme conditions. Leachate ana-
lytical results for certain petroleum constituents in both hot-mix and cold-mix asphalt incor-
porating affected soil are presented in Table 3.
X. GEOCHEMICAL ASPECTS
The chemical aspects associated with the incorporation of metals-affected soil (and other con-
taminants) has been extensively studied with respect to pavement properties, leaching behavior,
sensitivities to moisture damage, and functional group analysis[15,16]. These studies provide
information that can be used to evaluate the stability of metals and other contaminants in soils
that have been asphalted. The studies indicate that asphalted contaminated soil willbe highly
stable and will perform adequately as an end product.
Table 3 Leachate Analysis of Qpical Asphaltic Concrete Samples

Concentrationa
Unit
method
Analytical
Parameter limit
Detection
Cold-mix asphalt (EPA)
SM412 total Cyanide, EVD ND mag 1
point Flash 1010 >220 "F 5
PH 9045 7.62 - .01
Sulfide EPA 376.1 ND mag 1
mg/L
Gasoline ND EPA 8015 .5
Diesel EPA 418.1 ND mg/L .5
Hot-mix asphalt
SM412 total Cyanide, E/D ND mag 1
point Flash >220 "F 5
PH 9085 8.43 - 0.01
Sulfide EPA 376.1 ND mag 1
Gasoline EPA 8015 ND mglL .5
Diesel ND EPA 418.1 mgIL .5
(') ND = not detected above the respective dection limit.
For the best chemical performance, the asphalt should have high contents of pyridinic,
phenolic, and ketone groups, which can be achieved by carefully choosing the source material.
If the situation requires special stability
or redundancy, small amounts of shale oil and lime can
be used as additives. Situations and conditions that favor the presence of inorganic sulfur,
monovalent salts, and high ionic strength solutions in the asphalt should be avoided, because
these conditions decrease the chemical stabilityof the asphalt cementby disruption of the func-
tional groupaggregate bonds and by increasing the overall permeability. However, these con-
ditions are not expected in the anticipated uses of asphalt cement to stabilize contaminantsin
metals-affected soil using environmentally processed remedial technology.
XI. DISCUSSION OF USE

Environmentally processed asphalt can at best be described as user-friendly. There currently
exist a multitude of uses for cold-mixEPA incorporating affectedsoil. One of the more viable
and creative is keeping contaminated soils outof landfills as a waste and placing itin landfills
as an end product [7]. The imminent closure of many of the nation's Class 111 and municipal
landfills creates the potential use for hundreds of thousands of tons of contaminated soils in-
corporated into asphalt for use as a landfill liner or cap. The cost effectivenessof this method
of capping landfills is very attractive to financially strained municipalities.Prior to the advent
of EPA for useas a liner or a cap, clay wasthe specified material. In addition to environmental
concerns associated with mining vast quantities of clay for these uses,the cost of landfill clo-
sure had no cost recovery options. By using EPA, the municipalities and landfill owners can
charge attractive fees for the acceptance of affected soil.In mostcases, this acceptance fee pays
for the cost of on-site processing of the affected soil into the asphaltend product. The effec-
tiveness of the cost recovery is obvious as the capping materials production process becomes
a profit center. By the use of on-site material, not only is the cost of obtaining the clay can-
celed, but transportation costs also are eliminated. In essence, the capping processof landfill
closure is more affordable, makesuse of a product far superior to the traditional clay method,
and reduces a broad spectrum of environmental concernsby keeping affected soil outof land-
fills as a waste. Instead it places affected soilas environmentally sound end products such as
caps or liners.
Soil Remediation 305
Studies of asphalt, clay, and other membrane liners subjected to a variety of aging tests in
exposure columns at various temperatures, pH conditions, oxygen concentrations, and hydro-
static pressures havebeen discussed [ 8 ] . The conclusions were that the asphalt liners mem- and
branes were extremely stable chemically and physically. An aging period equivalentto 7 years
produced penetration of reaction products to only 0.5 mm (0.5% of the 10-cm liner thickness).
The results showed that if the asphalt content of the liner exceeded about 6%, these linerswould
perform adequately under impoundment conditions for over 1000 years, conditions that are
similar to those expected for cold-mix EPA [17]. Catalytically blown asphalt was considered
the best liner material and was selected for long-term field testing. Field testsof catalytically
blown asphalt over a 2-year period showed superior performance of the asphalt liners compared
to thatof the clay liners. This will be especially true for the petroleum constituents in cold-mix
EPA’s liner; overall, asphalt is a much better liner material for this application than clay.
Its use as a cap or liner is only one exampleof this product’s cost effectiveness and ver-
satility, but what of its more traditional useas a pavement? To best describe “user-friendly,”
one should visualize a typical multilane high-traffic-volume freeway and the load-bearing ca-
pability and durability that must be designed into the asphalt product used in its construction.
Now visualize the typical bicycle path windingway itsthrough our urban areas. The point being
that both the freeway and the bicycle path are asphalt pavements, but their end uses are dras-
tically different. Cold-mixEPA pavement is certainly nothingnew. There are very few, if any,
state and county road departments that do not use variations of cold-mix EPA. The end use of
asphalt dictates its specifications, or better said, if the asphalt mix will perform its required
function, from freewayto bicycle path,it is within specifications. In fact, the ASTM procedure
for cold-mix asphalt design includes a section that states that the mix must fulfill the require-
ments of its intended application. Recalling the term “user-friendly” it becomes apparent that
the function of the end product will determine the asphalt mix design.
Pavement for a heavy equipment yard has been constructed from EPA made with affected
soil recovered from leaking underground tanks. By producing parking lot pavement for on-site
use, the generator eliminated the inherent liability of disposing of their contaminated soil in a
dump site. Approximately $80.00/ton of disposal taxes were saved as the materials were re-
cycled and not disposed of. The pavement produced not only kept the project’s pricing below
any other option but created a paved parking lot of extremely low permeabilityto prevent fur-
ther adverse subsurface impact. The mix design was not the same as that required to construct
a freeway, but then a freeway was not the intended use. The intended use was for low traffic
volume but required extremely high load-bearing strength. Another project used affected soil
from an oil tank spill for paving loading and unloading facilities at an oil refinery. Again, the
affected soil was not disposed as of hazardous waste but was recovered and used in a cold-mix
asphalt pavementto remediate the affected soil and prevent further contamination, and the mix
design was consistent with the end use.
Stability or strength (as measured by the Marshall test) achievedby various mix designs of
cold-mix EPA is presented in Table 4. The minimum Marshall stability required for paving
mixtures, for example, is 2224 [18]. Mix designs used for actual applications range 95% from a
contaminated soil (native silt, sand, and gravel contaminated with diesel fuel to 32,000 ppm
total petroleum hydrocarbons) with a 5% emulsion, to a 5% contaminated soil (heavy black
clay contaminated with machine cutting oils to 55,000 ppm total petroleum hydrocarbons) plus
90% Class I1Y4-in. or less base rock and 5% emulsion. To date, EPA has been successfully
used on projects ranging from road base and road pavement to containment dikes and drain
channels. The procedure wasto determine the requirements, then design the EPA mix to fit the
use. AS the equipment used to produce EPA is portable and certainly not complex, field test
batches of20 tons or more are used rather than bench-scale tests. In this manner the actual field
306 Patton Testa and
Table 4 Summary of Marshall Test Results for EPA Stability

number:5 Sample 4 3 1 2 6 '
75/25 Blend; 314-in. Class I1
base and contaminated soil
Asphalt in emulsion" 62-64 62-64 62-64 62-64 62-64 62-64
Residual asphalt in mixtureasb 5 5 5 6 6 6
Total mix watef 5.2 5.2 5.2 5.2 5.2 5.2
Compacted specimen data
(emulsion in percent)
Bulk density 2.08 2.07 2.11 2.05 2.07 2.05
Weight in air 1116.1 1125.1 1130.0 1120.1 1122.6 1120.7
Weight in water 584.4 586.5 599.0 577.2 584.4 577.5
Weight SSD 1120.1 1129.0 1134.1 1124.0 1126.5 1124.9
Thickness 2 5/8" 2 11/16" 2 518" 2 11/16" 2 11/16" 2 11/16"
Stability 3100 2350 2800 2450 2250 2200
Adjusted stability 2880 2090 2600 2180 2000 1960
Flow 30 27.5 31 31 30 24
Average stability NTW 2520 NT NT 2050 NT
number: Sample
9 8 7 10
Residual asphalt in mixtureasb
6.5 6.5
6.5 6.5
Bulk density 2.002.022.00 2.02
Stability 3548 NT 3260 NT
24-Hour soak NT 1410 NT 1056
14number: Sample
13 12 11
mixtureamb
in
Residual
asphalt 6 . 6 6 6
Bulk density2.01
2.03 2.03 2.01
Stability 3158 NT 2640 NT
24-Hour soak NT 1577 NT 1201
absorbedMoisture X X X
total Maximum X X X
' In percent
Emulsion
e Not tested
Soil Remediation with Asphalt 307
3000
I
0
z
- 2500 - Moximumdrydensity = 122pcf
Optimummoisturecontent = 10.47,
W
$ 2000 -
0
1500
CK
W X Standard 100.4
Q
1000
v,
n
Z % Standard 95.5
1 500
2
0
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4
PENETRATION INCHES
Figure 4 California bearing ratio for Class I1 base using cold-mix EPA.
mix is tested rather than a small hand-mixed batch. The bearing ratio for processed EPA for
Class I1 base is presented in Figure 4.
XII. CONCLUSIONS
In consideration of certain factors including durability, chemical resistance andaging, biolog-
ical resistance, permeability, and leachability, cold-mix EPA is anticipated to perform more
than adequately under normal conditions fora long period of time, probably over lo00 years.
The use of EPA as a liner, cap, or any number of other site-specific applications has vast po-
tential. Hazardous waste cleanup projects become cold-mixasphalt production projects. Con-
taminated soil becomes a recoverable resource and is within the letter, spirit, and intent of
current regulations.
Under Californiaregulations, for example, non-RCRA regulated recyclablematerials used
in a manner such that they are not considered to be “used in a manner constituting disposal”
are not subject to the provisions of Health and Safety Codes of the State of California, sub-
section 25143.2(b). Thus, if the recyclable materials satisfy the conditions of subsection
25143.2, then (1) they are not considered hazardous waste and (2) they are conditionally ex-
empt from the California Departmentof Health Services hazardous waste regulations. Provid-
ing the conditions summarized above are met, permanent fixation of petroleum- and metals-
contaminated soils via asphalt incorporation is a viable, cost-effective soil remediation option
that can be accomplished withina relatively short period of time with minimal long-term lia-
bility [18]. Furthermore, although highway-type paving material as a resultant product is lim-
ited, multiple secondarymarketsexist,includinglinersandlandfill caps, roadbase, dust
abatement, bank stabilization, and paved storage areas, among other uses.
Table 5 EPA Costs vs. Disposal Costs for Non-RCRA Hazardous Wastea
~ ~ ~~
Task description costs

Disposal
costsEPA Difference
Site investigation Same Same 0
Characterization and work Same Same 0
Plan
Profiling and agency approval Same Same 0
Excavation Same Same 0
Transportation 0 for on-site processing 0
$5.00 per ton for central plant
processing
$25.00 per ton $ 10.00
Disposal costs NA $65.00 per ton NA
Processing costs $35.00 per ton (avg) NA $ 30.00
Taxes and fees'
Superfund (HS) 0 $7.88 $ 7.88
HAMY 0 $26.25 $ 26.25
County tax (10% of dis- 0 $6.50 $ 6.50
posal costs)
Site restorationd Same Same 0
Product cost recovery $20.00 per ton (avg) 0 $ 20.00
Total per ton $100.63
All costs in 1992 dollars.
NA = notapplicable.
State taxes and fees shown are from a recap of hazardous waste fees for fiscal year 1991-92 compiled by the State
Board of Equalization. Disposal costs shown above do not includegenerator fees or hazardouswastereporting
surcharge.
Site restoration costs where cold-mix EPA was used on site would be the same; however, the product cost recovery
would be deducted from the gross site restoration costs, thereby providing a much lower actual net cost.
REFERENCES
1. Asphalt Institute, Principles of Construction of Hot-Mix Asphalt Pavements, The Asphalt Institute,
College Park, Md., Manual Ser. No. 22, 1982.
2. Preston, R. L., and Testa, S. M., Permanent fixation of petroleumcontaminated soils. Proc. Nut.
Res. Develop. Conf. on the Control of Hazardous Materials, Anaheim, Calif., 1991, pp. 4-10.
3. Testa, S. M., and Patton, D. L., Paving market shows promise, Soils, Nov.-Dec. 1991, pp. 9-11.
4. Testa, S. M., Patton. D. L., and Conca, J. L., The use of environmentally processed asphalt as a
contaminated soils remediation method,Proc. Hazardous Materials Control Res. Inst. Conf. (Haz-
ardous Materials Control South), New Orleans. La., 1992.
5. Testa, S. M., Patton, D. L., and Conca, J. L., The use of environmentally processed asphalt as a
contaminated soil remediation method,Petroleum in Conmminated Soils, Vol. 4, E. J. Clarence and
F? T. Kostecki, eds., Lewis, Chelsea, Mich., 1992.
6. Testa, S. M., Patton, D. L., and Conca, J. L., Fixation of petroleum contaminated soils via cold-mix
asphalt for use as a liner, Proc. Hazardous Materials Control Res. Inst. Conf., HMC South, New
Orleans, La., 1992, pp. 30-33.
7. MRM Partnership, Bituminous and Asphaltic Membranes for Radioactive Waste Repositories on
Land, Report to Dept. of the Environment, DOuRW187.009. Bristol, England, 1988.
8. Buelt, J. L., Liner Evaluationfor Uranium Mill Tailings, Final Report,PHL-4842, Pacific Northwest
Laboratory, Richland, Wash., 1983.
9. Eschrich, H., PropertiesandLong-TermBehavior of BitumenandRadioactiveWaste-Bitumen
Mixtures, SKBF KBS Tech. Rep. 80-14, Swedish Nuclear Fuel and Waste Management Company,
Stockholm.
Soil Asphalt 309
10. Benedetto, A. T., Lottman, R. F?,Cratin, F? D., and Ensley, E. K. Asphalt Adhesion and Interfacial
Phenomena, Highway Research Record No.340, Nat. Research Council Highway Research Board,
Washington, D.C., 1980.
11. Hickle, R. D., Impermeable asphalt concrete pond liner, Civil Eng., 1976, 56-59.
12. Atlas, R. M. Microbial degradation of petroleum hydrocarbons,an environmental perspective,Mi-
crobiol. Rev. 1981, 180-209.
13. Harris, J. O., Preliminary studies on the effect of micro-organisms on the physical properties of
asphalt, Trans. Kansas Acad. Sci., 61, 110-113 (1958).
14. Jones, T. K., Effects of bacteria and fungi on asphalt,Material Protection, 4 , 39 (1965).
15. Testa, S . M., and Conca, J. L., When contaminated soil meets the road, Soils, December 1992,
pp.32-38.
16. Conca, J. L.,and Testa, S. M., Chemical aspects of environmentally processed asphalt, Int. Symp.
Asphaltene Particles in Fossil Fuel Exploration, Recovery, Refining and Production Process, Las
Vegas,Nev.,1992.
17. Haxo, H. E., Jr., Assessing synthetic and admixed materials for liner landfills, including gas and
leachate from landfills, in Formation, Collection and Treatment (E. J. Genetelli and J. Circello.
eds.), EPA Rep. 600/9-76-004,U.S. Environmental Protection Agency,MTIS Rep. PB251161, Cin-
cinnati, Ohio, 1976, pp.130-158.
18. Testa, S. M., and Patton, D. L. (1992). Add zinc and lead to pavement recipe, Soils, May-June
1992, pp, 22-35.
Additional Reading
Asphalt Institute (1990). Asphalt Cold Mix Manual, 3rd d.,Asphalt Inst. Manual Ser. No. 14 (MS-14),
The Asphalt Institute, College Park, Md.
of Hazardous Waste, Van Nostrand Reinhold,
Conner. J. R. (1991). Chemical Fixation and Solidification
New York.
U.S. Environmental Protection Agency (1991). Treatment of lead-Contaminated Soils, Superfund Engi-
neering Issue.
14
Lead Decontamination of
Superfund Sites
Ann M. Wethington, Agnes Y. Lee, and Vernon R. Miller

US. Bureau of Mines
Rolla. Missouri
1. INTRODUCTION
The U.S. Bureau of Mines and the EPA entered into a Memorandum of Understanding in June
1987, that provides for the Bureau to supply technical assistance to the EPA in the area of
treatment of inorganic wastes on Superfund sites. Bureau researchers had already developed an
award-winning processto reclaim lead fromscrap batteries electrolytically [l-31. On the basis
of this experience, interagency agreements were signed to conduct the treatability studies of
waste at five battery-recycling Superfund sites.
In recent years, the numberof lead-acid battery recycling plants in the United States has
been reduced from over 1 0 0 to about 20. When some of the plants closed, they left behind
hundreds of thousands of tons of lead-contaminated wastes and soil. To date, 23 such sites,
ranging in size from 26 acres to about 4 acres, have been designated as Superfund sites by
the EPA [4].
Environmental engineers have investigated new techniques to excavate, stabilize, vitrify,
incinerate, biodegrade, and encapsulate materials considered to be hazardous. Most of these
treatment methods will leave heavy metals in the waste body, which will require subsequent
monitoring, and do not result in a permanent solutionto the problem. None of these methods
can remove lead or lead compounds from the lead battery casing wastes, the adjunct sulfate-
oxide sludge, or the contaminated soils that surround the casing wastes.
This chapter discusses the studyon a site in Ohio, but material from other lead-acid bat-
tery sites has been treatedby the Bureau-developed process. Although the battery casing wastes
The Comprehensive Environmental Response Compensation and Liability Act or Superfund, as it is now commonly
known, was passed in1980. This trust fund, administered by the EPA, was created
to help pay for cleanup of hazardous
waste sites that threatened the public health or environment.
311
312 Wethingtun et al.
from various sites are very similar,the soil composition and level of contamination vary widely
from site to site.
The 26-acre Ohio site is located in a rural area with farmland to the north and south. The
north boundary of the site is bordered by a gravel road. The south boundary is a tributary of
the Miami river witha small industrial plantto the south of it. A railroad is adjacent to the east
boundary with woods and undeveloped land beyond. To the west, the site is bounded by four
residential or business properties and a county road. There is one residence across the road,
directly west of the site. The site drains to the southeast into the tributary, through a swampy
area overgrown withtrees and understory materials. Theoffice, loading dock, and a couple of
sheds remain on the site from the original operation.
The estimated amount of material to be cleaned is55,000 yd3 of waste batter casings and
approximately 85,000-100,000 yd3 of lead-contaminated soil under and around the waste pile.
These battery wastes consist of ebonite battery cases, lead sulfate-oxidesludge, metallic lead,
and the associated soils and debris.Lead contamination of the cases ranged from 900 to 3000
ppm Pb, the lead content of the adherent sludge rangedfrom 20 to 36%, and the lead content
of the soils ranged from 0.05 to 2%.
Initially, EPA's criteria for success were that the battery waste material and soils had to
pass the EP toxicitytest and contain less thanlo00 ppm Pb after cleanup. Later, the criteria for
the battery casings (since they will be shipped off-site) were changedso that the casings had to
pass the TCLP test instead of the EP toxicity test. The EP toxicity was test retained forthe soils,
and the standard for lead content in the soil and casing residue was reduced to 500 ppm. The
criteria were accepted by the State of Ohio. Generally, state laws cannot be less strict than
federal laws or conflict with the intent and purpose of the federal law.
After initial treatability studies, a process was developedto decontaminate the ebonite bat-
tery casings and lead-contaminated soils. The process consists of physical separation of the
different components, carbonation to convert PbSO, into PbC03, and acid leaching to solubi-
lize the PbC03. After a solid-liquid separation and rinsing, the lead levels in the casings and
soils meet the EPA requirements. For the carbonation, two reagents [(NH,),CO, and Na2C03]
were investigated. For the acid leach, two effectiveacids (HNO, and HzSiF6) were investigated
and compared.An electrowinning method was used to strip lead fromthe H,SiF, leachate prior
to acid recycling.
The cleaning battery chips, with a heating value of 13.78 X lo6 Jikg, may be suitable as
a fuel, and the decontaminated soils canbe replaced on the site. The metallic lead and sludge
removed from the battery casings pile may be recycled by a secondary smelter.
II.CHARACTERIZATIONSTUDIES
A. ScreenAnalysis
Casing and soil materials shipped from the Ohio site were split and sampled. Throughout the
treatment process,the casings and soilwere handled separately. The lead contentof the sludge
clinging to the battery casings, the different handling characteristics of the soil, and the sub-
sequent changein the criteria for the casings were all factorsin that decision. Screen analyses
were conducted onthe as-received materials to determine the relative weight of each constit-
uent and the lead concentration in each fraction. The plus 18 mesh fractions from battery cas-
ing wastes were mixtures of casing chips, rocks or gravel, metallic lead grids, and twigs. A
screen analysis on battery casing material is listed in Table 1. (In a screen analyses, standard
nomenclature is to refer to material that remains on a given screening surface as the plus size
and material that passes through the screening surface as the minus size.)
Lead Decontamination of Superfund Sites 313
Table 1 ScreenAnalysis of As-ReceivedBatteryCasings

Size wt %
Plus 318 in. 78.0
Minus 318 in.,17.1
mesh
plus 8
Minus 8, plus 18 mesh 0.3
Minus 18 mesh 4.6
Table 2 BatteryCasingsSample-LeadContentandDistribution (%)

Casings
Rocks
Sludge metal
Pb
~
Sample weight distribution 60.55 4.95 30.7 3.75

Pb weight distribution 0.53 0.08 74.1 25.3
Pb analyses 0.13 0.25 35.8 96"
'kur to six percent antimony is associated with the lead metal.
Table 3 Screen Analysis of As-Received Soil Sample

Size Wt %
Plus 318 in. 9.4
318
Minus mesh in.,8 plus 16.9
Minus 8, plus 18 mesh 2.0
Minus 18 mesh 71.7
Table 4 SoilSampleDistribution (%)

Size Other WtRocks
% Casings
Plus 318 in. 9.4
94.3 2.7 3"
Minus 318 in., plus 18 mesh 18.9 1 99 -
Minus18mesh 71.7 - - -b
'Wood, tramp iron, and metallic lead. No lead metal was discerned in any other mesh
size. Samples from other sites contained significant amounts of metallic lead in the other
mesh sizes, depending upon the individual battery recycling operation.
bo.71-0.85% Pb compounds; 15-20% moisture.
A typical lead analysis and the distribution of the different fractions in the casing wastes
are listed in Table 2. The total lead distribution in the sludge and metal fractions was 99.4%.
The screen analyses of a composite of as-received soil waste sample is listed in Table 3,
and the distribution of this composite sample is shown in Table 4.
B. MicroscopicExamination
One set of casing samples was studied using an electron probe X-ray microanalyzer[7]. These
studies were performed to (1) determine what mineral phases, particularly the lead phases,
were present in the soils and casings; (2) quantify the various lead phases; and (3) determine
complete chemical composition. The casing sample was washed free of sludge, ground, cast in
epoxy, and polished before being examined with the electron probe.
These studies showed the presence of PbSO,, PbO,, Pbo, and metallicPb in all fractions.
The characterization studies of the sludge removed from the battery casings indicated almost
314 Wethington et al.
Table 5 Analysis of theWashedChips

(13/8-in. Chips)
Element PPm
W 3000
As 11.1
Ba 44
Cd 1.1
Cr 22.2
Sb 55
Se 0.001
60% of the lead compounds were PbSO, and the remainder was a mixture of oxides and me-
tallic Pb. The examinationof the casing fragments underthe electron probe revealed numerous
small fractures throughout that were filled with PbSO, and, occasionally, metallic Pb.
This was
a significant finding sinceany successful lead treatment would be dependent on removal of the
PbSO, from these cracks.
C.ChemicalAnalyses
A partial chemical analysis of the washed 3/8-in. battery cases is listed in Table 5 .
A partial chemical analysis of the sludge washed from the casing material is shown in
Table 6 .
The partial chemical analysis of as-received soil samples is given in Section V.B.
111. PRELIMINARYTREATABILITYSTUDIES
Initially, studies were done on the battery casings and soils to determine if physical methods
could be used to concentrate the contaminants and reducethe volume of material that had to be
treated. Since lead compounds have a relatively high density, gravity separation was a logical
choice. The finenessof the soils (<37 pm) suggested that a Bartles-Mosely vannerbe used for
the gravityseparation since it is the only gravity separator that has had any success on<37 pm
materials. The soils containeda high percentage of fines (approximately 15% was <2 pm) that
the vanner could not separate, so there was little or no upgrading. Next, a series of flotation
tests were done using a xanthate collector, mercaptobenzothiazole, andan amine. The best en-
Table 6 Analysis of BatterySludge

~~ ~ ~~
Element PPm Element %
Ag 6 AI 0.52
As 122 Ca 2.8
Ba 245 Fe 1.3
Cd 6 Mg 0.72
Cr 24 K 0.09
Hg ND Na 0.02
Pb 52,000 C 21.2
Sb 858 S 0.22
Se ( 5 Si ND
ND = not determined.
richment ratio was 2:l at a recovery of 20% Pb. Feed grades were reduced, on average, from
0.7% to 0.5% in one pass. Although this test work showed that there was some selectivity
toward the lead minerals present, better reduction of the feed grade wouldbe necessary to con-
sider flotation as a removal method for the lead. Tests using carrier flotation or an air-sparged
hydrocyclone were also applied but showed no improvement. A series of hydrometallurgical
approaches were investigated next.
Preliminary tests on the casings included a water soak. The battery chips were first broken
into minus 3/8-in. pieces and then soaked-stirred in water for 4 days. Various chemical addi-
tions were made to the water along with more aggressive scrubbing methods. An ultrasonic
cleaner was used with various surfactants, detergents, and known lead solubilizers [disodium
ethylenediamine tetraacetate (EDTA), ammonium acetate, sodium citrate, acetic acid,H,SiF,,
and HNO,]. One approach consisted of soaking the material in EDTA for 3 days. After this
treatment, the cleaned battery casings passed theEPA EP toxicity test with <5 ppm Pb in the
extract and also met the standard of <500 ppm Pb in the residue. However, the chips disinte-
grated badly, making solid-liquid separation very difficult, and lead removal from the spent
EDTA was not achieved. Based on previous scrapbattery research, it was known that con-
verting the sulfates to carbonates [8] and reducing the dioxides to oxides would form readily
soluble compounds of all lead except the metallic Pb, which is slightly acid-soluble when finely
divided [9].An acid wash could then be usedto remove the lead. Size reduction would helpto
expose the lead trappedin the cracks and fissuresof the casings. The larger pieces of metallic
lead would be removed by a gravity separation method,and the finely divided (minus18 mesh
and smaller) pieces would be soluble in the time frame used for acid leaching.
IV. CLEANING PROCEDURE, TESTS, AND RESULTS

A.BatteryCasingWastes
The bench-scale cleaning process developed (see Figure 1) consisted of prewashing, gravity
separation, granulation and sizing, carbonation, and acid leaching.
1. Prewashing
Prewashing the battery casings removed most of the adherent sludge and fine metallic lead.
This prevented the sludge and metallic lead from becoming embedded in the casings during
subsequent size reduction. The as-received battery wastes weremixed with water, tumbled in
a ball mill without a grinding medium for 1 hr, and then screened through an 18 mesh screen
to remove the freed sludge and small pieces of metallic lead. This sludge, containing
20-36 wt
% lead compounds and metallic lead, was set aside withoutfurther treatment since it was as-
sumed that it could be sent to a secondary smelter for lead recovery.
2.GravitySeparation
The second step entailed separation of the casing material from the metallic lead, rocks, and
foreign matter by screening and elutriation. Since metallic lead has a much higher density
than the rocks and casings, a gravity separation is possible. The separation technique used in
this work was water elutriation, but air or other density separation deviceswould be effective.
The feed material was screened through 3/4-and 3/8-in. screens, and in both plus fractions
the metallic lead and rocks were separated from the pieces of battery casings by elutriation.
The minus 3/8-in. material was rescreened through 4 and 8 mesh screens. Because the sus-
pension of the different materials is a function of the surface area as well as density, it was
preferable to screen the material into similar size fractionsto provide a consistent feed forthe
laboratory-scale water elutriation system. A schematic diagram of the equipment used is shown
in Figure 2.
316 et Wethington al.
m SPRAYS
rT1-p
WATER PbS04 SLUDGE
JI
I I SEPARATION ROCKS, Pb METAL, ETC.
CARBONATE
CARBONATION Na ,SO, +RECYCLE
'
i 1 * T
ELECTROWINNING
ELECTROWINNING 1I
Pb METAL
CLEANED CASING WASTES
Figure 1 Flowdiagram for decontamination of casing wastes.
3. GranulationandSizing
All the separated casings over 3/8 in. in size were reduced to less than 3/8 in. by granulation
to facilitate carbonation and leachingof the lead compounds entrained in the cracks. Othersize
reduction equipment, such as a hammer mill or shredder, could also be used.
4. Carbonation
The prewashed minus 3/8-in. casings from the separation and size reduction steps were com-
bined, and the residual PbSO, was carbonated at room temperature for 30 min to 1 hr.
The carbonate solution contained 4 g/L carbonate, to ensure excess above the stoichio-
metric amount of (NH4)*C03needed to convert the PbSO, to PbC03. A reducing agent, am-
UATERIAL
FEED
TO C A T M CHIPS
LEAD/ R X K
TRAP
monium bisulfite (47% NH4HS03), wasadded to reduce anyPbOz to PbSO,andthen to

PbCO, according to the equations
PbS04 + (NH&CO3 "* PbCO3 + (NH4)2S04 (W
PbO2 + NhHS 03 + PbSO4 + N&OH (1b)
The carbonate solution was recycledfive times and then used to neutralize the rinse water be-
fore discarding. Although it is an effective carbonating agent, there are drawbacks in using
(NH4)&03, such as odor, disposal problems, and highercost. Sodium carbonate and NaHSO,
were substituted without any problem in the carbonation of the chips. Any carbonate should be
equally effective; however, CaC0, would be the least desirable because the CaS04 produced
has little value and is difficult to dewater and diicard.
5 . AcidLeachwithNitricAcid
After a solid-liquid separation, the chips were rinsed and then leached with5.0 g/L HNO, at
ambient temperaturefor 1 hr. The reaction occurring during the leaching operation can be rep-
resented as
The cleaned battery casings were well below the EPA requirement of S500 ppm residual lead
and 5 5 ppm in the EP toxicity extract. When the TCLP test was designated as the standard, the
HNO, acid concentration of the leachate had to be increased fourfold to pass the 5-ppm ex-
traction portion of the test. The conditions and results of several tests are shown in Table 7.
To minimize the volumes of leachate and rinse, recycling of all waste streams is critical.
The Na2CO3 solution, water rinse, and HN03 leach solutions were each recycled five times.
Makeup reagents were addedto the carbonate and leach solutions. There was no reduction in
cleaning efficiency even by the fifth recycle. Since there are few contaminants except lead in
the chips, this recycling should be feasible until the lead levels are high enough to warrant
precipitation as a lead sludge.
6. Disposal of Nitric Acid Solution and Lead Removal by Lead Sulfate Precipitation
Attempts were made to remove the lead by precipitating as PbSO, with H2S04. The solubility
of PbSO, in water is 38 ppm, with solubility increasing as pH decreases. The drinking water
standard is 0.05 ppm; therefore, before discarding the HNO, it had to be treated to remove the
residual lead. After an H2S04 precipitation, the lead remaining in solution was 250 ppm. By
raising the pH to -8 with a hydroxide, adding sodium borohydride anda flocculant, and mix-
ing for -1 hr before filtering, the lead content was reduced to <0.2 ppm. The small amount
of sludge produced by this procedure would have to be sent to a hazardous waste landfill. The
spent HNO, is more troublesome todiscard. Nitrates must meet drinking water standards of 10
ppm or less before being discarded to a waterway; possibilities include regeneration by a bi-
polar membrane water-splitting system. This processmay be too expensive for the volume of
acid to be cleaned.
7. AcidLeachusingFluosilicicAcid
An alternative to HNO, for the leach is fluosilicic acid (H2SiF6), whichis produced as a by-
product of the fertilizer industry. The major advantage of using H2SiF6 is that the lead can be
recovered directly as pure metallic lead by the Bureau’s patented electrowinning process [3].
Additionally, the acid is regenerated during electrowinning and thereby made available for re-
cycling. The problems associated with the disposal of nitrates are also eliminated. The pre-
Table 7 Battery Casings Leached with HN03-Results of TCLP Tests
m03 (&) Leach residue TCLP filtrate

20.2 213 2
30.2 160 1.4
40.4 128 1
50.4 125 < l
100.8 137 4.1
Note: AI1 tests were on carbonated chips at m m temperature for 1 hr, leach solution
was 1 U125 g of chips.
Lead Decontamination
Sites of Superjknd 319
liminary steps are the same as with the HNO,; the battery casings are prewashed, separated
from the sludge and metalliclead, granulated, and carbonated. The NaHSO, is omitted in the
carbonation step. Instead, the Pb02 is reduced to PbO by additions of hydrogen peroxidein the
acid leach.
The process reactions for using H2SiF6 as the leach reagent are described as follows:
Carbonation:
PbS04 + Na2C03 --$ PbCO3 + Na2S04
Acid leach:
PbCO, + "f PbSiF6 + H20 + c02
Pb02 + Pbo "* 2 PbO
+ +
PbO2 H202 4H+ + PbO + 3H20
+
PbO H2SiF6 + PbSiF6 + H20
Electrowinning:
2 PbSiF6+ 4 H+ + 4 e- 2 Pbo + 2 H2SiF6,
"f €: = -0.126 V (5)
O2 + 4 H+ + 4 e- + 2 H20, = +L23 V (6)
2 PbsiF6 + 2 H20 + 2 Pb + 2 H2SiF6 + 02, €F = €: + E: = - 1.36 V (7)
E,: cathode cell potential
E ~ anode
: cell potential
E,: total cell potential
The cathodic and anodic reactionsoccurring during electrowinningare given in Equations
(5) and (6), respectively, and the overall reaction is given in Equation (7).
As an alternative to electrowinning for cleaning and regenerating the acid, H2S04 was
used to precipitate PbSO, from the lead-rich H2SiF6 leachate.At ambient temperature,the sol-
ubility of PbSO, is high enough to leave -IO00 ppm Pb in the leachate. This lead level is
excessive, and, in addition, the sulfate ions remaining in solution will form PbSO, when the
solution is recycled. This option was not pursued further.
8. Results of Decontamination of Casing Wastes Using Fluosilicic Acid
Several tests using H2SiF6 were completed onthe battery casings. After leaching, TCLPtests
were done on the residues. For each test, enough fresh acid was diluted to the noted concen-
tration to make 0.5 L lixivantll25 g granulated, carbonated chips. Leaches were at ambient
temperature for 1 hr. The acid concentration, amount of 30% H202, and TCLP results are
shown in Table8. All residues metthe - 3 0 0 ppm Pb standard. However, using 80 g/L acid was
considered only marginally successful.
B. Soil Wastes
Tests on the soil samples were conducted simultaneously with the research on the battery cas-
ings. Since upgrading by gravity separation, flotation, etc. were not effective, the hydromet-
allurgical approach used for the casings was followed for the soils (see Figure 3). First, the
as-receivedsoilsamples were characterized andchemicalanalyseswereperformed. The
amount of lead in the soils varied widely, depending onthe specific site and the area within that
site. Partial analyses on one shipment of six samples are listed in Table 9. In addition to the
analyses, sample 3 was identified as vegetation, and samples 1, 2,4, 5, and 6 were identified
H,SiF6
Test (g/L) 30% H202 ( m L ) Filtrate
Residue
Test No. l
leach First 80 2 ND ND
leach Second 80 2 116 <1
Test No. 2, single leach 80 2 468 2.3
Test No. 3, single leach 200 2 129 1.3
CONTAMINATED
SOIL
WATER
Ne2C0, “ 1 7 - N a $ O , ~ RECYCLE
RECYCLE
I I
ACID MAKEUP + ACID

LEACH
l WtETAL
=b ACID TO RECYCLE -
CLEANED SOIL, TO SITE
Figure 3 Flow diagram for decontamination of soil wastes.

Table 9 Partial Soil Analyses

Sample No.
2 1 5 6
Elements, pprn
Ag <5 C5 c5 c5
<5 <5
As 6.6 11 <S 8.7 8.1 c5
Ba 492 442 725 109 698 419
Cd <S c IO c5 c5 < 10 <5
Cr 40 43 34< 20 44 21
Hgc5 c5 c5 <5 c5 <5
Pb
477 517 47 87 4067 2200
Sb <5 <S c5 <5 1 11 22
Se < 5 <5 c5 c5 <5 <5
Elements, pct
AI 5.7 6.2 5.6 .8 6.2 3.5
Ca2.1 2.2 1 5.2
Fe 4.3 3.5 3.9 3 .41 1.5
Mg
1.1 1.5 1.4.82 .82
Si 27.7 28.3 25.6
30.6 29.5
Table 10 Results of EPToxicityTests

Filtrate, ppm
Element Soil 1 soil 2
As < 0.5 < 0.5
Ba 1.1 < 0.5
Cd c 0.1 < 0.1
Cr C 0.5 0.21
Pb 3.2 1.o
Hg < 0.2 c 0.2
Sb C 0.5 1.5
Se < 0.5 < 0.5
as soil. One significant feature observed in samples1, 2, and 6 was the presence of dolomite
[CaMg(C03)2] and, in sample 6 only, bassanite (CaSO,-!h H20). Sample 6 also had more
rocks than the other samples. Since lead in samples of 500
1 and 2 analyzed below the standard
ppm, only an EP toxicity test was completed to verify that lead content would not exceed the
5 ppm extraction standard. Table 10 outlines the results.
Approximately 100 g of the vegetation sample(No. 3) was cut into smaller pieces, washed
with 1.6 L of room temperature tap water for0.5 hr, drained, and then rewashed for a total of
five times. The EP toxicity test results were< l .O ppm Pb in the filtrate and<l10 ppm in the
residue. This indicated that the majority of the lead contamination was in the soil clingingto
the plants and not assimilated into the plant.
In the fourth and fifth soil samples, 6 % of the material was larger than 18 mesh. The
sixth sample contained -28% rocks, wood, and battery casings. The distribution of this last
sample is shown in Table 11. Lead analyses of the minus 18 mesh material in this sample varied
from 7100 to 8500 ppm.
Table 11 Characterization of Soil by Size,Weight,

and Material Distribution
Wt %
Plus 318 in., 9.4 wt %
Rocks 94.3
Casings 2.7
.Wood 3.0
b Metallic 0
Minus 3/8, plus 18 mesh, 18.9 wt %
Rocks 99.0
Wood and casings 1.o
Metallic Pb 0.0
Minus 18 mesh, 71.7 wt %
Soil 100.0
Nore: The minus 18 mesh soil included “35-208 moisture.
1. SoilCarbonation
The following procedurewas used with soil samples 4-6. The sample was wet-screened, and
the plus fraction, which was mostly rock, was set aside and studied with the subsurface sam-
ples. The minus 18 mesh fraction of the sample was mixed with tap water and a carbonate in
a ball mill to give a pulp density of 25 wt %. Since preliminary testing proved that PbSO, in
the soil could notbe leached to pass the standard andhad to be converted toPbCO, before acid
leaching, all subsequenttesting was on carbonated materials. The soil slurry was tumbled with-
out a grinding medium at room temperature for 1 hr with more than the stoichiometric amount
of the chosen carbonate. Initially, the carbonate used was (NH4),C03; however, as with the
chips, there were objections to the cost and odor. Of the other carbonates used, K2C03 and
MgCO, were too expensive and CaC0, was ineffective; therefore, Na2C03 was chosen. So-
dium carbonate at room temperature for l hr in concentrations of 8-100 glL was an effective
carbonating agent. The amount of bisulfite added dependedupon the amount of PbO,, usually
about 30% of the lead analysis. When H,SiF, was used as the lixiviate, bisulfite was omitted
and, instead, H202was added with the acid to reduce the PbO,.
2. Soil Dewatering-Trommeland Flocculant
After carbonation, the minus 18 mesh fraction of the soil sample was dewatered and rinsed.
However, with the soils, extreme difficulties were encountered with the solid-liquid separa-
tions. Pressure filtration at 60 psi, vacuum filtration, settling and decanting, and centrifuging
were all tried with little or no success. The filtration problems may have been caused by the
formation of a sodium silicate or theextremely fine particle size of the soils. This problem was
finally solved by using a flocculant, polyethylene oxide (PEO)[lo]. PE0 is a nonionic, water-
soluble polymer with a molecular weight of 5 million. Published studies have confirmed that
PE0 and its degradation products are nontoxic and do not have an adverse effect on the envi-
ronment [l l]. The dewatering process using PE0 was developed at the Bureau’s lhscaloosa
Research Center, Tuscaloosa, Alabama, where it was used for dewatering phosphate slimes and
other fine-grained wastes. The process consistsof mixing a small amountof PE0 with the car-
bonate or leachate solutions, allowing theflocs to form, and dewateringthe flocs on a trommel.
The trommel (Figure 4) consisted of an 8-in.-diameter pipe, 32 in. long, fitted on the in-
side with a slightly smaller diameter 35 mesh screen that was 4 in. longer than theouter pipe.
A %-hp motor supplied the power to rotate the trommel. A variable controller was used to
change the rotationspeed, and the trommel was mounted ona frame so the angle of inclination
could also be altered. The dewatering efficiency of the system is affected by the slope and
speed of rotation and the feed rate of the flocculant. The soil slurry (12 kg soiY60 L lixiviate
or rinse) was pumped into a small tank, mixed with sufficient PE0 solution to create flocs, and
then overflowed into the rotating trommel. The PE0 solution concentration used was 2.5 g
PEO/L H20. In the 12-kgtest, -3.5 L of PE0 solution was needed in each solid-liquid sep-
aration. This created a product that dewatered rapidly, forming loose rolls containing 50 wt %
solids. A drier solid could be generated by increasing the quantity of PE0 added [lo]. The
amount of PE0 needed depended upon the variables in the process, including soil character-
istics, amount of carbonate used, acid concentration of the leachate, temperature, and solid/
liquid ratio.
3. AcidLeach-NitricAcid
The soil (0.8%Pb) was carbonated with Na2C03and NaHSO, and leached twice with HN03.
Studies were conducted at ambient temperature,70"C, and 90°C. Thefirst leach used 50.4 g/L
HNO,, followed by a solid-liquid separation and a second 20.2 glL acid leach. There was no
rinse between the two acid leaches. After the last acid leach and solid-liquid separation, the '
slurry was rinsed with water until neutrality was reached. The conditions and results of tests on
minus 18 mesh soil are given in Table 12.
As the cost of heating is high, lower temperatures were preferred for all steps. The leaches
at ambient temperaturehad to have twice the leach volumes and greatly increased leachtimes
(2-3 hr per leach) to achieve the objective of <500 ppm Pb in the residue. The increase in
leach solutions required a corresponding increase in rinse volume.
The volumes of leachate and rinse water used require recyciingto make this a viable pro-
cess. In cleaning the chips, there was no difficulty in recycling, but in the soil, HN03 solubi-
lizes Ca, Fe, Mg, organics, etc., leaving no free acid to be recycled. Fresh acid equal to the
original concentration had to be added before any new soils could be leached. This procedure
quickly built up the NO3- ion concentration in the leachate and in the rinse. Since nitrogen
levels have tobe reduced to<10 ppm before discharge of the waste stream, reducing the nitrate
level in the wastewater would have a major impact on the cost of site cleanup.
4. AcidLeach-FluosilicicAcid
Similar acid leaching tests were performed using H2SiF6 based onits successful use in the re-
cycling of scrap batteries [2]. The samples were carbonated using established conditions [8]
and leached with various combinationsof time and acid concentration. For each test, the soils
were treated in two stages. First a leach, using the given parameters, then a solid-liquid s e p
aration and a releach. Tests were conducted at 50"C, 70"C, and ambient temperature. Results
of tests using minus 18 mesh carbonated soil (0.8% Pb), 80 g/L HzSiF6, and varying time,
Table 12 Leachingwith HNO,

Temp, ("C) First leach (hr)' Second
leach (hr)b
Residual Pb (ppm)
25 l 1 1058
25' 2 2 166
70 1 1 229
90 1 1 133
"Acid concentration, 50.4 @L.

bAcid concentration, 20.2 @L.
Tests used I L leach solutionll25 g soil instead of 0.5 U125 g.
Table 13 Effect of Temperature, Time, and H20z on Soil Cleaning Using 80

g/L H2SiF6, Two-Stage Leach
Time (hr) Temp. ("C) H202
(mUL) Residual Pb (ppm)
4" mom 0 5332
4 room 0 1210
lb 70 0 ND
1 70 4 180
lb 50 0 ND
1 50 4 168
lb room 0 ND
1 room 4 337
ND = notdeterminednotdeterminedonthe first stage.

"125g soiV0.5 L leach solution.
b125 g soil/L leach solution.
Table 14 Effect of H2SiF6Concentration on Soil Leaching,

Two-Stage Leach
~ ~~
(gL) H202 (mUL) Residual Pb (ppm)

10" 1 ND
10 1 3580
40" 1 ND
40 1 983
100" 2 ND
100 2 387
2Oob 4 ND
200 4 317
ND = not determined on first stage.
'125 g soil/L leach solution.
b125 g soiV0.5 L leach solution.
temperature, and amount of 30% H,02 are givenin Table 13. Tests using ambient temperature,
1 hr leach time, and varying concentrations of H2SiF6 and amount of 30% H202are shown in
Table 14.
Using H,SiF6 as the lixiviate, the conditions adopted
as a standard with125-g soil samples
were (1) a two-step leach using1 L of 80-100 g/L H2SiF6 each leach, (2) ambient temperature,
and (3) 2-5 mL/L H202. The amount of H202 required for cleaning the soil is more than the
stoichiometric amount forPbO, and had to be determined experimentally for each type of soil
waste. Organic materialsas well as iron and magnesium in the soil catalyze the decomposition
of the H202.
All wash, rinse, and acid solutions used in the process are recycled in a closed loop. Before
recycling the leachate, the lead was removed from thebyacid electrowinning, and any acid loss
was replenished.
5 . LeadStripping by Electrowinning
The acid leachates, containing600-1200 pprn lead, were strippedto <100 ppm using aPm 2 -
coated titanium anode and a stainless steel cathode. Figure 5 shows the rate of lead removal
from 1 L of PbSiF, (80 g/L H2SiF6) by electrowinning at ambient temperature for 2 hr at a
l4O0C
1000 -
E 800-
Current Density 300 A/rn *
si
2c 600-
.-
n
a -
400
200 -
I
0 0.6 1 l .6 2 2.6
Time, h
Figure 5 Leadstripping by electrowinning.
l
0' t I I
0.6 1 l.6
l
2 2.6
Time, h
"CD. 1 6 0 f-CD.200 -%+C.D.400
Figure 6 Effect of current density on the rate of lead stripping. Current density: (W) 150; (+) 200; (*)
400.
current density of300 Mm2. After 2 hr, the lead level was reduced from 1240 ppm to 11 ppm.
The effect on strippingrate of varying the current density from 150 to 400 A/m2 was studied
(Figure 6). In these tests the acid was-95 g/L and the leachate had been recycled four times.
As impurity levels increased with the continued recyclingof the leachate, therate of lead strip-
ping was degraded. After 2 hr, the lead level was reduced from 1100 ppm to 220 ppm. In the
studies shown(see Figure 6), the current efficiency was about15-20% at all current densities.
During these tests, no attemptwas made to optimize current efficiency. For mostof the recy-
cling tests, a current density of 300 Mm2 was used for stripping the lead.
Lead Decontaminationof Superfund Sites 327
Table 15 Results of Using Recycled H,SiF6to clean soils

No. of recyclesa
Test No. HzSiF6 (g/L)
4 13 2
1 80 720 10oOb 1086b 2mb

2 520 640 585 593
3 100
393 369 476 489
‘Lead in cleaned soil residue, ppm.
bNo makeup acid added during recycling leach.
6. Soil Cleaning with Recycled Fluosilicic Leachate

Results from soil cleaningtests using recycled H2SiF6 with concentrations adjusted to 80 and
100 g/L are shown in Table 15. Asindicated in tests 1 and2, 80g/L acid did not decontaminate
the soil to meet the criteria.All tests were at ambient temperature on minus 18 meshcarbonated
soilcontaining0.8% lead. The acid was replenished as necessarybeforeeachrecycling leach. ’
Test 3 (see Table 15) was continued by recycling the 100 glL H2SiF6 solution to clean eight
carbonated soil samples. After the eighth recycle, the soil still met the residual lead standard
by containing only 448 ppm Pb. The test procedure was (1) acid leaching a carbonated soil
sample, a solid-liquid separation; (2) electrowinning to remove lead from the acid leachate,
followed by makeup additions to replenish the acid to 100 g/L, the desired concentration; and
(3) a second leaching of the same soil sample using the replenished acid. These three steps
were repeated to continuously leach carbonated soil samples. Experiments indicated that the
most important criterion for acid recyclingwas to reduce the lead level in the acid leachate to
<l50 ppm before each recycle. Preliminary screening tests indicated that the clays in the soil
acted like ion-exchange resins and reabsorbed any lead remaining in the acid fromthe previous
leach [121.
It was necessary to replenish the acid prior to the second leachof the soil sample because
of acid dilution by the water retained fromthe carbonation step and depletionby reactions with
other ions in the soil. Makeup acid additions were about 8 v01 % on average. A schematic of
the procedure is given in Figure 7.
The impurity buildup in the first and second acid leaches during the eight recycling tests
is given in Tables 16 and 17. After eight recycles, the impurity levels began to reach an equi-
librium value. The impurity buildup during the current tests did not adversely affect the soil
cleaning as long as the lead level was reduced to <l50 ppm prior to the second leach.
One problem encountered in the leach-electrowin-recycle process was dilution of the
acid. After each solid-liquid separation, the soil retained about 50% moisture; therefore, a
bleed stream was necessary to maintain theconcentration of lixivant and to controlthe volume.
About 8 v01 % was bled offafter the electrowinning step, and additionsof fresh acidwere made
to bring the concentration back to the working level.This bleed also helped controlthe buildup
in impurity levels.
7. Recycling ofAcidRinseWater
-
After the final leach step, therinse water had a pH of 1.3 and contained about5 g/L H,SiF,
and 50 ppm Pb. When the lead levels were above 20 ppm, the rinse water was cleaned before
recycling. Initially, this was achieved by adding pure Na2C03 to the rinse to adjust the pH to
-5. A flocculant was added to aid in coagulation of the hydroxide precipitates and improve the
filtration. By this treatment the lead was reducedto <5 ppm, and the rinse water was recycled
successfully. The relationship between the pH, adjusted with pure Na2CO3, and lead content in
the rinse water is shown in Table 18.
H,SiF,
H,SiF6 I Rinse
H!P
1
Figure 7 H,SiF6 recycling test:Procedureandresults. EW = electrowinning; F = filtering;
R = rinsing.
Table 16 FirstLeachate:ImpurityBuildupandH,SiF6Concentration (@L)

Number of
recycles H,SiF6 Ca AI Fe Mg
1.34 1.10 .72 1.04 84.5
2.34 2.10 1.27 2.13 86.9
3.02 3.08 1.79 3.04 84.5
3.78 3.47 2.08 3.48 77.8
4.51 3.89 2.34 3.87 76.8
4.44 3.79 2.32 3.74 77.3
4.87 3.87 2.56 4.22 ND
5.24 4.21 2.91 4.82 ND
In later tests, instead of using pure Na2C03, the spent 10 g/L Na2C03 solution from the
carbonation step was used to adjust thepH in the rinsewater. The results were comparable and
furnished an opportunity to utilizethiswastestream.However,theadditionof the impure
Na,CO, solution to the rinse. water formed a gelatinous compound that would not filter. The
parameters investigatedto improve the lead removal and filterability included pH, additions of
alum and flocculants, and reduction of the metals with sodium borohydride. Optimum filtra-
tion was achieved by adjusting the pH to 5.0 and using 0.5 mL of Superfloc 320 per liter of
solution. Maximum lead removal was achieved by adjusting the pH from -5 to 8, and adding
0.75 g of alum and 0.3 mL of Superfloc 320 per liter of solution.
Lead Decontaminationof Superfund Sites 329
Table 17 SecondLeachate:ImpurityBuildupandHzSiF6
Concentration (glL)
Number of
Ca recycles Fe Mg AI HzSiF6
1 1.69 0.77 1.57 107.0
2 2.15 2.90 1.35 2.73 104.0
3 3.43 1.73 3.32 96.0
4 3.76 1.93 3.47 93.1
5 3.54 3.81 2.06 3.66 96.0
.83 6
.41 7 ND
.88 8 ND
Table 18 LeadContentVersus pH
PH content Pb (ppm)
l 50
2.0
3.0 14
4.0
5.0
5.8
Table 19 ScreenAnalyses of Subsurface Samples (wt 95)

Sample no.
e Mesh A B C
Plus318 in. 0.5
46.0 70.3
Minus26.6
318 plus 4 6.5 10.1
Minus13.4
4 plus 8 4.2 7.7
Minus23.2
8 plus 18 4.5 7.8
Minus18 36.3 14.5 28.4
C. SubsurfaceSamples
Portions of boring samples were submittedby the EPA contractors for testing. These samples
were from depths of 0.5-25 ft, both under the casing pile and around the perimeter. These
lower level samples consisted of mostly gravel and sand, with very little clay, and varied widely
in size distribution. Of the samples received, screen analyses for three are shown in Table 19.
Lead was not determinedon every fraction.EP toxicity tests (no leaches) were done on the
plus 38, plus 4, and plus 8 sizes. These passed both the filtrate (<5 ppm Pb) and residue
(C500 ppm Pb) standards. Leadin the minus 8 plus18 fraction ranged from970 ppm down to
60 ppm. In the minus 18 mesh fractions, lead content ranged from0.12% to over 1S % . Lim-
ited tests were completed on these fractions to determine the effect of usingH,SiF, on a high
calcium and silicon medium. When leaching the minus 4 plus 8 and minus 8 plus 18 fractions,
a silica gel formed that greatly inhibited rinsing and dewatering. A sample of the minus 18
mesh material was carbonated, then leached twice with 100 g/L of H2SiF6. This fraction fii-
tered rapidly. There was a 44% weight loss, but the residue still analyzed 850 ppm Pb-too
high to meet the criteria of <500 ppm. Depending onthe amount of material and lead content,
these fractions may need to be ground and blended with the surface soils for treatment.
V. CONCLUSION
The Bureau of Mines, under several interagency agreements with the EPA, has successfully
developed a process to removethe lead contamination from lead-acid battery breaker sites. The
cleaned materials can pass the requirements ofthe EPA’s EP toxicity or TCLP test with ( 5 0 0
ppm Pb remaining in the soil and battery casings. The choice of acid would depend on the
economics, the ability to clean the waste acid streamsto the discharge limits, and the type of
lead product desired.
At completion of the cleanup at a particular site, lead would be removed from the waste
streams prior to discharge to meet the limit of 50 ppb, f i t by pH adjustment to remove most
of the lead and then by polishing methods such as ion exchange or precipitation.
ACKNOWLEDGMENTS
The suggestionsand assistance of Dr. E. R. Cole, Jr., retired Research Supervisor,U.S. Bureau
of Mines, Rolla Research Center, Rolla,Missouri, have been most valuable.Thanks are due to
Steve Paulson and staff of the analytical services group at l b i n Cities Research Center, Min-
neapolis, Minnesota, for the characterization studies and analyses performed.
REFERENCES
1. Cole, E. R., Jr., Lee,A. Y., and Paulson. D. L., Electrolytic method for recovery of lead from
scrap batteries, BuMines Report of Investigations, Vol8602, 1-19 (1981).
Lee.
2. Cole, E. R., Jr., A. Y., and Paulson, D. L., Recovery of lead from battery sludge,J. Met., 35
(8). 42-46 (1983).
3. Cole, E. R., Jr., Lee, A. Y., and Paulson, D. L., Electrowinning of lead from H,SiF6 solutions,
U.S. Patent 4,272,340 (June 9, 1981).
4. Tetta, D. A., Recycling of battery casings at a Superfund site,Proc. 10th Natal.Conf., Hazardous
Materials Control Research Institute, Washington, D.C., 1989, pp. 301-305.
5 . U.S. EPA, 40 CFR Ch. 1, Part 261, App. 11, Extraction Procedure Toxicity Test (EP).
6. U.S. EPA, 40 CFR Ch. 1 (7-1-89 Ed), Pt. 261, App. I, Toxicity Characteristic Leaching procedure
(TCLP).
7. Paulson, S. E., Petrie, L. M., and Mamas, D.C.,Geologic-geochemicalcharacterization of
heavy metal contamination in soil, Proc. 1992 Fed. Environ. Restoration Con$ & Exhibition, Vi-
enna, va., Apr.15-17, 1992, pp.363-367.
8. Gong, Y.,Dutrizac, J. E., and Chen, T. T., The conversion of lead sulfate to lead carbonate inso-
dium carbonate media, Hydrometallurgy, 28, 1-22 (1992).
9. Mellor, J. W., A Comprehensive Treatise on Inorganic and Theoretical Chemistry, Vol. 7, Long-
mans, Green, London, 1947.
10. Smelley, A. G., and Feld, I. L., Flocculation dewatering of florida phosphatic clay wastes, Bu-
Mines Report of Investigations, Vol8349, 26 (1979).
11. Zatko, J. R., An environmental evaluation of polyethylene oxide when used as a flocculant for clay
dwastes, BuMines Report of Investigations, Vol8438, 1-13 (1980).
12. Gomer. J. S., S. W. Yopps, S. E? Sandoval, and A. L. Clark, Copper exchange capacityof clays and
potentialeffectonin-situcopperleaching, BuMinesReport of Investigations, Vol 9396, 1-10
(1992).
15
A Secure Geologic Repository for
Hazardous Waste Residuals
Thomas R. Nos
Envirovest Management
Houston, Texas
1. INTRODUCTION
The Resource Conservation and Recovery Act of 1976 (RCRA) and the more recent Hazardous
and Solid Waste Amendments of 1984 (HSWA) have mandated the development of innovative
technologies for the destruction, treatment, andlor secure containment of hazardousas waste an
alternative to land disposal methods currently in use. The Hunter Industrial Facilities, Inc.
(HIFI) North Dayton Containment Facility is designed to use innovative technology that will
meet the objectivesand demands of the hazardous waste regulatory programand the needs of
industry for a secure waste containment facility. HIFI has developed and engineered a facility
suitable for treated wastesand raw waste streams that cannot be further treated, recycled, in-
cinerated, or eliminated by improvements in the manufacturing process. The concept of the
North Dayton Containment Facility is to isolate treated and solidified waste by containment
in a stable geologic salt formation, preventing the release of hazardous constituents into the
environment.
The need for secure, long-term hazardous waste disposal facilities that ensure protection
of
human health and the environment has increased in recent years for several reasons.The en-
forcement of new federal and state pollution control laws and regulations has expanded the
universe of wastes regulated as hazardous and has provided for the impositionof fines to re-
move hazardous compounds from wastewater discharges and air emissions. The intensified reg-
ulation and treatment of such discharges has resulted in increasing the volume of controlled
hazardous waste. The regulation of a greater number of generators HSWAunder
and the cleanup
of abandoned disposal sites under the Comprehensive Environmental Response, Compensation,
and Liability Act (CERCLA) amended by the Superfund Amendments and Reauthorization Act
of 1986 (SARA) have also increased the volume of hazardous waste requiring disposaland the
resulting demand for environmentally secure disposal facilities.
The disposal method developed by HIFI involves the solidification and stabilization
of in-
dustrial and commercially generated regulated waste and its placement in caverns constructed
331
332 Klos
deep within a geologically securesalt dome. This waste management concept uses the follow-
ing engineered and natural geologic protection systems.
1. Waste is solidified to reduce the mobilityof regulated constituents and improve handling
characteristics.
2. Solidified waste is deposited in a dry, geologically stable, solution-mined repository,a salt
cavern.
3. The repository is isolated from all groundwater aquifers by the impermeable salt formation
and is constructed belowthe deepest potable aquifer and underground sources of drinking
water in the area.
4. Solidified waste in caverns is permanently contained away from the erosional effects of
rain, wind, and freeze-thaw cycles.
5 . Solidified waste is permanently isolated from humanactivities and inadvertent intrusion.
6. Salt is self-healing, thereby providing its own inherent mechanism for perpetual mainte-
nance.
Salt formations, both domal and bedded strata, originated from saltwaterseas an estimated
150-300 million years ago. Repeated cycles of evaporation and recharge createdthe regional
accumulations of bedded salt with which weare all acquainted (Figure1). Eventually the cycles
of salt deposition ended andwere followed by cycles of sediment deposition. After millionsof
years this sediment deposition and other geologic andclimatic influences culminatedin the salt
formations encountered today.
Throughout this period, salt strata experienced a variety of temperature and pressure in-
fluences determined in part by their depth and their proximity to interior or coastal areas of
continents. Influencesoccurring at the relatively stable interior areas tended to consolidate the
salt into horizontally stratified formations termed bedded salt. In the less stable coastal areas,
buoyancydifferentialscausedverticalmovement of the salt formation, forcingitupward
Figure 1 U.S. salt deposits.

A Secure Geologic Repository 333
through the overlying sediments. Salt beds of the coastal plains tend to be deeper than those
encountered in interior areas, and at this additional depth, temperatures as high as 400°F
greatly reduce the viscosity of the formation, addingto its relativebuoyancy and vertical flow.
This flow, arising from the salt’s plasticity, functions also as a mechanism that expels impu-
rities, including liquids (brine) and solids (rock). Over geologic time this resulted in the for-
mation of underground mountains of homogeneous pure salt (Figure 2). The North Dayton
dome, which actually resembles a column (Figure 3), extends to a depth of45,000 ft below land
surface and has anm a of more than 4 mi2 at its top (Figure4). It is estimated that there may
be 500 similar structures, termed salt domes, in the Gulf Coast region.
Proven solution-mining techniques are employed to create the caverns. Fresh water is in-
jected into thesalt formation under controlled conditions to dissolve salt and leach the caverns.
The water and salt combine to form a brine that ispumped from the cavern and injected into
a saline aquifer using conventional deep well injection techniques. Cylindrical caverns 125 ft in
diameter will be completed approximately 600 ft below the surface of the salt and extend an
additional 1800 ft deep (Figure5). The approximate depthbelow land surface to the top of the
salt is about900 ft. Therefore, the topsof the caverns willbe created about 1500 ft below land
surface, with the bottoms of the caverns 3300 ft below land surface.
All waste will be solidified, cured, then pulverized on-site prior to disposal. During the
solidification process, waste willbe mixed with fly ash, cement, and other additives. The so-
lidified, pulverized waste will be pneumatically conveyed into the underground caverns. After
a cavern is filled with solidified waste, it will be sealed permanently with cement grout, the
open bore hole filled with salt, and the cased hole cementedto the surface.
Solution-mined caverns in salt formations are currently being used by the U.S. Govern-
ment to store crude oil. Since1978, the U.S. Department of Energy has stored more than 750
million barrels of crude oil in solution-mined salt dome caverns for the Strategic Petroleum
Reserve. Contractors engaged by HIFI have been responsible for the development of these
crude oil storage caverns for DOE. These same contractors, who will be developing HIFI’s
caverns, have well over 1000 man-years of experience in this process. In addition to the gov-
ernment’s use of salt dome caverns for secured storage, private industry operates over 1800
caverns in the UnitedStates for the storageof liquid petroleum products, petrochemicals, and
natural gas. The North Dayton salt dome already contains two naturalgas storage caverns that
have been in operation for over 4 years for the benefit of a local utility.
Figure 2 Salt structures.

334 Klos
NORTH SOUTH
SEA LEVEL
-1 000
"
-2000
-4000
-6000
-7000
-8000
-10000
Figure 3 Cross section of North Dayton dome area.
European countries also use caverns in salt formations as containmentsites for hazardous
and nuclear wastes. Based on the fourth amendment to the lawof waste disposalof the Federal
Republic of Germany,certain West German states now require the disposal of irreducible solid
waste in salt caverns.
Domal salt is attractive as a containment medium because ofthe following characteristics.
1. Salt in salt domes is uniquely homogeneous. During salt dome formation, portions of the
surroundingbedded materials, notablyclay, carbonate, andanhydride, are selectively
sorted and displaced by buoyancy and plasticity mechanisms as development of the salt
dome proceeds toward the surface.
2. Domal salt generally has no intrabedded sedimentary layers of impurities to serve as path-
ways for water toenter the body of the dome or asdiscontinuitiesalong which cavern roof
cave-ins may occur.
3. Domal salt is geologically stable and has been stable for millions of years.
4. During formation, salt domes evolved through repeated stages recrystallization
of that left
these structures dense and impermeable to fluids.
5. A relatively impermeable cap rock layer often develops between the salt dome and the
overlying sediments, thereby further isolating the salt stock from shallow groundwater in-
fluences.
6. Salt domes are sufficiently large, typically occupying several square miles, that lateral and
vertical salt buffers exist around the actual repository. A cavern repository wouldbe sub-
stantially separated from the nearest aquifer, typicallyby hundreds of feet of salt.
7. Salt in dome structures is a nonreactive material and will not react with solidified hazard-
ous waste.
4000 2000 0 4000

SCALE FEET
IMPROVED ROAD
"_ PROPERM BOUNDARY
-70'- CONTOUR WITH ELEVATION (FEET MSL)
--1000- SALT DOMECONTOUR
WITH ELEVATION (FEET MSL)
Figure 4 Structure map.

336 Klos
NATURALGROUND
*h%Y>%my>xmay~$
. .......
... ................ .. 36" CONDUCTOR
.*...:.. .... 3 4 CASING (DRNEN)
.
:.......
e.
(....:.'.':*-.:
.......... 30" SURFACE
CASING
.;
: : *. .*.
'
,m.". : *.; :
..e :. L34" HOLE
..'.".,.*.x
.....
..... *.
24" 1ST
CASING
SALT
TOP I
.
........
4..
28" HOLE
SECONDARYSEAL
OF CEMENT
13.38" CASING
17.50" HOLE
BLANKEf FLUID
.- .
10.75" LEACHING
(BLANKET) STRING
7 LEACHING
(WASH) STRING
NOT TO SCALE
Figure 5 Caverncompletion.
The designof the HIFI disposal cavernsis in compliance withthe Texas Injection Well Act
and regulations and guidelinesof the Texas Water Commission Underground Injection Control
program relativeto well construction, siting, and monitoring.Multiple cemented steel casings
prevent any contact between waste and the upper freshwater aquifers. Monitoring of operational
parameters ensuresthe mechanical integrity of casings and verifies that excessive pressuresare
not experienced during cavern development and disposal operations.
Figure 6 Site area map.
II. SITESELECTIONCRITERIA
HIFI has developed an innovative approach to hazardous waste management that meets the
environmental objectives of the Texas Water Commission, U.S. EPA, and other agencies as
well as the needs of the Texas economy. The waste management facility located in Liberty
County, Texas (Figure6 ) will permanently isolate solidified waste deep within the North Day-
ton salt dome.
A. Location
The proposedsite is about40 mi northeastof Houston, Texas. Dayton, the nearest municipality,
is about 5 mi southeast of the proposed site. In 1986, approximately 48,000 people lived in
Liberty County, 6OOO of them in Dayton.
B. Market
The HIFI facility is in close proximity to the Texas coastal area, a major center of hazardous
waste production within Texas and within the Gulf Coast region. This location will offer a sig-
nificant long-term market for the waste disposal facility while minimizing transportation dis-
tances and costs for the greatest volume of wastes. Minimizing shipping distances also reduces
the potential for accidental releaseof waste during transportation. The entire capacity of this
facility could be used by in-state demands alone. HIFI expects that an increasingly stringent
338 Klos
regulatory environment and an increased scope of waste subject to disposal regulations will
further enhance the existing east Texas market for HIFI services.
Even with waste minimizationby industry, expanding regulationof industrial and commer-
cial waste has resulted in greater numbers of regulated generators and of wastes regulated as
hazardous. In addition, Congress has enacted increased restraints on handling certain wastes in
landfills, substantiallyrestricting landfills as a viable methodof hazardous waste disposal. EPA
estimated that in 1984, 1.5billion gallonsof hazardous wastewas disposed of in off-site facili-
ties. A review of Texashazardous wasterecords, after elimination of large one-time shipments,
indicates that in 1984,359 million gallons of hazardous waste was shipped from industrial
fiims in Texas for off-site disposal.Of this 359 million gallons, 85% was generated within east
Texas. In 1987, Texas generated 1,783,480 tons of liquid non-water-based hazardous waste.
The federal Superfund Amendments and Reauthorization Act (SARA) of 1986as amended
(CERCLA, also known as Superfund), Section 104 (C) (9), requires the President to withhold
Superfund monies fromthose states not providing disposal capacity for hazardous waste gen-
erated in-state. HIFI’s NorthDayton Containment Facility will help Texas meet the demands of
SARA.
C. Area Geology
The facility is located overan outcropping of the Beaumont Formation. Thisarea consists pri-
marily of calcareous clays withlow permeability and limited recharge potential. The salt dome
itself is essentially impermeable. The major saline aquifer, Frio,
theis separated from the fresh-
water systemby 800-1OOO ft of aquitards and aquicludes consisting primarilyof multicolored
shales, mark, redeposited cretaceous shells, and lenticular sands.
Major freshwater aquifersin the North Dayton dome area are the Chicot, Evangeline, and
Jasper. Most wells tap the Chicot and uppersection of the Evangeline aquifers. Water levels in
wells completed in the Chicot and Evangeline aquifers generally range from 40 to 130ft below
land surface. Regional groundwater flow in the Chicot and Evangeline aquifers is generally
southwestward. The reasonable upper limit for groundwater flow within the Chicot aquifer is
less than 2 Wday. Because the aquifers do not outcrop over the dome and the overlying clays
are largely impermeable, there is no potential for groundwater rechargein the facility area.
D. SurfaceFacilities
The surface and subsurfacefacilities, when evaluated in lightof the proposed design, construc-
tion, and operational features, minimize any potential for contamination of air, surface water,
andgroundwater.Design, construction, andoperationaldetails to accomplish this include
plans for zero dischargeof wastewater and storm water; redundant controls for potentially con-
taminated storm water; containment of waste operations in buildings, secondary containments,
and curbing; RCRA training and contingency planning; inspection; tank designs; and many
other aspects.
E. 100-Year Flood Plain

The 100-year flood plain, as delineated by the FederalEmergencyManagementAgency
(FEMA), does notintrude into the facility area. Therefore, all surface
facilities and caverns will
+ be outside the 100-year flood plain.
F. Wetland Areas
A survey of soils and plant species in the area has determined that no wetlands exist on the
facility site.
G. AquiferRechargeAreas
The facility is not located withinthe recharge area of any sole source aquifer. Nonetheless,the
facility design incorporates multiple containments to preclude migration of waste to surface
water or groundwater.
H. RegionalAquifer
The regional aquifer is separated from the solidified waste by nearly lo00 ft of imperme-
able salt. In addition, the surface facility is isolated from the regional aquifer by design and
site geology.
1. Soil Units
The entire North Dayton dome area is overlain by the Beaumont Formation of the Houston
Group. Five soil series have been identified at the North Dayton dome site: Beaumont, Ber-
nard, Morey, Lake Charles, and the YatodMocarey series. Although eachof these soils exists
within the overallsite boundary, the Morey and YatodMocarey series cover the major portion
of the actual facility. These series are composed of easily weathered calcareous clay,
silt, clayey
silt, and silty clay. These soils are known to have very low permeability.
J. LocalBodiesofWater
The North Dayton dome is located in the Cedar Bayou watershed, a small coastal basin that
drains to TrinityBay. There are no surface waters adjacent to the facility except for some
ephemeral or constructed ponds. A canal that drains to Cedar Bayou is the only transmissive
water body located closer than 2.5 mi from the proposed facility. The drainage area does not
include a public drinking water supply.
K. ActiveGeologicalProcesses
The North Dayton dome is not undergoing active geological processes. No major low-lying
areas or areas with high subsidence rates exist on the site.
L.EndangeredSpecies
No critical habitat of endangered species is known to exist in thearea. Field studiesof the site
did not locate any such species or related critical habitat.
M. Faults
There is no evidenceof any active fault within the facility area
that would adversely affectthe
operation of the HIFI North Dayton facility.
111. RELATED OPERATIONS IN SALT FORMATIONS

There is a substantial body of technical literature that is related to storage and/or disposal op-
erations in salt formations. Of this, a large portion pertains to operations in salt domes of the
Gulf Coast. Cavernsin U.S. salt domes were first used to store liquefiedgases in 1951; it fol-
lows that many issues affecting containmentproperties of caverns in domes have been previ-
ously addressed over the past 40 years. The largest bodyof written information about salt
domes has been derived from “energy”-related studies. This includes reports, papers, etc.,
340 Klos
emanating mainly from national programs funded by the U.S. Department of Energy (DOE)or
one of its predecessors. Oneearly Atomic Energy Commission-funded study dealt with design
principles for the disposal of nuclear waste in salt, and it was performed at The University of
Texas over 30 years ago. Long-term isolation of waste in salt formations has been recom-
mended by the National Academy of Sciences-National Research Council.
More recent national programs relating to energy include the Strategic Petroleum Reserve
(SPR), which is sited entirely in coastal basin salt domes. In addition, from around the early
1970s through the late 1980s, many studies relating to nuclear waste disposal inU.S. salt
domes were performed through the Office of Nuclear Waste Isolation (ONWI), managed for
the DOEby Battelle Memorial Institute, and its predecessor, the Office of Waste Isolation
(OWI), managed by Oak Ridge National Laboratory(ORNL). These studies focused mainly on
domes in the inland basins of the Gulf Coast as potential sites for nuclear waste repositories;
however, considerable research was also performed in several of the rock salt mines of the
Texas-Louisiana Coastal Basin. Another national program that incorporated field tests in salt
mines in domes dealt with compressedair energy storage (CAES)in salt domes. This program
was managed by the Pacific Northwest Laboratories (PNL) and operated for the DOEby Bat-
telle Memorial Institute.
A major national program in salt research that has been maintained for some time is the
Waste Isolation Pilot Plant (WIPP) near Carlsbad, New Mexico. The objective of WIPP is to
demonstrate the feasibility of disposing of nuclear wastesof the Defense Departmentin bedded
salt. Despite the significant differences between domes and bedded salt formations, the nu-
merical modeling, tests, and field measurements that have been used to study the mechanical
behavior of salt in the WIPP facility are thorough, and the associated reports and papers are
essential referencesfor describing the current state of the art in the analysisof salt containment.
This work is applicable to both domal and bedded salt structures. Additionally, the number of
publications on energy-related national programs involvingsalt formations is also very large.
For example, the list of SPR-related reportsand papers produced solely by Sandia National Lab-
oratories exceeds 120 items, and other contractors for the DOE involved in this program also
have published papers and reports. The number of publications related to the disposal of nuclear
wastes in salt domes probably exceeds those of the SPR program by an order of magnitude.
Considerable experience hasbeen accumulated in the private sector in the practice of min-
ing and storage in salt domes. As noted previously,the first use of salt dome cavernsfor storage
and/or containment was by private industry around 40 years ago. Because of the proprietary
character of commercial enterprise, advances madein cavern storage technology by industrial
operators have not always been reported as promptly or with as much detail as those made in
national programs. However, the many working examplesof containment provided by properly
designed and operated salt dome storage cavernsin the private sector provide verification for
much of the technology proposed for the disposal of solidified wastes in salt dome caverns.
Many storage caverns in salt domes have safely contained materials for decades that are haz-
ardous in character (e.g., hydrocarbons), and thus the experience gained from such operations
is directly related to the HIFI project.
Rock salt mines in Gulf Coast salt domes provide the opportunity to make first-hand ob-
servations of certain characteristics of salt domes thatare issues for storage/disposaloperations
in caverns. The first rock salt mine in the United States was at Avery Island, located west of
New Iberia in southern Louisiana, and is it still operatingtoday. This mine figured prominently
in the national program for nuclear waste disposalin salt. Three other operating mines in the
Texas-Louisiana coastal basin include Hockley, northwest of Houston, and Weeks Island and
Cote Blanche in Louisiana. Another rocksalt mine is the Grand Saline minein the salt domes
of the northeast Texas basin of the Gulf coast.
Regulations for hydrocarbon storage caverns insalt domes were promulgated in Louisiana
as early as 1978. These regulations were formulated initially by a committee whose members
were selected mainly on the basis of their expertise in solution mining andstorage operations
in Gulf Coast salt domes. This committee representedmany decades of accumulated first-hand
experience in utilization of Gulf Coast salt dome caverns. Regulationsfor SPR caverns in salt
domes were set forth in a Boeing PetroleumServices (BPS) documentin 1983. The SPR guide-
lines incorporate some of the early considerations used in designing cavern fields of large ca-
pacities. The Underground Injection Control (UIC) department of the Railroad Commissionof
Texas also has in place regulations pertaining to operations of “brine wells” and storage cav-
erns in salt formations in Texas.
In summary, there exist a very large body of technical literature and considerable experi-
ence related to the construction and operations of salt dome caverns and the solidification of
hazardous waste. This literature and experience was used as guidance for the HIFI project.
W. CAVERN-LEACHINGTECHNIQUES
The fundamental technique of cavern development involvesdrilling and cementing concentric
casings into the salt dome, then drilling an uncased hole to expose thesalt for dissolution.W O
concentric leaching strings of pipe providecirculation of water throughthe well to dissolvethe
salt (Figure 7). Water is injected through either the inner leach string or the annulus, depend-
ing upon the leach phase. As water is injected and cavern development proceeds, a flow of
brine is circulated back to the surface. The result is
the development of a cavern by dissolution.
The brine is filtered for solids removal, then pumped through a pipeline to brine disposal wells
located offthe dome. Alternatively, thishigh purity brine may be used in chemical production
activities.
The rate at which the cavern enlarges depends on two parameters, the flow rate and the
brine concentration achieved within the cavern. These parameters are essentially a function of
the water injection rate, existing cavern volume, contact surface between salt and water, and
method of leaching.
The two basic leaching methods are direct circulation and reverse circulation. The direct
circulation leaching method is used in the first phase of the leaching process to enlarge the
initial bore hole and formthe cavern chimney and sump. Directcirculation involves the injec-
tion of raw water through the inner leach tubing suspended near the bottom of the cavern and
the withdrawal of brine through the annulus positioned above the raw water injection point.
With this method, maximum diametersoccur near the bottom of the cavern, and the diameters
decrease toward the cavern top.
The reversecirculation method is used in the final stage for developmentof the upper area
of the disposal cavern. In reverse circulation, water is injected down the annulus between the
inner andouter suspended strings, causing brineto circulate into the inner string below the raw
water injection point. Reverse circulation causes cavern enlargementin the top half of the cav-
ern. Cavern shapes resulting from reverse circulation depend on the positions of the suspended
strings within the cavern. By raising or lowering the strings, salt dissolution can be controlled
to achieve favorable shapes. In this manner, direct and reverse leaching result in a nearly cy-
lindrical cavern.
Both direct and reverse leaching methods will dissolve salt on all exposedsalt surfaces. To
prevent salt dissolution above the planned caverntop, the salt in this region is protected from
leaching by injection of a material that is immiscible and lighter than water. This material blan-
kets the exposedsalt at the cavern top, prevents leachingof the salt from aroundthe cemented
casing, and protects the casing from internal corrosion. The blanket is injected in the annulus
342 Klos
NOT TO SCALE
Figure 7 Directinjectionprocess.
between the last cemented casing and the leaching string. Careful control of blanket withdraw
near the end of the leaching program permits the development of an arched roof in the caverns
to enhance roof stability.
A. Operational Controls
Maintaining the levelof the blanket and careful monitoring of injection pressures are critical in
leaching a cavern. Pressures imposed upon the final casing shoe should not exceed 0.9 psi per
foot of depth.An alarm system is installed to prevent overpressuringand possible fracturing of
the salt. A high-pressure actuator will close the valve to the well and shut down the pumps
automatically.
A Secure 343
Control of the leaching program consists of control of flow rates, brine salinity, blanket
injection, and periodic downhole geophysical logs and sonar surveys in conjunction with re-
positioning of leaching strings and changes of circulation patterns.
B. DailyControls
rate of fresh water of2000-
The daily routine is oriented toward maintaining a constant flow
2500 gpm and equivalent brine return.
C. Flow Meters
Flow rates are monitored by in-line flow meters and controlled by control valves. Over a period
of days, flow rates and brine density readings can be used to calculate the mass balance of the
process and thereby the progress of the leaching operation. The blanket used to protect the
cavern roof is measured as it is injected into, and recovered from, the cavern. This allows for
an approximation of the depth of the interface level between the brine and blanket layer and
therefore of the cavern roof. The exact interface level is checked
by a measurement survey such
as a density log.
D. PressureIndicators
The pressure on both the brine line and the raw water injection is line
monitored and recorded.
A slight increase in water pressuremay be indicative of an increase in brine salinity and spe-
cific gravity, thus causing a higher differential pressure to exist between the raw water and
brine. The maximum fluid pressure that will be allowed at the last cemented casing shoe at
1500 ft will be no more than0.9 psi per foot of depthto avoid the possibilityof fracturing the
salt-cement bond. A maximum of 1180 psig leaching pressure has been specified for this
application.
E. HydrometerMeasurements
The specific gravity of the brine produced from the cavern is monitored and provides accurate
measurements of the volume of salt dissolved,which can be related to the volume of the cav-
ems at any point in the process.
F. PeriodicControls
During each repositioning of the leaching string, sonar surveys are conducted in the cavern to
determine the cavern shape. If sonar surveys indicate any anomalous development, adjustments
to the leaching plan may be necessary. These adjustments could include a temporary change
in the leaching rate or a changein the depth settingof the leaching strings for subsequent leach-
ing phases.
During the final days of leaching, the blanket is withdrawn in stages in order to form a
stable arched roof with a top about100 ft below the long string casing.
G. Cavern ModelSimulations
The physical basis for cavern construction is the solubility of salt in water. Through develop-
ment of a patented solution-mining laboratory simulator, it is possibleto quantitatively identify
the chemical solubility of different salt minerals. This simulator has been used andtoleach
plan
caverns for the Strategic Petroleum Reserve, and the results have been verifiedby sonar sur-
veys. HIFI will use these simulator profiles for establishment of the solution-mining plan. If
344 KLos
any changes are required in the plan, additional computer simulations of cavern growth are
performed. The computer simulationsincorporate new casing setting depths and salt properties
as determined through brine analysis and sonar surveys.
H. Schedule of Leaching
Each cavernis developed through two phases of leaching. These phasesare engineered to pro-
vide a cylindrical cavern at the completion of the solution mining. The development program
is the samefor each cavern and requires about 340 leaching days to complete. Variationsin the
salt body may require changesin the duration of each leaching phase and modifications of the
leaching plan.
Phase I consists of about 240 days of solution miningby the direct-injection method. This
phase provides for initial mining and development ofa sump forcollection of insolubles during
the remainderof the solution-mining process. At the end of phase I,a sonar survey is conducted
in the cavern to compare the actual cavern configuration tothe simulation plan.
Phase I1 lasts for about100days and uses reverse injection to develop the cavern to its final
design shape. Another sonar survey is conducted at the end of phase 11.
Dewatering and dryingthe caverns and retrofittingthe wellhead in preparation for disposal
operations requires an additional 12 months.
V. WASTEPROCESSINGFACILITY
The facility (Figure 8) includes five distinct waste storage or processing areas (Figure 9). This
section identifies these areas and the process flow sequence from the receipt of waste to the
disposal of solidified material (Figure 10).
A. Waste Receiving, Handling, and Temporary Storage

The process involved in the handling and storage of regulated waste can be summarized as
follows.
1. Trucks enter the facility through the regulated waste entranceand remain in the iegulated
waste truck holding area until an unloading bay in the appropriate storage building be-
comes available.
2. As space becomes available, the trucks are directed to the appropriate building for un-
loading and testing.
3. Waste is unloaded and tested according to the waste acceptance procedure establishedat
the facility and in the permit.
4. Waste accepted for disposalis allocated space in the chemically compatible storage area
within the storage building. Waste not accepted will be managed appropriately.
5. Unloaded trucks are taken to the truck wash station and washed before being permittedto
leave the facility.
6. Oversized debris and drums are collected for shredding andseparate disposal at thefacil-
ity. Separate disposal is required for all solid waste that is not suitable for feed to the so-
lidification process.Oversizedmaterialandshreddeddrums is sized as necessary for
disposal into the salt caverns.
7. The wastesolids are sized and dewateredas necessary before conveyanceto the wastesol-
ids hoppers for temporary storage and subsequent processing.
A Secure 345
+
X X X-
g
Y
r -...-"
, ;
.
LEGEND
PEDESTRIANCROSSING
CONTROLLED ACCESS GATE
-X-X- PERIMETER FENCE
-- -- PROPERTY BOUNDARY
Figure 8 Wasteprocessingfacility.
346 Klos
NO. IDENTIFICATION
200 GATE AND GUARD HOUSE 507 TRUCK HOLDING AREA No. 2
(REGULATED ENTRANCE) (NONRECUUTED)
201 TRUCK SCALES 508 DRIVER WAmNC AREAS
(REGULATED ENTRANCE) 509 FIRE PROTECTION AND
202 REGULATED WASTE TRUCK HOLnlNG RAW WATERSTORAGE
AND SAMPUNC A R U (COWFR 510 WATERTREATMENT P M
203 ANDFIREPUMPHOUSE
51 l ELECTRICAL SUBSTATION
204 512 BACKUP POWER
205 NONFLAMMABLE DRUM BUILDING
206 BULKLlOUlDS AREA (COVERED) 513
207 PROCESSING BUILDING 514
208 SOLIDIFIED HATERIAL BUILDING 515
209 TRUCK WASH WATER HEATER/BOILER
210 FLAMMABLE DRUM BUILDING
600 GATE AND GUARD HOUSE
300 PLANT OPERATIONS, (NONREGULATED ENTRANCE)
PROCESS MATERIALS SUPPLY 60 l VISITOR PARKING
301-310 DISPOSAL CAVERNS 602 ADMINISTRATION BUILDING
603 EHPLOYEE CLOCK ROOM
400 STORMWATER TANKS LOUNGE.AND CAJTTERIA
40 l STORMWATER PONDS 604 EMPLOYEE SHOWER AND
EOUlPMENT ROON
500 TRUCK SCALES 605 LABORATORY
(NONREGULATED ENTRANCE) 606 EMERGENCY RESPONSE AND
50l OIL STORAGE TANK FIRST-AID STATION
503 MAINTENANCE EUllOlNG 608 EHPLOYEE PARKING
504 WAREHOUSE BUILDING
506 TRUCK HOLDING AREA No. 1 70 1 RAWWATER A N 0 BRINE
(NONREGUUTED) DISPOSAL PUMPHOUSE
702 DESANDER AND LINED
BRINEPOND
7a3 I”NG OPERATIONS BUllDlNC
Figure 9 Functional areas.
B.Blending,Neutralization,andHolding
A waste process formulationfor liquids, sludges, and slurries is established by laboratory test-
ing based on the following criteria.
Available waste feedstocks
Forecast of waste to be received in the next 4-10 days
Chemical compatibilityof available feedstock
Prior formulation experience
The liquids, sludges, and slurries are pumped from their respective bulk storage tanks into
the blending tank. Thereare two processing systemsthat can simultaneously processthe waste
mixtures and feedtwo solidification lines. The equipmentin each of the two systems has been
sized to processa batch formulation every24 hr. The process design allocates time in the hold-
ing tanks for batch formulation and adjustments and allows for solidification curing. The use
of two processing trains provides the needed flexibility for the batch processor.
The blended waste mixture is pumped into the neutralization tank, adjusted forpH control,
then pumped into the holding tank. Each of the five holding tanks is sized for a 16-hr batch.
C. Solidification
The solidification process involves adding portland cement, fly ash, lime, and other solidify-
ingreagentstothewaste.There are two solidification processingtrains,eachproviding
$1
X?
d
i
348 Klos
one-half of the total processing capacity. The sequence of activities in the solidification pro-
cess is described below.
1.Reagentand Solids Feed

Solidification reagents are conducted from elevated hoppers and combined with wastesolids in
proportions to ensure appropriate blends. The combinationis mixed to achieve a homogeneous,
dry batch, then held awaiting addition of liquid waste.
2. LiquidSolids Mixing
In the liquid-solids mixer, the liquid wastes are combined with the dry solids and mixed as
necessary for the cemenVpozzolanic reactions to occur. The liquid-solids mixers are sized for
50% void space to provide thorough mixing and initial solidification.
3. Curing Reaction
The curing reaction occurs in curing processors. Feed is introduced into the curing processor
from the liquid-solids mixer by a screw conveyor; additives may be used to supplement the
reactions.
The processor provides for agitation of the reactants during the curing and assists in the
discharge of the solidified mass when the cure is complete. The curing processor dischargesby
a screw conveyor located at its base that subsequently feeds the lump breaker. The 10 curing
processors are each sized to hold a batch that represents approximately 16 hr of normal pro-
cessing flow. The design allows forup to 72 hr of curing time in the processor for each batch
at normal production capacity.
4. Post-SolidificationDrying
The solidified material that exits the curing processor is a relatively dry solid with a free mois-
ture content of approximately 5-10% by weight. To further dry the solid to a sufficiently low
free moisture content for pneumatic conveyance, the product is fed into a rotary dryer,if
needed. The solidmaterial passes througha lump breaker to provide a free-flowing and reduced
particle size mixture before entering the two separate rotary dryers. The two rotary dryers
are consistent with the dual trains used elsewhere throughout the process. The solid material
flows through the rotary dryer to bring the free moisture content of the dried solid to within
the desired range neededfor pneumatic conveyance. Thedrying occurs in a nitrogen-enriched
atmosphere.
5. FinalSizing
The dry solid that exits the rotary dryer passes through a final size-reduction lump breaker to
provide a finely divided, free-flowing material that can be conveyed efficientlyin a pneumatic
conveyance system. The waste product has reached its final form and is conveyed to the so-
lidified material storage building.
D. Temporary Storage
Waste in the solidified material storage building has been solidified in a cement matrix and
sized for final conveyance to the caverns. Temporary storage of this material allows for oper-
ating flexibility in loading caverns and provides additional residencetime for curing if needed.
Storage allowsfor material testing prior to disposal or return to the waste solids handling and
storage building for reprocessing. In most cases, the material in the building is sufficiently
cured and in the proper form for direct discharge to the salt cavern.
E. Disposal
The solid material is pneumatically conveyed into the salt cavern. The pneumatic conveyor
system is composed of dual trains that operate independently. Each pneumatic conveying line
can discharge the final product into a separate cavern. The pneumatic conveyance system is
based on solids being conveyed by a nitrogengas stream. The nitrogen blanketing of the cavern
is established after each cavern is dewatered. Nitrogen is used in the conveyance system be-
cause its use minimizes the presence of humidity in the system and it is a nonreactive gas,
ensuring an inherently explosion-proof atmosphere.
Each pneumatic conveyance system is composed of the following major equipment items:
Three blow tanks
Three gas receiver surge tanks
Three gas blowers
One waste disposal well head assembly
One mobile blowdown tank
One return gas filter
The following procedures describe the basic process flow of solids and nitrogen in the
pneumatic conveyance system.
1. The solids are charged into a blow tank by a screw conveyor.
2. The blow tank is charged with system discharge pressure gas from the gas receiver tank.
3. The blow tank discharges to the conveying pipe and the salt cavern being filled.
4. The solids and gas mixture flows through the conveying pipe and well head assembly down
into the salt cavern.
5. The solidsaredepositedinto thecavern, and the gas returns to thesurfacethrougha
nitrogen-return annulus formed between the two hanging casings.
6. The return gas passes through a filter for particulate removal, then to the main blower
suction header, where it combines with makeup nitrogen as necessary.
7. The blow tank that just discharged its solids is now depressurized.
8. The next blow tank is charged with solids by the screw conveyor, and the sequence is re-
peated until the current conveying requirement is satisfied. The design allows blow for two
tanks on each trainto be used continuously during a conveying transfer while the remain-
ing blow tank and its ancillary receiver surge tank and blower are on standby. Each blow
tank is designed to hold and convey approximately a 15-min charge of solids based upon
the normal design flow rate of one processing train. Each of the pneumatic conveying
trains consists of three pipelines. These lines are the conveying line, the return gas line,
and the nitrogen booster line. Provisionally, a mobile blowdown tank will be located ad-
jacent to the two caverns being filled. This tank is designed to receive and contain the
solids blowdown in the event that a conveying line needs to be evacuated because of a plug
or leak. If this should occur, the conveying line with the problem be evacuated
will into the
blowdown tank. Automatic valve sequencing will divert the flow from the salt cavern be-
ing filled into the blowdown tank.
Ten disposal caverns are planned for the current well field. Each cavern is designed to
contain approximately 800,000 yd3 of solidified material.
VI. SOLIDIFICATION OF WASTE

The process of solidificatiodstabilizationor chemical fixation of liquid waste prior to land-
fill disposal is a commonly accepted practice in the field. The process has reached a sufficient
350 Klos
state of maturity that extensive experience and research literature are available. Since the
bans on land disposal of hazardous wastes that were included in the 1984 amendments to
RCRA, both research and practical useof the technologyhave greatly expanded.As generally
understood, the technology includes the use of organic polymers in addition to cementitious
and pozzolanic materials. In practice, cementitious solidification is the only form commonly
used in the field. Research into use of the technology most often focuses on the question of
whether hazardous constituents in the solidified material have been immobilized. In a landfill
situation, the solidified waste will be in contact with groundwater. The most likely means by
which the hazardous constituents will present a threat to human health or the environment
is through migration into groundwater and transport to an aquifer that is used for drinking
water. In the case of salt dome disposal,the salt itself presents an effectivebarrier to migration
to groundwater.
The solidifying agents in common use are portland cement, alone or mixed with fly ash,
lime, or cement kiln dust. The basic chemistry of the process is the same for each. The ce-
mentitious materials are combined with wastein the presence of moisture or free water, which
carries out hydration reactionsto produce the solidified end product. The solid acquires some
degree of additional structural strength through the formation of calcium carbonate.
There is a history of practical experiencewith lime mortars and cements extendingback to
ancient times. Late Greek constructionand that used throughout Roman times commonly em-
ployed lime mortars. Eventually the Romans developeda very close approximationof modem
portland cementby adding crushed volcanic ash (from the town of Pozzuoli-hence the modern
term “pozzolanic”) to lime. This effort culminated in the development of modern portland
cement in England. The important point is that there is over 2000 years of experience with
cements that can be used to judge the durability of the material under a wide variety of cir-
cumstances and varying technologies.
Although a wide variety of wastes will be received for disposal at the facility, the vast
majority willbelarge-volume,commonindustrialwastestreams, ash, contaminated soils,
and sludges. Materialsthat are gaseous will not be handled, nor will ignitables, explosives, or
radioactive materials.
Chemical analysis of the waste stream will be required of the generator of the waste, and
this will be checked periodically on-site. Upon receipt, wastes will be categorized in termsof
compatibilities, reactive potential, and treatment required. The treatment train will be estab-
lished according to the following steps.
Bench-scale solidification studies. Bench-scale solidification studies willbe carried out on
individual waste streamsor on blended wasteto ensure that satisfactory solidification can
be achieved. The determinationof mix design will draw on bench studies, literature, and
previous experience. The criteria to be used for establishing satisfactorysolidification are
the developmentof an unconfined compressive strength of more than50 psi, no free liquids
present in the solidified wasteas measured by the EPA Paint Filter Test, and no release of
liquids under compression as measuredby the EPA Liquids Release Test.
pH adjustment. Cement- or pozzolanic-based solidificationprocesses involve additionof very
alkaline materialsto the waste. If the waste is acidic, the reaction canbe very exothermic.
Therefore, pH adjustment under controlled conditions must be accomplished to prepared
the waste for subsequent treatment. The extent to which pH is adjusted will be assessed in
bench-scale studies.
Reagent mixing. The appropriate solid and/or liquid reagents are mixed with the waste in a
batch mixer. The output from this step is a semisolid materialwith a consistency similar to
that of concrete prior to setting.
Curing. The material is allowed to cure at ambient temperatures for a period up to 3 days.
This allows a hydration reaction to take place in the binding agents in order to produce a
completely solid material.
Drying. A drying process is carried out by heating the solidified material in a rotary dryer
in the presence of a stream of dry nitrogen-enriched air. The temperature in the dryer
can range from 70 to 160°C. The drying step reduces “free” moisture content to approx-
imately 3%.
Sizing. In order to be pneumatically conveyed into the cavern, the dried material is passed
through a lump breaker to achieve approximately pea-sizeparticles.
VII. CAVERNCLOSURE
Salt cavern repositories are ideal for safe isolation of solidified hazardous waste. The subsur-
face disposal facilities can be designed and constructed in sucha way that there is virtually no
possibility of escape of the contaminants withinthe time frameto perpetuity (defined as 10,OOO
years by EPA). Solution-mined caverns in dry domal salt meet the requisite criteria for this
demonstration and provide the only plausible solution to this problem, for the foreseeable
future. Fortunately, dry stable salt structures, of which the North Dayton dome is an excel-
lent example, are plentiful and providethe requisite qualities of strength, stability, flow prop-
erties, andimperviouscontainment capabilities for ultimate waste isolation. Thus, a salt
cavern repository provides an excellent natural systemthat excludes waste from contact with
the biosphere.
The bore hole from the land surface to the top of the salt cavern is the only pathway con-
necting the waste to the biosphere. For permanent isolation, this avenue must be eliminated,
not by means of an engineered solution, but by permitting natural isolationto occur. To achieve
a natural seal, the 100-ft section of uncased hole in salt (Figure 11) extending upward from the
top of the cavern, will be sealed by salt that has recrystallizedto a salt rock possessing physical
properties as good as or better than the in situ salt of the confining zone. This canbe accom-
plished; however, several yearsmay be requiredto achieve a permanent naturalsalt seal, during
which time an impermeable salt-saturated expansive concrete and chemical and asphalt seals
(Figure 12) placed above the waste at closure will provide a reliable interim shield.
Closure of bore holes in salt has been the focus of considerable researchin the last decade,
spurred primarilyby the need to develop methodsfor sealing openingsin bedded salt following
storage of military-generated radioactive waste at the Waste Isolation Pilot Plant (WIPP) and
openings in salt structures elsewhere including the HIFI project. In situ rocksalt has nearly
ideal containment characteristics, including very low, saturated, porosity and permeability in
the m/s range. This verylow permeabilitycan also beachievedsynthetically by con-
solidation of implaced salt particles. The effects on consolidation resulting from particle size,
water content (inherent and added), temperature, pressure, and stress and of the processes re-
sponsible for them have been addressed in numerous studies.
Figure 11 shows a schematic diagram of the seal, which is the only pathway from the
waste-filled caverns at the North Dayton dome to the surface. The seal is placed between the
cavern roof and the lowermost cemented steel casing at 1500 ft below the land surface. Prop-
erties of the salt-saturated expansive concrete and componentsof the plug other than salt will
provide an excellent sealfor the interim period, during which time the permanent salt seal will
become effective.
For the long-term seal, a thick section of salt has been provided for in the plug design.
Initially, the uncased hole to be filled with salt will be 1.46 ft in diameter. The hole diameter
willbe reduced by creep at an averageclosure rate of about 2.25 X Wyr.If closure is
352 Klos
l-[. . ...",.. ..
i
SWA
62.5' RP91115
____c1
NOT TO SCALE
Figure 11 Cavern closure sed.
unimpeded, the hole diameter will change from 1.46 ft initially to 1.235 ft in 100 years. The
closure/creep will result in a 29% reduction in volume over this period. Resistance to closure
of the hole will be provided by compression of the contained salt aggregate.
The time required for the salt to consolidate to >95% density depends only on the initial
consolidation state. There are several methods for maximizing this consolidation; however, re-
gardless of the procedure implemented,if the average void space in the salt column is less than
Figure 12 Cavern closure.
30% initially, an effective seal will be established in less than 100 years. On the basis of ob-
servations pertinent to consolidation rates, little difficulty is anticipated in achieving a preclo-
sure average salt particle density greater than 80%. Accordingly, the permanent salt seal will
achieve optimum consolidationin less than 60 years.
VIII. WASTE CONTAINMENT IN DOMAL SALT

The most widespread concern about hazardous waste containment is the perceived threat of
contamination of groundwater. This concern is warranted by the record of groundwater con-
tamination associated with traditional near-surface disposal technologies. Therefore, the key
question is whether a salt dome has a particular set of attributes that will prevent the release of
contaminants to the environment in both short-term and very long term time frames. From a
regulatory perspective,a “no migration” petition must be approved by the Environmental Pro-
tection Agency for the containment facility. By “no migration,” it is implied that the waste
354 Klos
, -I Injection Zone ,
I
II II
’‘ L,
I
Injection
Interval - 1
I
I , I I
Confining Confining
Zone Zone
Figure 13 Wastecontainmentzone.
must be contained for 10,OOO years. A demonstration that this condition will be met will re-
quire model calculations, and such models must be based on.the physical and chemical char-
acteristics of thewasteand the geologicenvironment. A unique characteristic here is
that no-migration petitions are routinely conducted for liquid waste injection wells, whereas
the waste form to be disposed at the Dayton facility is in solid form. As fluid flow in deep
formations is well understood, the tasks required in a no-migration petition for liquid wastes
are routinely performed by specialists in hydrogeology and by petroleum engineers. Well-
defined geologic units in such studies include an injection zone and a confining zone (Fig-
ure 13). Injection zones have a reasonably high permeability, and the confining zones should
be of low permeability. The tasks required in the no-migration petition for a domal salt fa-
cility are, however, not routine, for several reasons. First, solid (not liquid) waste willbe dis-
posed of in solution-mined caverns thatwill be on the order of 1800 ft in height and 125 ft in
diameter. For migration to take place, the solid waste would first have to be converted to a
liquid form. Second, the question of how this might take place in a salt dome is not a simple
one. Salt, particularly in salt domes, is not normally considered a flow medium because its
permeability, porosity, and water content are very low. Tests at the North Dayton dome, for
example, indicate that the total water content of in situ salt varies from 0.001 to 0.002 wt%.
For comparative purposes, the bedded salt at the WIPP site contains 0.1-1 wt% water. Even
if we assume that the wastes take on a liquid form some time after placement, the question
remains as to how they would be transported beyond the walls of the salt cavern. ’ h 0 mech-
anisms may be available to do this: fluid flow and molecular diffusion throughthe “porous”
salt rock. Last, the concepts of injection zones, injection intervals, and confining zones as
conceived for liquid injection wells have no geologic identity in an extensive salt environ-
ment. Some relief is provided here, however, as definitions have been provided by the Texas
Waste Commission.
Based on Figure 13, the injection interval is taken as the cavern measuring 38 m in di-
ameter and approximately 610 m in height plus an additional 15.24 m radially, making a cir-
cular cylinder 68.5 m in diameter. The injection zone extends another15.24 m in all directions
from the injection interval, and the confining zone is the remainder of the salt-rock environ-
ment. The task of the “no migration” petition is to demonstrate that the site conditions are
such that the waste will not migrate out of the injection zone. This constraint permits waste
transport over a distance not exceeding 30.5 m radially from the cavern wall,or approximately
49 m from the cavern axis.
The following issues must be addressed in the petition.
1. The potential for brine infiltration, infiltration rate, and how quickly an immobile solid
waste could potentially convert to a more mobile liquid state.
2. The potential for migration of dissolved wasteby advective transport and how far the waste
could be transported over the 10,OOO-year containment period.
3. The potential for migration of dissolved waste by molecular diffusion andhow far the
waste could be transported over the 10,OOO-year containment period.
4. The potential for gas transport out of the cavern and how far gas or gaseous waste could
be transported over the 10,OOO-year containment period.
5. The potential for transportof the waste components in the solid state and how far the waste
could be transported by solid-state diffusion over the 10,OOO-year containment period.
A. BrineInfiltration
Many studies of brine migration in salt bodies focus on the movement of intracrystalline
fluids driven by a thermal field associated with disposed radioactive wastes. As the solid waste
is not expected to affect the existing low-temperature gradientat a domal facility, movement
of this type would be insignificant. However, the possibility exists for brine transport into the
cavern by flow in the interconnected pore space, driven by a pressure gradient. The pressure
gradients can be caused by the condition of atmospheric pressure within the solution-mined
cavern and pore fluid pressures in the rock, which can vary between hydrostatic and lithostatic.
Mobilization of thesolid’wastecannot occurin the absence of transformation to fluid a (liquid
or gas) form.
%o conceptual models havebeen proposed to describe this flow condition. The first as-
sumes that there isat least some interconnected porosityin the salt massand that this porosity
contains some liquid brine. The grain boundary fluidsare likely held so tightly that flow can
occur only in response to large pressure gradients,as in the vicinity of the cavern. However, no
remote flow would occur because of an absence of strong driving forces on a localized scale.
The conceptual model predicts a limited inflow of brine that converges to near zero within a
short time period. Very likely, the only brine available to enter the cavern would be that held
in the mined or disturbed zone at the cavern wall.
A second conceptual model assumes remote field saturation and continuity of the effective
porosity in the salt stock. The pressure gradient is readily transmitted from the localized field
to the remote field, resulting in remote field flow directed toward the cavern. This porous-
media model predicts greater inflow volumes.
Cavern closure also affects this modeling. When the solid waste is initially disposed of
within the cavity, its porosity may be as high as 44% and the pressure is atmospheric. With
plastic creep, this porositywould be reduced considerably, perhaps to as little as lo%, and the
pressures within the cavern will eventually of bethe same magnitudeas in the undisturbed salt
rock. This means that the driving force for fluid movement into the cavernbewill eliminated.
356 Klos
B. AdvectiveTransport
Another important parameter is the permeability of the salt rock, which affects the estimates of
fluid diffusion. There are two values of permeability to be concerned with. The first is the
permeability of the localized disturbed zonein the immediate vicinity of the cavern wall. The
second is the permeability of the remote salt-rock body outside the disturbed zone. Disturbed
zone permeabilities in salt are not well documented although it has been suggested that the
“weeps” on the salt face at the WIPP site are due exclusivelyto the increased permeabilityof
the disturbed zone. As previously stated, bedded salt similar to that at the WIPP site contains
a “wet” salt, with 0.1-1 wt% unbound water. The disturbed zoneat the Asse Mine in Germany
has been determined to be about 3 m, where the permeability decreases from 10“’ m/s at the
rock facetoitsambientvalue of m/s at 3 m. The AsseMinehasbeenmechanically
mined, whereasthe HIFIcaverns wouldbe solution-mined. It is anticipated that solution min-
ing should result in a smaller disturbed zone than would be produced by mechanical mining.
Substantial informationon salt permeability comes from the WIPP site, where the concern
is the disposal of nuclear wastesin bedded salt. Domal salt, which is the proposed host rockat
this project, is noted for being considerably drier and of a lower permeability than beddedsalt.
In salt domes containing onthe order of 0.002 wt% total water(free and chemically bound),we
would anticipate a permeability somewhat less than lo-*’ m/s.
It has been demonstrated that mobilization of the solid waste by contact with the brine
is not a serious problem in domal salt. Even if the calculated inflow entered the chamber for
1OOO years, the cumulative fluid volume would be of the order of 912 m3, and it would be
contained within slightly more than 1% of the available pore space.
Eventually, because of host rock creep, the pressure conditions established in the cavern
would achieve equilibrium with thosein the outlying salt rock, and the driving force forfluid
movement would beeliminated. As mentioned previously,calculations suggest a time frame of
100 years.
During this time, as long as there is inflow toward the cavern, there can be no advective
outflow of solutes, and the diffusional transport out would go counter to an advective brine
inflow, greatly reducing the effectiveness of diffusion as an outward transport mechanism.
C. Molecular Diffusion
Molecular diffusion is one of the possible mechanisms of transport of chemical wastes outof
the salt caverns. In order for diffusion to occur, brine must first infiltrate the cavern and dis-
solve at least part of the solid waste. Additionally, outward diffusion would encounter an in-
ward flow of interstitial brine for some decades after waste disposal, which would reduce the
effectivenessof any diffusional flow. Thus more aggressive assumptions were needed to assess
this mechanism.
A numerical model was developed that assumed that molecular diffusionof waste intothe
salt mass was not affected by the counterflow of molecular brine intothe waste-filled cavern.
It was also assumed that a sufficient quantity of brine surrounded the cavern to transform solid
waste into an aqueous state immediately after disposal, thereby allowing diffusion to occur
throughout the entire 10,OOO-year containment period.And finally it was assumedthat the 3-m
disturbed zone became saturated with contaminants immediately, that is to say, at time zero,
and that the pore space in the adjoining salt rock was liquid-filled.
Although this model approached the subject of long-term containment froma different and
more aggressive perspective than the previous demonstration, it reached essentially the same
conclusion: Disposal cavernsin salt provide strong containment, evenfor dissolved wastes for
time periods far beyond conventional consideration.
D. GasTransport
Gas transport of waste out of the cavern’s unfilled pore space into the brine-saturated pore
space of the surrounding salt rock is an additional mechanism for containment migration. The
gas transport models dealt with gas
a that might form within the cavern from any source what-
ever, including organic and inorganic processes.
The main condition for containment of dissolved contaminants migrating out of a salt
cavern is their attenuation within the injection zone boundary.Three modes of gas migration
were modeled:
1. Dissolved gas diffusion. A soluble gas within the cavernmay dissolve in the brine from the
cavern wall to the injection zone boundary. For a safe-side model, no allowance was made
for counterflow of the brine into the cavern.
2. Volume expansion of gas. For an insoluble gas, the pressure difference between the gas
in the cavern and the hydrostatic pressure of the brine in the salt rock may cause the
gas to expand and drive the brine outward, in the direction of the injection zone bound-
ary, until the pressure of the expanding gas has declined to the level of the hydrostatic
pressure. At this point, there would be no driving force for further flow of gas out of
the cavern.
3. Expansion and d i m i o n of gas. In a combination of the two preceding processes, some
expansion of thegas takes placebeyond the cavern wall, and dissolution of thegas in the
brine transports it by molecular diffusion further toward the injection zone boundary.
E. Dissolved Gas Diffusion

Gas filling the pore space within the cavern may dissolve in the salt brine at the cavern wall
and diffuse in the brine-filled interconnected pore space of the salt rock outwardto the injec-
tion zone boundary. The attenuation of dissolved gas at the injection zone boundary after
10,OOO years can be estimated by the same procedure that was used for modeling dissolved
contaminants.
In either case, however, the attenuation of the dissolvedgas at the injection zone boundary
is as strong as the attenuation of other dissolved species that were modeled and discussed
previously.
We conclude, therefore, that sufficient containment of water-soluble gases is providedby
the salt cavern model system, consistent with the no-migration guideline conditions.
F. Volume Expansion of Gas

A gas occupying the pore space within the cavern
at some pressure higher than the hydrostatic
pressure of the brine in the surrounding salt rock may expand through the cavern wall and dis-
place the brine in the direction of the injection zone boundary. For such a process to occur, a
certain threshold pressure must be exceeded to overcome the capillary resistance of the brine in
the salt rock. Displacementof the brine by gas expansion would continue until the initial gas
pressure within the cavern decreased to the hydrostatic pressure. The pressure decreases with
distance from the cavern wall and is affected by the porosities of the cavern and salt rock.
Models show that the expected travel distancesof an expanding gas in 10,OOO years would be
less than 4 m.
From this we have concluded that the salt cavern system can provide the regulatory guide-
line containment for gases that are either weakly or strongly soluble in salt brines over a period
of 10,OOO years.
358 Klos
G.Solid-stateDiffusion
Solid-state diffusion at temperatures encounteredin salt domes is expected to be extremely low,
particularly for the time frame and distances associated withthe project. Solid-state migration
has been ruled out over the 10,OOO-yearcontainment period.
H. Conclusions
HIFI has examined the containment capabilities of domal salt and has reached the following
conclusions.
1. A nominal volume of brine will seep into the cavern.
2. Most voids between the injected solidified hazardous waste pellets will remain unsatur-
ated.
3. Very small quantities of hazardous constituents will be leached from the saturated waste
pellets.
4. Hazardous constituents in a liquid state will not breach the injection zone boundary,
5. Hazardous constituents in a gaseous state will not breach the injection zone boundary.
6. Hazardous constituents in a solid waste will not breach the injection zone boundary.
7. The containment capabilities of domal salt are exceptional.
IX. FAULTING, FRACTURING, AND SELF-HEALING PROPERTIES

The faulting and fracturing of overlying sedimentary strata associated with a salt dome are
related primarily to volume reduction of the upper portion of the salt mass as it invades zones
of fresh groundwater. This volume reduction occurs over periods that can only be measured by
geologic time. Secondarily, faulting and fracturing may be related to upward geologic move-
ment of the salt mass. In either case, there is no reason to assume that fractures in rock pe-
ripheral to or overlying the dome would propagate fractures in the salt mass itself. Generally,
the salt rock is surrounded by a circumferential fault that is the focusof differential movement
between the salt and surrounding strata. At most domes, including the one at North Dayton,
there is no surface expressionof this fault. This circumferential fault, usually with a thick gouge
or brecciated zone, forms a sheath of limited permeability aroundthe dome.
Fractures createdby stress relief creep withina cavern are of an exfoliation type. Similarly,
fractures created by reloading stress in mine pillars are of this type. Brittle response of the skin
of salt is common when strain dictates movement at a free face. Exfoliation is parallel to the
strain or open wall and results in dislocated laminae that may fall into the opening. In an evac-
uated cavern, the pressure differential at the wall is atmospheric versus lithostatic,,whereas in
the brine-filled cavern, it is hydrostatic versus lithostatic. Exfoliation might be enhanced by
dewatering the cavern. The processwill rapidly diminish as the cavern is filled with granular
solids and stop when the cavern is plugged and abandoned. Cavern integrity is not compro-
mised or threatened.
The cavern spacing and the timing of Cavern construction, dewatering, and filling rela-
tive to construction of the next cavern preclude the possibility of cavern coalescence due to
wall spalling.
To appreciate the phenomenon of self-healing of salt at intergrain or intercrystallinebound-
aries, the operation of pellet, block, or tablet presses in use bymost salt processors can be
reviewed. These synthesized forms of granular salt have nearly the density and compressive
strength of in situ rocksalt, even though short-term pressure, no heat, and no moistureis used
to form the pellets.
X. COMMERCIALIZATION
A. Overview of Hazardous Waste Regulations
Since its establishment in 1970, the U.S.Environmental Protection Agency (EPA) has been
the primary federal entity charged with protecting the nation’s air and water resources. To
date, this mission has been guided by more than a dozen federal statutes, including the Re-
source Conservation and Recovery Actof 1976 (RCRA) and the Comprehensive Environ-
mental Response Compensation and Liability Act of 1980 (CERCLA). These two acts embody
whatisreferred to as the“cradleto graveand beyond”perspectiveonhazardouswaste
management.
RCRAprimarilyaddressesthemanagementanddisposal of wastesproduced as by-
products of current production and consumption activities. They are commonly categorized
according to characteristics of ignitability, corrosivity, reactivity, and toxicity. These are the
wastes produced daily by numerous chemical plants, automobile manufacturers, pharmaceuti-
cal producers, and households.
CERCLA,commonly known as theSuperfund program,providesformanagementof
waste produced in the past, much of which was originally stored or disposed of improperly.
Superfundfocusesonremediatingenvironmentalcontaminationresultingfrominadequate
management practices.
B. Market Size and Description

The scopeoftheRCRAmanagementprogramcan be assessedfrom many perspectives
and levels of detail. From a national perspective, America produces annually approximately
1 ton of RCRA-regulated industrial hazardous waste for every man, woman, and child in
the nation, at a cost of management and disposal exceeding $20 billion per year. Texas pro-
duces 20% of the national total, but hazardous wastesare produced in every city and state in
the country.
These wastes must be managedin compliance with federal RCRA standardsand at facil-
ities permitted under federal or state authority. As a result of complex permitting standards and
economic considerations, the market for commercial waste management services has evolved
from what was previously a localor regional marketto a market that is effectively national in
scope. No individual state has the capabilitiesto manage all of the typesor quantities of waste
produced within its jurisdiction. All states participate in the interstate importation and expor-
tation of waste, and, on average, each state exports hazardous wasteto 19 states.
The Superfund program identifies and responds to environmental contamination resulting
from abandonedor improperly controlled waste sites. In most instances, the materials managed
at Superfund sites is RCRA waste, suitable for treatment or disposal at appropriately permitted
commercial facilities. However, the contaminants may also be non-RCRA waste such as ra-
dioactive material and require different handling.
Currently there are more than 1200 sites on the Superfund National Priority List (NPL).
These sites have gone through environmental impact assessments, as a result of which eachhas
been characterizedas posing an imminent risk to human health and the environment. Each NPL
site will undergo additional, more detailed assessment including a determination of remedy,
sources of funding, and implementation scheduling. In addition to the 1200 listed sites, there
are an estimated 20,000 locations nationwide awaiting characterization.
In 1990, the federal funding for this program was reauthorized through the end of fiscal
1994 with a budget of $5.1 billion. This amount is in addition to the billions spent on reme-
diation by private industry.
360 Klos
I( U INCINERATIONU -e U LANDFILL U
Figure 14 Matrix of technologies for liquids.
C. Pretreatment Technologies and Residuals Management

RCRA waste, regardless of whether it is generated as a by-product of current production and
consumption or reenters the waste management arena viaa Superfund cleanup, must by law be
managed at an appropriately permitted facility. For the majority of wastes this dictates waste
management by either recycling, waste water treatment,incineration, or landfilling (Figures 14
and 15). It is important to realize that each of these technologies, with the exception of land-
filling, functions in part as a volume reduction or chemical separation process. Recycling re-
covers a reusable by-productby separating components in a waste stream; wastewater treatment
removes organics and inorganicsin an effort to restore water’s natural characteristics; and in-
cineration destroys certain types of waste while simultaneously achievinga volume reduction.
Each technology yields a by-product residue, chemicallyor physically altered in the process but
still ultimately requiring disposal.In today’s hierarchy of waste management alternatives, the
“end-of-the-pipeline” disposal technology is landfilling.
D.CommercialFacilities
The number of commercialfacilities available for managing hazardous waste has been declin-
ing for the past decade (Figure 16). This is the result of regulatory pressures brought about
by the passage of increasingly stringent regulations. Owners of many facilities either could
not afford the increasing cost of compliance or were incapable of meeting the new technical
standards. Having fewerfacilities available for management of waste has pushed costs higher
for treatment and disposal whilealso increasing transportation distances.Today, a haul distance
of 500 mi is notuncommon.This attrition hasresulted in significantcapacity shortfalls
nationwide.
E. Waste Disposal Application of Salt Dome Technology

HIFI has received draft permits to construct andoperate a waste treatment facility and a series
of 10 solution-mined disposal caverns within the North Daytonsalt dome in Texas. Each cavern
will be capable of containing approximately 800,000 yd3 of material. This equates to two to
four times the capacity of a typical hazardous waste landfill.
As is the case with other states, Texas does not have the capacity to manage the types or
quantities of waste produced by its industries. As a result Texas is a net exporter of hazardous
Figure 15 Matrix of technologies for solids.
waste, shipping an estimated 235,000 tons per year to out-of-state facilities for commercial
disposal. TheHIFI facility will provide additional in-state capacity
for Texas to manage its own
waste for an estimated 10-20 years.
F. Dayton HlFl TechnologyPark

Adjacent to the waste containment facility, HIFI is developing the Dayton HIFI Technology
Park, a 6600-acre masterplanned industrial complex. Park development is envisionedas a 20-
year project designedto accommodate a wide range of heavy industrial, manufacturing, office,
L - LANDFILL
I - INCINERATOR
Figure 16 Location of commercialfacilities.

362 Klos
Table 1 PlannedLand Use forDayton HIFI TechnologyPark

Land use Acreage
Heavy industrial 3606
General industriahanufacturing 644
Manufacturing 335
Light industrial 421
Industriallcommercial 116
Servicehetail 56
Waste treatment and disposal 197
Recreatiodpreservdreserve 618
Road, rail, utilities, ponds, drainage 607
Total land area 6600
and commercial uses. In addition to the waste disposal and chemical storage capabilities pro-
vided by the existence of the salt dome, the park is directly served by interstate pipeline sys-
tems and includes nearly 3 mi of frontage on the Missouri Pacific Railroad. Highway and water
transportation are readily available as well as access to international markets through the Port
of Houston. The planned utilization program for the DaytonHIFI Technology Park is summa-
rized in Table 1.
XI. CONCLUSION
Disposal of hazardous wastein solution-mined salt caverns will be cost-competitive withother
technologies-more expensive than landfill disposal but lower in cost than incineration. How-
ever, the superior features of salt caverns in terms of the relative permanenceof the repository,
the impermeability of the salt, and its abilityto isolate waste from humansand our environment
provide this technology with incomparable advantages. Problems associated with near-surface
disposal in landfillsis common knowledge, and the costs in terms of both human health and site
remediation are tragic. Near-surface disposalin landfills is not capableof achieving truly long-
term isolation unless the landfill is continually monitored and perpetually maintained, both
above and below grade.
The relative size of salt domes is a unique feature for long-term recordkeeping purposes.
A history of activities conducted at a particular dome can be archived to indicate precise lo-
cations of past activities. Future generations can be cautioned as to appropriate uses of certain
dome areas. Occurrences at Love Canal inNewYork and elsewhere evidence the failure of
current practices in this regard. Disposal in salt domes provides a unique mechanism for pro-
tecting against inadvertent intrusion forcenturies into the future.
Disposal caverns constructed within a dome utilize a minimal amount of surface land and
achieve much moreefficient land use than current technologies. A near-surface landfill sized to
contain a quantity of material equal to one of the HIFI caverns would require 10-20 times the
amount of land needed for a cavern.
The HIFI project brings numerous favorable economic benefits to the host community.
When the containment facility reachesfull operation, it will employ an estimated 170 people,
and the host community will receive millions of dollars in taxes, fees, and contributions.
Development of the industrial park will provide the host community with a large and diversi-
fied economic base. In total, the benefits provided to Dayton and Liberty County will be a
significant boost to the area’s fiscal health.
16
Photocatalytic Degradation of
Hazardous Wastes
M. S. Chandrasekharaiah, S. S. Shukla*, and J. L. Margrave

Houston Advahced Research Center
The Woodlands, Texos
S. C. Niranjan
Rice University
Houston, Texas
I. INTRODUCTION
Nature has many built in checks and balances to maintain a healthy environment. But the in-
dustrial growth of the past twocenturies has been adversely affecting this balance.Thus, there
is an urgent need to regulate our environment-pollutingactivities before irreversible damage is
done to the environment.
The generation of wastes (hazardous and nonhazardous) is inevitable in our technologi-
cal society. Until very recently, no serious thought was given to the proper management of
wastesfrom the manufacturingsector.Large-scalelandfilldisposal or oceandumping are
two examples of the previousimpropermanagementofhazardouswastes.Thesemethods
do not remove the pollutants from the environment but only delay their catastrophic effects.
Pragmatic wisdom dictates the necessity of using waste disposal methodsin which the pollut-
ants are degraded into environmentally benign species prior to their discharge into the envi-
ronment. Increased public awareness of the consequences of improper disposal of hazardous
materials has placed the responsibility for safe disposal of such wastes squarely on the indus-
tries that produce them.
An ideal waste treatment process will completely mineralize all the toxic species present
in the waste stream without leaving behind any hazardous residues. It should also be cost-
effective. None of the treatment technologies at present approach this ideal situation. There
are a number of waste disposal methods currently in practice with varying degrees of suc-
cess. Figure 1 is a schematic representation of different treatment technologies either cur-
rently available or in varied stages of development. At present, the disposal of the bulk of
the industrialwastesisbasedon the processesdevelopedonphase-separationprinciples
[l-31, eventhoughnoneofthem is completelysatisfactory. The incineration of organic
wastes is the other widely practiced method.This in principle should destroy the toxic pollut-
*Currenfaffiliafion:Lamar University, Beaumont, Texas

363
364 Chandrasekharaiah et al.
WASTESTREAM
mm
Photocatalvtic
IDegradatidn 1
IMicellarMedia] I
Solidification/Stabilization
& Landfill
p gEi%-l
Activated Carbon
Figure 1 ‘Iteatment methods for hazardous wastes.
ant completely, but the incineration ofmany hazardous organic wastes releases other toxic
species into the air [4]. An example of this is the incineration of PCBs, which has resulted
in the release of dioxins that are as toxic as the PCBs themselves. Incineration as practiced
todayisthus also notan ideal waste treatment process. Biotreatment ofmunicipalwastes
has been practiced, but similar biotreatment of industrial wastes are not common methods of
waste management.
Photochemical degradation of wastes containing toxic species has many attractive fea-
tures. The process does not require exogenous chemical additions, thus eliminating the conse-
quence of residual chemical species in the effluents. Ultraviolet irradiation as an alternative
to chlorination for the disinfection of drinking water is probably the best example of a photo-
chemical detoxification process. Though there have been some attempts to treat toxic wastes
with direct UV irradiation [5,6], their success has not been such that large-scale commer-
cial waste treatment facilities using direct UV light irradiation have been built. One reason
for this may be the absence of a fully developed photochemical treatment process for the
management of large volumes of hazardous industrial wastes. The other reason may be the in-
commensurate cost of the direct photochemical degradation processes. If the process can be
made less expensive and more specific, then toxic wastes could be processed through photo-
chemical degradation.
Photocatalytic degradation of wastes rather than direct photochemicaldecomposition
shows promise. Recently,a number of investigators have reported the degradation of hazardous
chemical species in aqueous medium using microheterogeneous media as a photocatalytic agent
rather than direct photolysis [7-121. The potentialfor the development of waste treatment pro-
cesses based on photocatalytic reactions in microheterogeneous media appears to be very prom-
ising. Here, we describe the use of two such microheterogeneous media, namely, colloidal-
semiconductor sols and micellar systems, as photocatalytic agents.
Photocatalytic Degradation 365
II. PHOTOCATALYSISINMICROHETEROGENEOUSMEDIA
A. Photocatalysis
Photochemical reactions in solution media have been extensively studied. There are a number
of references on this subject, and the reader may refer to them for details [e.g., 131. Photoca-
talysis is a distinct subsection of photochemistry [14, 151. The term “photocatalysis” implies
a combination of photochemical reactions and a catalytic process. A chemical transformation
brought about in a molecular entity as a result of initial absorption of radiation in another mo-
lecular entity may be the simplest exampleof a photocatalytic process.
Photocatalysis in heterogeneous media will be exclusively considered. The catalytic pho-
toreduction of water to hydrogen in the presence of a reducing agent and semiconductingtita-
nium dioxide is a good example of a photocatalytic reactionin a microheterogeneous medium.
The titania particle initially absorbs the radiation and thencatalyzes the transfer of electrons to
water adsorbed on the surface of the particle. Capture of an electron from the reducing agent
on the surface regenerates the catalyst.
Serpone and Pelizzetti [l21 provide a basic in-depth discussion of photocatalysis. The re-
mainder of this chapter will concentrate on the application of photocatalysis in microhetero-
geneous media for hazardous waste management.
B. MicroheterogeneousMedia
Photochemistry in homogeneous solutions is a subject familiar to most chemists. Microheter-
ogeneous photochemistry is less so. The system here is somewhat homogeneous on a macro
scale, but it is heterogeneous on a microscopic level. Many of the processes in these systems
are taking placeat the interfaceof two phases. Thecolloidal semiconductor sols and surfactant
micellar systems are good examples of microheterogeneous media. Thus, all the microhetero-
geneous systems are at least two-phase systems in the true thermodynamic sense butmay ap-
pear to be a singlephaseonmacroscopicobservation [16,17]. Figure 2 is a schematic
representation of some of the microheterogeneous mediathat have been studied in detail. Some
of the implications of stating that a system is microheterogeneousare listed below.
1. Many physicochemical properties, e.g., the bulk density, concentrations, or chemical p-
tentials, are nonuniform throughout the volume.
2. There may be charged interfaces, and hence the local space-charge effects may influence
the reactivity rather significantly.
3. Most of these systems are generally optically transparent to light. (This aspect is of par-
amount importance in the photocatalysis.)
In this presentation, micellar media and colloidal semiconductor media will be used for
the discussion.
111. PHOTOCATALYTIC DEGRADATION OF HAZARDOUS WASTES IN

COLLOIDAL SEMICONDUCTOR SOLS
The results of the studies devoted to the splitting of water by solar light in the presence of
semiconductors formthe basis for the photocatalytic degradation of the toxic pollutantspecies
in aqueous solutions in the presence of semiconductor particles [18]. Stated briefly, when se-
lected semiconductor particles are illuminated with the proper light source, the absorption of
light is followed by the formation of electron-hole pairs at the surface of the semiconductor
particle. The excited electron-hole pairs thus created will react with the adsorbed species on
366 Chandrasekharaiahet al.
~ ~~~~
I
I 1
Molecular Aggregates Polymeric Systems
J
I
I
Colloidal
I
I
Sols I
I
Surfactant Media
I
ILipids
I
1 I
r-l
I
Vesicles
Membranes
Liquid Crystals
"IMicroemulsions I
Figure 2 Microheterogeneous media.
the surface of the semiconductor. It has been shown that under certain circumstances adsorbed
water will also oxidize to oxygen. The efficiency of this photodecomposition of water is in-
sufficient to develop an economically viable process for the conversion of solar energy into
hydrogen fuel. However, the photogenerated electron-hole pairsat the surface of the semicon-
ductors can oxidizea number of species present in the solution rather efficiently [7-9,19-371.
Many of the species observed to degrade under theseconditions are included inthe EPA list of
priority pollutants. Thus, the scientific basis for the photocatalytic degradation of hazardous
species was established. Thougha toxic waste treatment process based on this phenomenon has
not yet been built, the photocatalytic degradationof toxic pollutantsat the surface of semicon-
ductor particles has the potential for an energy-efficient and safe waste management process
commensurate with the economy of disposal.
A. Photocatalysis at the Semiconductor Surface: Principles

A necessary condition for the absorption of the photons by the semiconductor particle is that
the energy of the photon should exceed the energy of the bandgap of the concerned semicon-
ductor [38]. This threshold wavelength for the absorption, Abg, can be expressed according to
the equation
(nm) = 1240/Ebg(eV) (1)
where is the threshold wavelength of a photon and Ebs is the bandgap energy. Table 1 lists
the and Ebg values for some important semiconductors as determined by the flat band con-
dition. These values for the bandgap energies may be altered when the semiconductor surface
is in contact with an electrolyte solution [18,38]. The band edge positions and the bandgap
energies of a few semiconductors of importance in the photocatalytic degradation studies are
shown in Figure 3. The data refer to the conditions where the semiconductors are in contact
Table 1 ThresholdWavelengthsandBandgapEnergies
for Some Semiconductors
ThresholdBandgap
Semiconductor
Energy (eV) wavelength
(nm)
SnO, 3.5 354

ZnO 3.2 388
SrTiO, 3.2 388
TiO, 3.0 413
CdS 2.4 517
2.1 590
Si 1.1 1128
Source: Finklea [38].
withanaqueoussolution ofpH 1. These values are derived from the flat band potential
measurements [181.
The knowledge of the band edge position is particularly useful in the discussion of photo-
catalysis [18,21,39]. In Figure 3, the standard potentials for several redox systems are also
listed. The relative positions of the standard potentials and the band edge positionsare indicative
of the thermodynamic limits for the photochemical reactions at the surface of the illuminated
semiconductor particles. For example, if an oxidation of the species in the electrolyte is to be
performed, the valence band edge position of the semiconductor mustbe positioned below the
relevant redox level. Thus it can be seen that colloidal TiO, will be a strong oxidizing system.
The free energy of the charge carriers generated by photoexcitation of semiconductors is
directly related to the chemical potential. In the dark, under thermal equilibriumthe chemical
potential of the electron is equal to that of the hole and corresponds to the Fermi level of the
solid. But under illumination, the system departs from the equilibrium, and the chemical po-
tentials of electrons and holesare no longer equalas they are under equilibrium, nonirradiated
conditions. As a result, the Fermi level splits into two quasi-Fermi levels, one for the electron
and one for the hole. The chemicalpotentials become functions of the nonequilibrium concen-
trations of electrons and holes. These concentrations are dependent on the absorbed ,light in-
tensities. These differences are useful in redox reactions involving the electroactive species in
the medium.
The transfer of mobile charge carriers between the semiconductor andthe electrolyte is an
important step in the photocatalytic degradation of toxic species. When anelectroactive species
is present in the electrolyte solution, the charge transfer can take place directly across the semi-
conductor-solution interface. This will create a space charge layer at the interface, and the
valence and conducting bands will be bent. This will affect the effectiveness of the redox pro-
cesses possible in the presence of the illuminated semiconductorparticles. If the majority car-
riers are depleted from a colloidal semiconductorin solution and the particles are too small to
develop a space charge layer, the electric potential difference resulting from the transfer of a
charge from the semiconductor to the solution must drop in the Helmholtz layer (neglecting
diffusion layer contributions). As a consequence, the positions of the band edges of the semi-
conductor particle will shift. For example,if after photoexcitation of a colloidal n-typeparticle,
holes are transferred rapidly to an acceptor in solution while electrons remain in the particle,
a negative shift in the conduction band edge at the surface will take place.
In the case of colloidal semiconductors, the band bending is small, and charge separation
occurs via diffusion. The absorption of light leads to the generation of electron-hole pairs in
E
“[NW
- CdS ~ e d o xPotential
-0.5 - -1
(n)
- Eu[+2]IEU[+3]
- i
Z
0.0 - I H[OlM[+l]
f
- I
% -
i2.5
- ieV
1.0
- i i3.2 I
I
1: eV -- Cr[+q/Cr[+3]
Cl[O]/Cl[-l]
- I
- 1 iI -
-
Cl[+1]/C1[-1]
~e[+4]/Ce[+3]
2.0 I-“
l
I - AS[+214t[+11
1
I 3.0
eV
1
i
J
3.0
4.0
Figure 3 Bandgap energies and band edge positions for some semiconductorsin contact with an elec-
trolyte solution at pH 1. (From Ref. 18.)
the particle that are oriented in a spatially random fashion along the optical path. These charge
carriers subsequently recombine or diffuse to the surface, where they undergo chemical reac-
tions with suitable solutes or catalysts deposited onto the surface of the particle.
The depletion layerof the semiconductor-solution interface, sometimes referredto as the
Schottky barrier, plays an important role in light-induced charge separation. The local elec-
trostatic field present in the space charge layerserves to separate the electron-hole pairs gen-
erated by illumination of the semiconductor. For n-type materials, the direction of the field is
such that holes migrateto the surface, where they undergoa chemical reaction, while the elec-
trons drift through the bulk to theback contactof the semiconductor and subsequently through
the external circuit to the counter electrode. Charge carriers that are photogenerated in the
field-free space of the semiconductor canalso contribute to the photocurrent. In solids with low
defect concentrations, the lifetime of the electron-hole pairs is long enoughto allow for some
of the minority carriers to diffuse to the depletion layer before they undergo recombination.
Since in colloidal semiconductorsthe diffusion of charge carriers from the interior of the
particle surface can occur more rapidly than the recombination, it is feasible to obtain quantum
yields for photoredox processes approaching unity. Whether such high efficienciescan reallybe
achieved depends upon the rapid removal of at least one type of charge carrier, i.e., either
electrons or holes, upon the arrival at the interface.
The theroretical basisof semiconductor photochemistryis well established [12,18]. For re-
actions occurring at the semiconductor-liquid interface, either the semiconductor itselfor any
of the adsorbed species may act as the light harvester. If the semiconductor is the absorbing
unit, a light photon will promote an electron from the valence band to the conduction band,
ox
RED
Electrolyte Dlffusion
Figure 4 A schematic presentationof photocatalyzed oxidation atan illuminated, n-type semiconduc-

tor. (From Ref. 18.)
thereby generating a hole in the valence band. Afterthese charges migrate to the surface of the
particles, the reaction of the photogenerated electron with a reducible absorbed species and/or
the reaction of the hole with an oxidizable species can take place. Figure 4 is a simple repre-
sentation of the photocatalyzed reactionat the surface of an n-type semiconductorparticle [18].
These principles have found extensive application in the field of light-induced generation
of fuels and that of organic transformations, but only recently in the field of environmental
chemistry and pollution control. In fact, with the exception of a few reports concerning some
contaminants, photoeffects at semiconductor interfaces have been largely ignoredby environ-
mental chemists [7].
B. Applications
The observation that a number of solute species present in the solution were photocatalyzed at
the illuminated semiconductor surface evolved fromthe photodecomposition studies of water
with solar radiation. Bard and coworkers [26-301 have shown that many hazardous species,
including someof the EPA priority pollutants, could be degraded into innocuous speciesat the
illuminated titania semiconductor surface. Their work formed the nucleus for the concept of
photocatalytic degradation of hazardous wastes using semiconductor particles. Following this
lead, our laboratory demonstratedthat ferricyanide species could be completely mineralized in
the presence of illuminated colloidaltitania semiconductor sol [8]. Table 2 shows someof these
results. Other investigations have shown the photocatalytic oxidation of a number of organic
species at an illuminated semiconductor surface. Ollis and coworkers [7,9] summarized the
available results.
The use of chlorine as a disinfectant in urban water supplies is not without its problems.
The halomethanes that are formed during the chlorine treatmentbecomehazardousspe-
cies. Therefore, a number of investigations were carried out to study the fate of these halo-
methanes in the presence of near-ultraviolet-irradiated TiO,. The results were very encouraging.
Table 2 Photocatalytic Degradation of Ferricyanide in Presence

of Illuminated Titania Sol"
Fraction of
Time (hr) Fe(CNp- converted
0 0.0
1.5
3.0
-46%
1009bb
6.0 78%
9.0 93%
'Initial conc. of ferricyanide = I M , pH = 10.
bIIluminated to midday sunlight in a fused silica vessel. All the others were
exposed to a 4-W mercury lamp.
Source: Taken from Bhakta et al. [8].
ing. Pruden and Ollis [32,34] clearly demonstrated that the trichloromethane (chloroform) is
completely oxidizedto chloride and carbon dioxide. Theyalso established that the degradation
reaction was indeed photocatalyzedat the surface of the illuminated Ti02 particles. In a series
of papers, Ollis and coworkers [31-371 have shown that not only the chloroform but also a
numberof other low molecular-weightchloro-organiccompounds (e.g., CH2CI2,CHCl,,
CH2ClCH2Cl, CH2C1COOH, andCHC1,COOH) were photocatalytically completely mineral-
ized at the surface of UV-illuminated titania semiconductor slurries. In all these systems,
they did not observe the formation ofany intermediate species. From their results, itwas
concluded that the photocatalytic degradation oflow molecular weight chloro-organics was
complete if the carbon atom bondedto the halogen also had a hydrogen atom attachedto it. On
the other hand, they notedthat the halocarbons containing halide-saturated carbon (e.g., CCl,,
CC1,COOH) did not degrade into carbon dioxide.
Trichloroethylene and perchloroethyleneare two chloroalkenesthat have widespread use,
and hence the wastes containing these compounds are considered hazardous. The photocata-
lyzed destruction of these at the surface of illuminated TiO, slurries has been studied. Both
have been shown to mineralize completely into carbon dioxide and chloride [34,35]. In the
presence of dissolved oxygen, it was shown that the degradation of perchloroethylene goes
through an intermediate of 1 ,I-dichloroacetaldehyde.However, the intermediate species was
also observed to degrade under the experimental conditions. Pruden andOllis [34] established
that the photodegradation of trichloroethylene in the presence of UV-irradiated anatase slurries
was a photocatalytic process and not photodecomposition. The degradation products were
shown to be chloride (measured witha chloride ion electrode) and carbon dioxide (precipitating
barium carbonate from barium hydroxide solution by bubbling the effluent gases through it).
For a reaction time of about 120 min. they reporteda conversion factorof about 97-100%. Ollis
[36] expressed the reaction rate in terms of the equation
l/rate = l/k + l/kK X I/c (2)
where k and K are the parameters deduced experimentally and c is the concentration of the
reactant. Ollis [36] has listed the values of k and K for several of the chlorocarbon photoca-
talysis reactions from whichthe photocatalytic degradation rates could be evaluated. Some of
these data are presented in Table 3.
A very wide rangeof aromatic hydrocarbons and their haloderivatives find their way into
the environment throughthe use of these compounds as preservatives (woods, paints, drilling
muds, photographic emulsions, hides and leathers, textiles), antimicrobials (industrial cooling
Table 3 Rate Parameters for the Photocatalytic Degradation

of Halocarbonsa
Reactant K-Value k-Parameter
C1H2C-COOH 5.5 0.002
C1,HC-COOH 8.5 0.003
CH,CI, 1.6 0.02
CHCI, 4.4 0.003
CCI, 0.18 0.005
CH2Br2 4.1 0.02
CHBr, 6.2 0.01
ClH,C-CH,CI 1.1 0.01
CI,C=CCCIH 830.0 0.01
CI,C=cCI, 6.8 0.02
Br2HC-CH2Br 2.2 0.02
Br,HC-CH, 3.9 0.02
“k = ppm/(min. g catalyst); K = ppm - 1.

Source: Ollis [9].
waters, pulp and paper mill operations, etc.), herbicides, insecticides, and disinfectants and
other health care products. Most of them are hazardous. A great dealof attention has been paid
to removing these species from the wastes containing these compounds. Several investigators
have examined the application of photocatalytic degradation at the surface of semiconductors
with varying degrees of success.
Direct photodecomposition of monochlorobenzene at h. = 254 nmby Tissot et al. [40]
resulted in the formation of phenol, which is also a toxic compound. Ollis et al. [35] studied
the reaction of chlorobenzenein the presence of illuminated Ti0, slurry with light ofh > 300
nm and foundthat the primary photocatalytic productswere chlorophenols. The chlorophenols
subsequently dechlorinated and formed benzoquinones. The use of anatase (another form of
TiO,) of a much higher specific surface area had resulted in complete mineralization of chlo-
robenzene. Oliver et al. [41] showed that 1,4dichlorobenzenewas also rapidly mineralized in
the presence of UV-irradiated 1% TiO, slurries. The results of several investigations [7,42-441
have clearly shown that photocatalytic destruction of several chloroaromatic hazardous com-
pounds is almost complete. The haloaromatics that have been shown todegrade in the presence
of illuminated semiconductor slurries are Cchlorophenol, 3,4-chlorophenol, 2,4,5-trichloro-
phenol, pentachlorophenol, chlorobenzene, 1,4-dichlorobenzene, trichlorobenzene, 2,3,5-tri-
chlorophenoxyacetic acid, 4,4’-dichlorodiphenyltrichloroethane,3,3’-dichlorobiphenyl,and
2,7-dichlorodibenzo-p-dioxin.With many of these compounds, the conversionrates of the in-
termediates is sufficiently fast that no intermediate species are observed via gas chromatog-
raphy/mass spectrometryof the liquid-phase samples. Almost all of the studies have usedTiO,
slurries. Ollis et al. [7]summarize the data and present the half-life values for the photocata-
lytic degradation of some of the haloaromatics.
These values for half-lives are generally for the initial reaction rates and vary from a low
of 10 min to a high of 90 min. Therefore, one can conclude that the complete photocatalytic
degradation of the species at concentrations of about 6-45 ppm will be onthe order of 1-6 hr.
There are exceptions. For example, 2,7-dichlorodibenzo-p-dioxin,with an initial concentra-
tion of about 18 ppm, required 90 hr for its complete disappearance (7,42). Thus, the photo-
catalytic destruction of these toxic species present in wastewaters shows great promise as a
treatment process.
In addition, there have been some studieson the photodegradation of common surfactants
in the presence of Ti02 slurries [43,45,46]. At least one member of each of the three types of
surfactants (anionic, cationic, nonionic) has been shown to exhibit complete photocatalyzed
conversion. Total mineralization into CO2, though, has not been demonstrated in all cases.
And, for all three typesof surfactants, degradation of the initial reactant is found to relatively
rapidly destroy the surface activity of the surfactants.
The majority of the studies have used semiconductorslurries asthe photocatalytic media.
As the photochemical reactions take place primarily at or near the surface of the semiconductor
particle, the use of colloidal sols of semiconductors will definitely enhance the conversion
rates. The complexed cyanide species, which are very resistant to the chlorine oxidation pro-
cess, can be easily degraded at the surface of colloidal TiO, sol. Even solar radiation was
shown to photocatalyze the degradation process [8].
A review of the literature has shown that many of the hazardous pollutantsin waste streams
can in principle be completely mineralized into innocuous species using semiconductor sols.
However, no commercial treatment planthas been built and none is in operation that is based
on this principle. Recently, Ollis and Turchi [37] discussed the engineering design aspects of
such photoreactors for waste treatment processes.
IV. PHOTOCATALYTIC DEGRADATION OF TOXIC SPECIES IN

MICELLAWMICROEMULSION MEDIA
Micelles and microemulsions havealso been observed to act as photocatalysts for the decom-
position of some organic pollutants. Micellar and microemulsion media are particularly attrac-
tive for the photocatalyticdegradation of nearly insoluble organic pollutants such as PCBs and
insecticides. The ability of these microheterogeneous media to solubilize the organics is an
added advantage in these processes. The photochemical degradation of such organic species
catalyzed by the surfactant-generated micelles or microemulsion medium has been observed.
Thus, micellar mediamay catalyze photochemical decompositionof a few very important pol-
lutants on the EPA priority list. The remainder of this section will review the available data on
microheterogeneous micellar media.
A. Micellar and Microemulsion Media

Surfactants are the most common surface-activeagents, and their use is varied and vast in in-
dustrial as well as consumer markets. Surfactantsare amphiphilic molecules witha hydropho-
bic tail attachedto hydrophilic head group. In aqueoussolutions, above a critical concentration
(called the “critical micellar concentration,” cmc), a surfactant dynamicallyassociates to form
large molecular aggregatesof colloidal dimensions termed micelles. Abovethe cmc, there ex-
ists a dynamic equilibrium betweenthe monomers and the micelles. Each micelleis composed
of a certain number of surfactants molecules(the aggregation number) that dictates thegeneral
size and geometryof the particular micellar system. Thestructure of a normal micellar system
is such that the hydrophobic tails are all directed away from the aqueous phase and toward the
center of the micelle, forming the core. The hydophilic head groupsare directed toward andin
contact with the aqueous solution phase, thus formingthe polar surface. The nature of the hy-
drophilic moietydetermines whether the micellar systemcan be classified as anionic, cationic,
zwitterionic, or nonionic. Extensive compilations of the preparation, properties, and critical
micellar parametersof these classes of surfactants have been published, andone should consult
them for further details [17].
The charge distribution at the surface of the micelle playsa dominant role in the behavior of
the micellar system.A two-dimensional schematic representationof a spherical, ionic micellar
Photocatalytic 373
Degradation
system is shown in Figure5 [47]. The structure is one in which the hydrophilic head groupsare
directed toward and in contact with the aqueous phase and the hydrophobic tails are directed
away from the water phase, forminga central nonpolar core. In the Stern layer, the drop in the
electric potential is very sharp, while in the Guoy-Chapman layer it is rather gradual.
Solubilizing power is the most useful and practically important property of micellar sys-
tems. Solubilization is a dynamic equilibrium process and depends on the temperature, surfac-
tant concentration, the nature of the solute, and the type of micellar system. Thereare several
possible sites for solubilization in a micellar system, and the site occupied by the solubilizate
depends onthe nature of both the soluteand the micelle. In a normal micelle, a nonpolar solute
may be located nearthe center of the hydrophobic core. An amphipathic solute may be oriented
in the micelle so that the hydrophilic moiety is either near to or far from the Stem layer. Ionic
solutes may be adsorbed on the polar micellar surface.
Another important feature of micellar systems is their ability to serve as a novel reaction
medium in which the rates, equilibrium position, products, and even stereochemistry may be
affected. They caneither inhibit or accelerate the rates of chemical reactions as well as shift the
mHydrophoblcTall, 0 Head GWP, f CounterIon
Figure 5 A two-dimensional representation of an ionic spherical micelle.

position of the reaction equilibrium depending on the nature of the reaction and the type of
micellar system. These effects are the consequence of solubilization and are attributed to the
balance of the hydrophobic and electrostatic interactions occurring between the micellar system
and the reactants.
Microemulsions are similar to micellar systems. A simplistic description of them is that
microemulsions are swollen micelles. A common microemulsion is obtained by proper process-
ing of water, surfactant, another hydrocarbon, and a cosurfactant. One significant difference
between the two is the average size. While ordinary micelles are about 2-3 nm in size, oil-
in-water microemulsions have an average size in the range of nm. As a consequence, the
20-40
solubilizing capacity of microemulsions is far greater than that of micelles. Their structural
characteristics are very similar to those of micelles.
In summary, micellesand microemulsions affect the redox equilibrium concentrations and
solubilize very many sparingly soluble organic pollutants. This makes them attractive photo-
catalysts in the photochemical degradation of toxic species that are not easily brought so- into
lution in aqueous media. Like the semiconductor sols, micellar and microemulsion systemsare
generally optically transparent.
B. Photocatalytic Studies in MicelladMicroemulsion Media

Though extensive investigations of micellar and microemulsion systems have been reported,
photochemical degradation studiesof toxic pollutantsare limited. The presence of the micellar
or microemulsion medium alters the photochemical reactionsof a species from its behavior in
a homogeneous medium. A comprehensive account of the photochemical processes in micellar
and microemulsion media is given in the book edited by Kalyanasundarum [48].
Though micellar media offer several unique advantages for the photochemical decompo-
sition of nearly water insoluble organic toxic species (insecticides, pesticides, pentachlorophe-
nols,etc.),photocatalytic or photochemicaldegradationstudiesofhazardouswastesin
micellar media are very limited. Shukla et al. [49] recently reported the resultsof their inves-
tigation of photodegradation of pentachlorophenol in sodium didecylsulfate (SDS) and cetyl
trimethylammonium bromide (CTAB) micelles and microemulsions. The micellar solutions
consisted of 0.1 M solutions of either SDS or CTAB. The microemulsions were prepared by
mixing the surfactants, mineral oil, and pentanol in appropriate amounts (4.2 wt % mineral oil
+ 26.2% pentanol + 9.2% SDS + water; 4.0% mineraloil + 16.0% pentanol + 28.00%
+
CTAB water). An alkaline solution of pentachlorophenol (PCP;0.5 n M ) was mixed with the
micellar solutionor microemulsion, and the resulting mixture was illuminated withUV a light
source. The concentration of the PCP in the solution system was monitored spectrometrically.
The details are presented elsewhere [49]. The results are presented in the Table 4. The photo-
degradation rates are relatively slow comparedto the rates shown in Table4 for the photocat-
alytic degradationat the surfaceof the semiconductor sols. But the results indicatethe potential
of these media where the toxic substances are water-insoluble. Pellizzetti et al. [46] reported
complete mineralization of nonylphenol ethoxylated surfactants.
V. CONCLUSIONS
Photocatalytic degradation of toxicspecies in waste streamsis the best alternative processing
method for better management of hazardous industrial wastes. The results of many investiga-
of hazardous species (in-
tions have demonstrated the feasibility of mineralization of a number
cludingseveralspecies on the EPA prioritypollutantslist)intoenvironmentallybenign
products using microheterogeneous media, especially the semiconductor slurries. Thus, a sci-
Table 4 Photodegradation of PCP in Micellar Media

dPercent Medium (hr)
DS 0.1 M
72 micelle
0.1 M CTAB 56
23
CTAB microemulsion 12
CTAB 4 microemulsion* 35
~~ ~~~
"100-W UV light source. All the other results were obtained using a 4-W UV lamp.
Source: Shukla [50].
entific basis for the photocatalytic degradation ofmanytoxic species inhazardouswaste

streams has been established. Having established feasibility, development of these treatment
processes can now be addressed. The solubilization properties of micellar systems for nearly
insoluble organic toxic species offersa distance advantage for further studies.
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NewYork,1990.
2. ProceedingsofHMCSouth1992ConferencesponsoredbyHMCRI, Feb. 22-28,1992,New
Orleans.
3. Proceedings of the National Research and Development Conference on Control of Hazardous Ma-
terials, Feb. 20-21, 1991, Anaheim, Calif.
4. Benested, C., Hagen, I., Jebens, A., Oehme, M., and Ramdahl, T., Waste Manage. Res., 8, 193
(1990).
5. Cesareo, D., de Domenico A., Marchini, S., Passerini, L., and Tosato. M. L., in Homogeneous
and Heterogeneous Photocatalysis (E.Pelizettia and N. Serpone, eds.), D. Reidel, Amsterdam,
1986, pp. 593-627.
6. Ku, Y., and Ho, S . C., Environ. Prog., 9, 218 (1990).
7. Ollis, D. F., Pelizzetti, E., and Serpone, N.,in Photocatalysis: Fundamentals andApp1ication.s(N.
Serpone and E. Pelizzetti, eds.), Wiley, New York, 1989, Chapter 18, pp. 603-637.
8. Bhakta, D., Shukla, S. S., Chandrasekharaiah, M. S., and Margrave, J. L., Environ. Sci. Tech-
nol., 26, 625 (1992).
9. Ollis, D. F.,J. Catal., 97, 564 (1986).
10. Gratzel. M. (ed.), Energy Resources Through Photochemistry and Catalysis, Academic, New York,
1983.
11. Schiavello,M. (ed.), Photoelectrochemistry, Photocatalysis and Photoreactors, D. Reidel,
Dordrecht, The Netherlands, 1985.
12. Photocatalysis: Fundamentals and Applications,Serpone, N., and Pelizzetti E. (eds.), Wiley, New
York,1989.
13. Rabek,J.F. (4.). Photochemistry and Photophysics, Vols. I-IV, CRC Press, Boca Raton, Ha.,
1991 .
14. Schiavello, M,, and Sclafani, A., in Photocatalysis: Fundamentals and Applications (N. Serpone
and E. Pelizzetti, eds.), Wiley, New York, 1989, pp. 159-173.
15. Kisch, H., in Photocatalysis: Fundamentalsand Applications (N. Serpone andE. Pelizzetti, &S.),
Wiley.NewYork,1989,pp.1-8.
16. Fendler, J. H., Chem. Rev., 87, 877 (1987).
17. Hinze, W. L., in Solution Chemistry of Surfacmnts, Vol. 1 (K. L. Mittatl, d.),Plenum, New York,
1979, pp. 79-127.
18. Gratzel, M., Heterogeneous Photochemical Electroni'Fansfr, CRC Press, Boca Raton, Ha., 1989.
19. Kalyanaundarum, K., Gratzel. M., and Pelizzetti, E., Coord. Chem. Rev., 69, 57 (1986).
20. Henglein, A., Pure Appl. Chem., 56, 1215 (1984).
21. St. Johno. M. R., Furgala, A. J., and Sommells, A. F., J. Phys. Chem., 87, 801 (1983).
22. Tangnay,J.F.,Suib, S. L., and Coughlin, R. W.,J. Catal., 117, 335 (1989).
23. Maser,, J., and Gratzel, M., Helv. Chim. Acra, 65, 1436 (1982).
24. Duonghong, D., Borgarello, E., and Gratzel, M., J. Am. Chem. Soc., 103,4685 (1981).
25. Fox, M. A.,Acc. Chem. Res., 16, 314 (1983).
26. Bard, A. J., J. Phys. Chem., 86, 172 (1982).
27. Frank, S. W., and Bard, A. J., J. Am. Chem. Soc., 99, 303 (1977).
28. Frank, S. W., and Bard, A. J., J. Phys. Chem., 81, 1848 (1977).
29. Krautler, B., and Bard, A. J., J. Am. Chem. Soc.,100, 2239, 4317, 5985 (1978).
30. Ward, M. D., White, J. R., and Bard, A. J., J. Am. Chem. Soc., 105, 27 (1983).
31. Child, L. l?, and Ollis, D. F., J. Caml., 66, 393 (1980).
32. Pruden,A. L., and D. F. Ollis, Environ. Sci. Technol., 17, 628 (1983).
33. Hsiao, C. Y., Lee, C. L., and Ollis, D. F.,J. Caral., 82, (1983).
34. Pruden, A. L., and Ollis. D. F., J. Caral., 82, 404 (1983).
35. Ollis, D. F., Hsiao, C. H., Budiman, L., and Lee, C., J. Catalysis, 88, 89 (1984).
36. Ollis, D. F., Environ. Sci. Technol., 19, 480 (1985).
37. Ollis, D. F., and Turchi, C., Environ. Prog., 9, 229 (1990).
38. Finklea, H. 0..J. Chem. Educ., 6 0 , 325 (1983).
39. Turner, J. A., J. Chem. Educ., 6 0 , 327 (1983).
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41. Oliver, B. J., Cosgrove, E. G . . and Carey, J. H., Environ. Sci. Technol., 13, 1075 (1979).
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17
Photocatalytic Oxidation
of Organic Contaminants
Allen l? Davis
University of Maryland
College Park, Maryland
1. INTRODUCTION
Contamination from organic compounds represents a significant problem bothin water supplies
and in industrial andother hazardous wastewaters. Studies conducted by the U.S.Environmen-
tal Protection Agency (EPA) between1977 and 1982 found that 21% of the approximately IO00
drinking water systems sampled contained detectable levels of one or more volatileor synthetic
organic compounds [l]. Many of these substances are suspected of being carcinogenic, and
their occurrence in potable water causes serious concern. Additionally, organic compounds
make up the majority of substances onthe EPA priority pollutants list and includechlorinated
solvents, petroleum products, phenols, and pesticides.
The application of a single process to treat contaminated waters is not possible owing to
variations in water characteristics and the physical and chemicalproperties of the organic con-
taminants. The effectiveness of remediation processes depends upon such factors as organic
volatility and solubility, pH, presence ofother compounds, required water quality, and volume
treated. Consequently, treatment of organic-contaminated waters must be specifically tailored
to the type and degree of contamination present.
Currently several processesare being used for the decontamination of waters tainted with
volatile or synthetic organic compounds. A comparison of organic removal methods was sum-
marized by Clark et al. [2]. A list of some of the various processes and an indication of the
effectiveness of the treatment for some selected compounds are presented in Table 1.
A processcommonlyused for the removal of volatileorganiccontaminants is air-
stripping, whereby air and the contaminated water are mixed,usuallyin a countercurrent
fashion. In this process, the volatile organic compounds are transferred from the aqueous to
the gas (air) phase. Consequently, the pollutants must be sufficiently volatile for successful
treatment. The efficiency of the process is controlled by mass transfer rates between the two
phases as well as the air/water equilibrium partitioning, quantified by the Henry’s law con-
stant. Due to stringent air pollution standards, most air-stripping processes currently require
377
Davis
Table 1 Summary of the Performance for Organic Decontamination Technologies

Removal efficiency"
Granular
Ozone Packed
activated
oxidation tower
bon compounds Organic aeration
ppm)
(2-6
vocs
Alkanes
Carbon tetrachloride ++ ++ -
1,2-Dichloroethane ++ ++ -
1,1,1 -Trichloroethane ++ ++ -
1.2-Dichloropropane ++ ++ -
Ethylene dibromide ++ ++ -
Dibromochloropropane ++ + -
Alkenes
Vinyl chloride + ++ ++
1, I-Dichloroethylene ++ ++ ++
cis-l ,2-Dichloroethylene ++ ++ ++
trum-l ,2-Dichloroethylene ++ ++ ++
Trichloroethylene ++ ++ +
Aromatics
Benzene ++++ ++
Toluene ++ ++ ++
Xylenes ++ ++ ++
Ethylbenzene ++ ++ ++
Chlorobenzene ++ ++ +
o-Dichlorobenzene ++ ++ +
p-Dichlorobenzene ++ ++ +
Styrene ++ ++ ++
Pesticides
Pentachlorophenol ++ - ++
2,4-D ++ - +
Alachlor ++ ++ ++
Aldicarb NA - NA
Carbofuran ++ - ++
Lindane ++ - -
Toxaphene ++ ++ NA
Heptachlor ++ ++ +
Chlordane ++ - NA
2,4,5-TP ++ NA +
Methoxychlor NA ++ NA
Other
Acrylamide NA - NA
Epichlorohydrin NA - -
PCBs ++ ++ NA
+
'++ = good, = fair; - = poor, NA = data not available.
Source: Clark et al. [2]
PC0 of Organic
minants 379
subsequent treatment of the off-gas. Vapor-phase carbon adsorption or a catalytic oxidation

process is commonly used.
Activated carbon adsorption is the other conventionally used remediation process. The ef-
ficiency of adsorption depends upon the physicochemical characteristics of the target organics
as well as the water chemistry, e.g., pH. Complications can result from various aspects of com-
petitive adsorption, either from multiple contaminants or with naturally occurring dissolved
organic matter.In addition, the costsof disposal/regeneration of spent carbon can be exorbitant,
and used carbon may be classified as a hazardous waste.
Other treatment processes for organic contamination that may be employed under various
conditions include biological oxidation, chemical oxidation, and membrane processes.
Concerns of secondary contamination from air-stripping off-gas and spent carbon and the
difficulties encountered in treating many recalcitrant substances have evoked interest in ad-
vanced oxidation processes (AOPs). Such processes involve supplementation of traditional ox-
idants with additional stimuli such as high temperature or UV light to create highly reactive
radical species to oxidize difficult-to-treat substances suchas saturated organic molecules and
pesticides. Examples of AOP include ozone-H202-UV combination systems, wet air oxida-
tion, and photocatalytic oxidation. The increasing concern over water contamination and the
need for ultimate decontaminationas opposed to phase transfer create an impetus and interest
in examining these novel treatment operations.
Recently, there has been a considerable amount of research and development examining the
phenomenonofsemiconductorphotocatalyticoxidation ( K O ) forthedecontaminationof
tainted waters. Most of the work with PC0 has been oriented toward low organic concentra-
tions (parts per billion or low parts per million) where oxidation processes can be competitive
with other organic treatment technologies. Compounds such as phenols, benzenes, and chlo-
rinated solvents, as well as PCBs (polychlorinated biphenyls), pesticides, and dioxins,are ox-
idized to simple, environmentally acceptable products such as carbon dioxide and chloride.
The majority of these investigations have been based on oxidizing organic solvents that are
present in contaminated waters; a full-scale PC0 process for treating solvent-contaminated
groundwater has shown promising preliminary results[3].
A. OrganicOxidation
The oxidationoforganiccompounds,althoughthermodynamicallyfavorable, is normally
kinetically limited and thus very slow. Processes that use strong oxidizing agentsare energy-
intensiveandusuallyhaveprohibitivecostsforwastetreatment.Someofthetradi-
tional compounds used for oxidation are oxygen, chlorine, ozone, permanganate, chlorine
dioxide, and hydrogen peroxide. Novel processes, such as the supplementation of radical-
initiating ultraviolet light, have been found to increase the reactivity of some of these common
oxidizing agents.
Oxidation is defined as the loss of electrons by a substance; concurrently, the oxidizing
agent is reduced by the electrons gained. Organic chemical oxidation typically occurs via ad-
dition or substitution.
1. Addition is the incorporation of the oxidant into the chemical structure of the organic
compound. An exampleofoxidativeadditionischlorine or ozoneaddingacrossthe
double bond of an olefin. Compounds with a high electron density (such as those with
double or triple bonds or an aromatic ring) are susceptible to addition of electrophilic
oxidants. Furthermore, the unsaturation of the organic molecule easily allows oxidant
addition.Thisdifferenceinreactivitybetweensaturatedandunsaturatedorganics is
380 Davis
noted in Table 1 by the promising use of ozone in oxidizing alkenes butits limited effec-
tiveness in reaction with alkanes.
2. Substitution is the replacement of a reduced atom or group in the organic substanceby all
or a portion of the oxidizer. For example, chlorophenol is formedby substitution of a hy-
drogen in phenol upon reaction with chlorine. Similarly, hydroxyl radical attack ona phe-
nolic hydrogen atom will result in the production of a dihydroxybenzene.
Recently there has been a renewal of interest inoxidative processes as a means of treating
hazardous organic materials. Oxidation hasthe potential to transform organic contaminantsto
environmentally acceptable forms such as carbon dioxide andchloride. Thus concern oversec-
ondary waste production, such as solid or gas-phase residuals, is relieved. The challenges with
chemical oxidation are to ensure complete oxidation of hazardous substances to compounds
that do not exhibit harmful or toxic characteristics and to enhance reaction conditions so that
this transformation is accomplished in an economically feasible manner.
B. PhotocatalyticActivation
two allowable elec-
As a result of solid-state quantum effects, semiconductor materials possess
tron energy bands. The lower energy region is the valence band; electrons in this energy band
are binding electrons and are somewhat restricted in movement. The higher region is the con-
duction band. These electrons, to a first approximation, are free to move throughout the solid
and produce conductivity similar to that of metals. Between these two regions is a forbidden
zone, or bandgap.
Photoexcitation in a semiconductor occurs as the absorption of radiation of energy equal
to, or greater than, the bandgap energyexcites an electron (e-) into the conduction bandof the
solid. There is, correspondingly, an electron vacancy or hole (h’) that remains in the valence
4
band (Figure 1).
hv
Semiconductor ”* e- + h+
Reduced
Product
Ti4 Conduction Band
-0.3
Oxidized
Reactant
Potential
(V)
Recombination
Reduced
2.1 Reactant
Ti02Valence Band
Oxidized
Roduct
Figure 1 Creation of electron-hole pairs in illuminated semiconductors, and subsequentphotocata-

lytic redox reactions.
P C 0 of Organic Contaminants 381
Table 2 Some Common Semiconductors, Their Bandgap Energy (pH 0),

and Corresponding Excitation Wavelength
Semiconductor Wavelength
Bandgap (eV) (nm)
TiO, 3.0-3.2 413-388
ZnO 3.2 388
ZnS 3.7 335
CdS 2.4 516
Fe203 2.3 539
WO3 2.8 443
Source: Maruska and Ghosh [4]; Sakata and Kawai [5]
These holes, having an affinity for electrons, are very strong oxidizing agents. The number of
electron-hole pairs is dependent on the intensity of the incident light and the material's elec-
tronic characteristics that prevent them from recombining and releasing the absorbed energy.
The electron is free to move throughout the solid in the nearly unoccupied conduction band.
Similarly, the hole can migrate by a valence band electron filling the vacancy, leaving behind
another hole in the previous position. The bandgap energy and corresponding wavelength re-
quired for excitation for some common semiconductorsare given in Table 2.
The semiconductor potentials for the valence band and conduction band are significantly
different. This difference avoids rapid recombinationof the e"h+ pairs. The band potentials
are a function of pH and decrease by 0.059 V per pH unit increase as predicted by the Nernst
equation [6,7].
The holes in the semiconductor solidare attracted to the oxide/sulfide surface, where they
oxidize an adsorbed water molecule or hydroxide ion.
h+ + HzO(ads) + OH. + H+
h+ + OH-(ads) + OH.
Hydroxyl radicals are very reactive neutral species with an unpaired electron. They ieact rap-
idly and nonselectively in the oxidation of organic compounds and are the common oxidizers
in AOP and high-pH ozone systems.
Reaction (2) is likely to occurfor two reasons. Oneis that large quantities of OH- and H20
groups are available as adsorbates, and the chances of holes reacting withthese groups on the
semiconductor surface are high. The second reason is that for several semiconductors the ox-
idation potentials of these reactions are above (more negative than) the potential forthe valance
band over the entire pH range. Reaction (2a) is favored at low pH and reaction (2b) at higher
pH values [7].
II. ORGANICPHOTOCATALYTICOXIDATION
Titanium dioxide (Ti0,) is the semiconductor material with the most promise for the photo-
catalytic treatment of hazardous wastewaters.TiO, is an active photocatalyst and is extremely
stable, i.e., it does not dissolve or corrode under photoexcitation.
Barbeni et al. [8] reported the photodegradation of several chlorinated benzenes and phe-
nols, 3,3'-dichlorobiphenyl, and2,7-dichlorodibenzo-p-dioxinusing illuminatedTiO,. A com-
parison among several semiconductors indicated that TiO, produced a faster rate than ZnO,
CdS, or WO,. The photocatalyticoxidation (PCO) of oxalic acid was also much more efficient
using TiO, than other semiconductors such as ZnO, WO,, and F%O, [9], as was the K O of
382 Davis
polychlorinated dioxins andPCBs [lo]. Oxidation of dioxin is much slower than that of simple
compounds, apparently because of the large size of the molecule.
Consequently, PC0 processes entail the addition of TiO, particles or powder to contam-
inated waters with concurrent exposure to UV radiation. An advantage of photocatalytic oxi-
dation over ozone-H202-UV processes is the higher wavelength (lower energy) requirement of
photocatalysis. TiO, photoactivation requireslight at wavelengths less than about 380nm (Ta-
ble 2), whereas ozone-H2O2-UV systems operate at approximately 254 nm. Thus PC0 pro-
vides the possibility of savings in both capital (lamps) and operating (power) costs.
A. Titanium Dioxide Surface Reactions

Titanium dioxide is rapidly hydrated in aqueous solution due to the partially uncoordinated
states of its surface titanium and oxygen atoms. The amphoteric nature of the hydrated TiO,
surface results in pH-dependent equilibrium between protonated and deprotonated hydrous sur-
face species [l l],
I I 1
I - T i -OH,* -H' I - T i -OH -H' I - T i -0'
I "-)
I "-> I
I-0-H,, I-0-H m-0-
I <"- l ("-
l
I - T i -OH,' +H' I - T i -OH +H' I - T i -0'
I I I
(a) (b) (c)
where Irepresents thebulk solid. The pH at which the overall TiO, surfaceis neutrally charged
is termed the zero point of charge or pH,. Reported values of the pHzpcfor TiO, range from
3.5 to 6.7 depending on purity and crystal structure [12-141. TiO, can be viewed as a solid
diprotic acid having two acidity constants. p&, represents the equilibrium between (a) and (b)
of reactions (3). Similarly, the equilibrium between 3(b) and 3(c)is denoted bypK,. The
theoretical maximum surface coverageof TiO2 with surface hydroxo groups is 5-15 OH groups
per square nanometer [1 l].
As discussed previously, thermodynamically permissible traps for valence band holes in
aqueous TiO, systems include adsorbed water molecules or hydroxide ions, which react with
the holes to produce hydroxyl radicals [reaction (2)]. Hydroxyl radicals have been detectedby
electron spin resonance(ESR) in illuminated aqueous TiO, suspensions [15,16] and are widely
believed to be the most important oxidizingspecies in these systems. Oxidizable species such
as hydrocarbons (RH)or other organic contaminantsin the solution subsequently react with the
hydroxyl radicals [171.
-H.
RH + OH. "* ROH
Continued radical attack will result in the complete oxidation of the organic compound via
pathways common to all hydroxyl radical oxidations.
It has also been proposed [l81 that adsorbed organic species may react with valence band
holes at the TiO, surface, resultingin the formation of an organic radical. Despitethe favorable
thermodynamics of such a reaction, however, there is strong evidence that H,O and OH-, and
not organic compounds, are the principal hole traps in TiO, photocatalytic systems. For ex-
ample, Cunningham -and Srijaranai [l91 found that substitution of deuterium (D) in C-H and
0-Hbonds in isopropanol and cyclobutanol did not affect the rate of oxidation of these com-
PC0 of Organic
aminants 383
pounds by TiO, photocatalysis. However, they found that use of 4 0 instead of H20 as the
solvent in the same system significantly decreased the initial oxidation rate of the two unla-
beled alcohols, suggesting that the rate-determining step in TiO, photocatalytic oxidation in-
volves H 2 0 and OH- and not organic species.
The electron migrates to the TiO, surface, where it reduces surface Ti(1V) ions.
+
Ti(IV)sufi e- ”* Ti(III)sud (5)
Subsequently, oxygenor another oxidizing agent reacts with the reduced metal center, trapping
conduction band electrons and producing the superoxide radical anion (0,”) [20-221.
OZ(ads) + Ti(II&,,fi + Oy-(ads) + Ti(IV)sufi (6)

This frees the flow of electrons (and therefore that of the holes) and inhibits the e--h+ re-
combination process. Hydrogen peroxide (H202) is consequently formed through various rad-
ical reactions [20,22,23].
Cleavage of H20pmay also result in the formation of OH. radicals through several reactions
[6,20,22,24].
H202 + Ti(III)sufi-+ Ti(IV)sufi+ OH. + OH-(Fenton-type)

+
H202 9 . - ”* OH. + OH- + 0 2 (Haber-Weiss)
H2025 2 OH. (photodissociation)
However, several studies have suggested that these routes of OH- formation for organic oxi-
dation are secondary to reactions (2a) and (2b) [20,24,25].
Within the last few years, interest in PC0 has exploded since a wide variety of organics
can be both nonselectively and completely oxidized using this process. A representative (but
not exhaustive)listing of the organic pollutants successfully treated
by photocatalytic oxidation
is given in Table 3.
B. Oxidation of Organic Compounds

The complete degradation of chloroform (CHCl,) to carbon dioxide, water, and chloride ions
has been demonstratedby Pruden and Ollis [271 using TiO,. A decrease in chloroform, along
with formation of carbon dioxide and chloride, was found according to the stoichiometry
CHC13 + H20 + 0.5 0 2 ”* CO, + 3 HCl (9)
Continued work by the same researchers has examined the mineralization of several simple
chlorocarbon solvents andacids [26,28,31,32]; complete degradation of these reactants to in-
organic products was observed.
However, the reaction to these products is not direct and involves several steps. Mineral-
ization of two organophosphorus insecticides to CO,, Cl-, P O
:
-
, and H+ was accomplished
at rates three to four times slower than the disappearance of the parent compounds, indicat-
ing the formation and subsequent destruction of intermediate substances [ 4 6 ] . Similarly, CO2
384 Davis
Table 3 organic Contaminants That Have Been Successfully Treated by Photocatalytic Oxidation
Using TiOz
Compounds Reference
Solvents
Chloroform. dichloromethane Hsiao et al.. [26]
Pruden and Ollis [27]
Trichloroethylene hvden and Ollis [28]
Benzene, perchloroethylene Turchi and Ollis [29]
Methyl vinyl ketone Muneer et al. [30]
Perchloroethylene, dichloroethane, mono-, di-, and triacetic acid Ollis et al. [31]
Trichloroethylene, trichloromethane Ahmead and Ollis [32]
Phenols
Phenol Okamoto et al. [24]
Augugliaro et al. [33]
Tseng and Huang [34]
Pentachlorophenol Barbeni et al. [35]
Fluorinated phenols Minero et al. [36]
4Chlorophenol Barbeni et al. [37]
Chlorinated phenols AI-Ekabi and Serpone [211
Tseng and Huang [38]
2-Chlorophenol, 3-chlorophenol D’Oliveira et al. [39]
2,4-Dichlorophenol Ku and Hsieh [40]
Barbeni et al. [41]
Trichlorophenoxyacetic acid, 2,4,5-trichlorophenol AI-Ekabi et al. [421
0 - , m-,and p-Cresols Terzian et al. [43]
Pesticides
Atrazine, simazine, prometryn Pelizzetti et al. [M]
Atrazine, simazine, propazine Pelizzetti et al. [45]
Dimethyl-2,2-dichlorovinylphosphate Harada et al. [46]
PCBs and Dioxins
PCBs and dioxins Pelizzetti et al. [lo]
Phenols, benzene, biphenyl, dioxin Barbeni et al. [8]
3 ,4-Dichlorobiphenyl Tunesi and Anderson [47]
Other organic compounds
Benzoic and salicylic acids, naphthalene Matthews [48]
Formic acid Bideau et al. [49]
Bideau et al. [50]
Acetic acid Bideau et al. [S11
Oxalic acid Herrmann et al. [9]
Chloral hydrate Tanaka et al. [52]
Azo dyes Hustert and Zepp [53]
Sodium dodecylbenzene sulfonate Hidaka et al. [54]
Nonylphenol ethoxylated surfactants Pelizzetti et al. [ S ]
Methylene blue, salicylic acid Matthews [S61
12 Nitrogen-containing organic compounds Low et al. 1571
4 Ring nitrogenous compounds Low et al. [58]
21 Organic compounds Matthews [S91
22 Solvents Matthews [60]
11 Organic compounds Matthews [61]
23 Organic compounds Sabin et al. [62]
aminants
PC0 of Organic 385
evolution was much slower than the photocatalytic disappearance of methylene blue [56] and
methyl vinyl ketone [30]. Matthews [59] noted that 21 different substances, including some
aromatic hydrocarbons, are degraded completely to COz. The general reaction presented is
C,H,X+702+6CO2+HX+2H20 (10)
First-order Pc0 rate constants for 23 organic compounds were evaluated by Sabin et al.
[62]. Their data show several trends; for example, alkanes are more difficult to treat than
alkenes or aromatics, and chlorine-substituted compounds have lower reaction rates. Both
of these trends are typical for organic oxidation processes.Somehighly fluorinated com-
pounds were very resistantto degradation. Meanwhile, Matthews [61] noted that Pc0 rate con-
stants for 10 different compounds (organic acids, phenols, alcohols, and nitrobenzene) were
quite similar.
C. Kinetics
The initial photocatalytic reaction rate follows a Langmuir-Hinshelwood type of relationship
with respect to initial organic concentration [9,26-29,31,33,39,42,48,49,59,6,63-651:
NCO
r, = rate = 1 +KC,,
where C, is the initial concentration of the target organic compound. The constants k and K
represent collections of oxidation, recombination, and possiblyadsorption terms. This expres-
sion describes a first-order reaction at low substrate concentrations, with a transition to a rate
independent of organic concentration at high substrate loadings (Figure 2).The rate expression
can be linearized by reciprocation, resulting in
thus describing a linear plot for llr, versus K,, (Figure 2, curve B). Secondary organic sub-
stances, formed via the oxidation process, complete with the original substrate for the oxidant
(hydroxyl radicals), so later reaction rates may be slower than the initial rate.
The effects of several operational and solution parameters on the PC0 reaction rate have
been evaluated. In numerous cases, effects of these parameters are compared using rate con-
stants (koh) derived from first-order plotsthat are linear over a short range. Others have made
comparisons among various reaction conditions using initial rates (r,), where a linear decrease
in concentration is measured over a brief time period.
A Langmuir-Hinshelwooddependenceonoxygen concentration has beendetermined
[33,63]:
k' K1[OJ
Rate =
+
1 K1[02]
Oxygen is necessary to complete the oxidation reaction by reacting with the photoproduced
electrons [surficial Ti(III)] to maintain electroneutrality via reaction (6).
The incident light intensity controlselectrodhole production and thusthe hydroxyl radical
formation rate. For example, a direct linear relationship between light intensity and PC0 rate
has been found for rn-cresol [43]. However, a transition from first-order to 1/2-order is found
at high light intensities [63,66]. This is apparently due to an increase in hydroxyl radical re-
combination,
386 Davis
0.2 1 2
C rnrnoll"
o/
Figure 2 (A)Initial 3-chlorophenol concentration versus initial Pc0 rate. (B) VC, versus W., (Re-
printed with permission from D'Oliveira et al. [39]. Copyright 1990 American Chemical Society.)
yielding a recombination rate proportional to [OH.]'". This consequently producesan overall

organic oxidation rate proportional to the square root of light intensity [67].
Quantum yield is a measure of the efficiency of light utilization and is defined as the ratio
of the number of photons entering into a photochemical reactionto the number of photons a p
plied. The former parameter is usually evaluated by the conversion of the substrate, the latter
by measurement of the incident light characteristics.
The degradation of 3,4-dichlorobiphenyl over illuminated Ti02 was examined by lbnesi
and Anderson [47]. ' b o light intensities were evaluated; increasesin light intensity result in a
faster removal rate but a smaller quantum yield, due to inefficient light utilization and in-
creased radical recombination, as discussed above. Intermediate products isolated include lin-
ear andbranchedhydrocarbonsandsomephenols.Quantum yields rangedfrom 7.4 X to
l .6 X IOF3. PC0 quantum yields of 0.06 for acetic acid [51] and 0.022 for salicylic acid [48]
have also been reported.
Since key steps to TiO, photocatalytic oxidation occur at the TiO, surface [i.e., reactions
(2) and (6)], thereaction rate would be expected to increase linearly with availablecatalyst. At
dilute TiO, concentrations, such a relationship is observed. However, above certain concen-
trations, the rate of oxidation does not increase [34,36,63], as shown in Figure 3, and may
decrease with further increasing TiO, concentration. For example, Matthews [20] found that
the rate of salicylate formation in the oxidation of sodium benzoate increased with the quantity
of titanium dioxide upto 2 g/L but decreased slightly at higher loading. Augugliaro et al. [33]
observed the same phenomenon with a maximum phenol PC0 rate at 1 g/L TiO,. Matthews
PC0 of Organic Contaminants 387
1 4-f luorophenol I
Figure 3 Dependence of kobs onphotocatalystconcentrationinthephotocatalyticoxidation of 4-

fluorophenol. The inset shows a linear reciprocation of a Langmuir-Hinshelwood expression. (Reprinted
with permission from Minero et al. [36]. Copyright 1991 American Chemical Society.)
[61], analyzing 4-chlorophenol degradation using Equation

(lla), found that k decreased while
K increased as TiO, loading varied from 0.2 to 2 @L.
These results are explained by the fact that above certain Ti02 concentrations, there is a
stoichiometric TiO, loading that is sufficient to use all available photons emitted at a given
intensity. Increasing the TiO, concentration above this level becomes inconsequential because
all available light is being utilized. In addition, other factors that contribute to the rate inde-
pendence on TiO, concentration include the reactor configuration, reflection, and solution
opacity, which may prohibit some of the light from activating available photocatalyst.
The effect of pH on PC0 reaction kinetics is still very much unresolved. Some typeof pH
dependence, although it is usually slight, is noted with almost every organic substrate. How-
ever, it has not been possible to draw any general conclusions with respect to pH about pho-
tocatalytic oxidationkinetics.Insome cases, there are discrepanciesabout the pHof the
maximum rate for the same organic compound. For example, the maximum rate for phenol
PC0 has been reported at pH 3 by Augugliaro et al. [33], at pH 4-5 by Okamoto et al. 1241,
and a pH 5-9 by Tseng and Huang [341.
The PC0 rates of some nonionic compounds, such as solvents, are affected by solution
pH. Matthews [65] found thatrates of CO2 production from benzene, nitrobenzene, and chlo-
roform [as quantified by the product kK using Equation (1l)] were faster at pH 4.5 than at pH
3.0. However, dioxin Pc0 was found to be more rapid under basic conditions [lo].
The effectof pH on the PC0 of dissociating organic acids is complicated by the speciation
changes of these compounds. In most cases, anionic organics are more reactive than the pro-
tonated molecularspecies, which is common for electrophilicoxidation. Oxidation of the pen-
tachlorophenolate ion at high pH proceeds faster than that of molecular pentachlorophenolat
pH 3 [35]. Similar results have been found for m-cresol [43] and 4-chlorophenol [37]. Palm-
isano et al. [68] studied the effect ofpH on the initial reaction rates of phenol and 2-, and
388 Davis
3-, and 4-nitrophenols.The highest photoactivity was foundtheinalkaline region. 3-Nitrophenol

photocatalytic oxidation was less pH-dependent than that of the 2- and 4-isomers. The PC0
rate of oxalic acid was maximumat pH 2.3 and decreasedat higher pH, apparently due to the
change in speciation from HC,O4- to C 2 0 2 - 191; however, acetic acid photocatalytic oxida-
tion is maximum at pH 3 [5 l]. The photocatalyticoxidation of three commercialazo dyes and
a model compound, 4-hydroxyazobenzene,was examined by Hustert and &pp [53]. Orange G
was oxidized much faster at pH 12 than at pH 7 , apparently due to the deprotonation of this
weak organic acid dye.
Mechanisms other than substrate speciation that may be responsible for pH dependencies
include surface hydrolysisof the TiO, (with subsequentchanges in the electrical double layer),
pH dependencies of any adsorption of products or reactants (O,, H20, OH-, or organic), and
pH dependencies of the reaction rates of specific organic substrates.For example, Kormannet
al. 1661 correlated photocatalytic oxidation rates as a function of pH with calculated surface
speciation for both trichloroacetate and chloroethylammoniumion adsorption onto TiO,.
Titanium dioxide has two common crystal structures, anatase and rutile. Several studies
have noted that rutile is not an active photocatalyst [24,33]. However, two of the three rutile
catalysts examined by Auguliam et al. [33] have specific surface areas significantly lower than
that of the anatase sample; thus a direct comparison may not be completely valid. Neverthe-
less, Sclafani et al. [69] noted an inactiverutile that has a specific surface arealarger (20 m2/g)
than that of an active anatase (14 m2/g). An active rutile photocatalyst was found by Davis et
al. [70]. Apparently the reactivity of rutile TiO, dependson the method of Ti02 synthesis [69].
The bandgap energy for rutile is 3.0 eV, as compared to 3.2 for anatase. Thus the oxidation-
reduction potentials are slightly less for the rutile phase and, thermodynamically, some reac-
tions may not be favored with rutile. Sclafani et al. [71] attributed PC0 activity differences
between anatase and rutile TiO, to the thermodynamics andkinetics of the reduction reactions.
Although crystal structure plays a role in the photocatalytic reactivityof Ti02, there are other
controlling parameters that must be considered when evaluating TiO2 from different sources.
In theory, a higher TiO, specific surface area will increase its photocatalytic activity due
to increased area for adsorptionof H,O and OH- and the corresponding subsequentgeneration
of OH. radicals [reaction (2)]. Supporting this assumption, Matthews [59] observed that the
degradation rate of 4-chlorophenol was much lower with an equal concentration of La Porte
TiO, (specific surface area = 9 m2/g) than with Degussa TiO,(50 m2/g), presumably because
of its much lower surface area.
On the other hand, this theory has not been found to be consistent in severalother studies.
Investigations by Cuendet and Gratzel [72] on pyruvate photocatalytic reactions found similar
rates for two TiO, samples with different specific surface areas (145 m2/g versus 50 m2/g).
Tanaka et al. [73] studiedthe degradation of trichloroethylene (TCE), methylchlorideacid, and
phenol on 12 commercially available TiOz samples. Thedegradation rates varied among TiO,
types, but there was no correlation with the specific surface area. The rates were found to be
dependent onthe crystallite size of the anatase form presentin the TiO, sample; the larger the
crystallite size, the faster the reaction rate. The two TiO, samples (with 100% anatase) in
which the fastest rates were observed had specific surface areas of 17.3 m2/g(Fujititan TP-2)
and 9.5 m2/g (Aldrich). Sclafani et al. [69] examined several commercial and synthetic types
of TiO, possessing a wide range of physical and chemical properties, such as differing crystal
structu~ and.~ specific surface areas; correspondingly,a wide range of PC0 rates was found.
There was no photocatalyst propertythat produced a correlation with respect to reaction rates.
Particle size may affect PC0 rates through an effect on the degree of electron/hole trap-
ping. As particle size increases, the distance that the electron-hole pair must diffuse through
the solid before reacting at the TiO, surface increases. This concurrently increases the proba-
PC0 of Organic Contaminants
Sampling Port
Magnetic
stirrer
. ,..
..
..
.. :
Temperature
Controlled
Reactor
TiO, suspension
1\\
L
Longwave
W Lamp
389
Figure 4 Qpical recirculating batch reactor used in photocatalytic oxidation kinetic studies.
bility that recombinationwill occur. Consequently, any decreased rate of PC0 for larger TiO,
particles may be due to the greater degree of electron-hole recombination. Davis et al. [70]
found that the photocatalytic activity of a specific TiO, catalyst depends onthe synthesis (manu-
facturer) of the TiO,, the crystal structure, and anypretreatment of the solid. No correlation was
found between particle size of the TiO, and initial PC0 rate of toluene.
Several investigatorshave reported onthe detrimental effect of chloride ions onPC0 rates
[26,31,33,38,66]. The presence of chloride significantly decreases organic oxidation rates,
possibly by scavenging an active radical species [74]:
Inhibition of the PC0 process by chloride is a serious concern becausechloride is formed dur-
ing the mineralizationof chlorocarbon compounds, many of which are found in contaminated
waters. Abdullah et al. [74] and Tseng and Huang [381 examined the effect of several other
anions on the PC0 rate of organic substrates. Phosphatesand sulfates decreased reactionrates,
apparently by adsorbing ontothe TiO,, resulting in the deactivation of some active sites; NO3-
and C104- had no effect on PC0 reaction rates.
Photocatalytic oxidationrates are decreased in the presence of bicarbonate ions. The pres-
ence of 500 mglL bicarbonate decreased TCErate constants by a factor of 2-5 in bench-scale
studies [75]. Bicarbonate ionsare well known as radical scavengers through work investigating
ozonation kinetics. Apparently the HC0,- acts in the same manner during K O , scavenging
hydroxyl radicals, thus preventing reaction with the target substrate.
Inmany instances PC0 kinetics have been investigated using recirculating systems in
which a mixed reactor feeds an isolated plug-flow photoreactor, similar to that in Figure 4. In
this manner, sampling and suspension chemistry monitoring and adjustmentsare performed in
the mixed reactor, away from the photoreactor. Studies have shown that PC0 first-order rate
constants (kobs)are a function of flow rate (FR)through these reactors andare described by the
equation [56]
k* FR
+
1 ~ F R
At small flow rates, an increase in flow results in a higher reaction rate constant; the rate
becomes independent of flow at higher flow rates. Similar results were found by Al-Ekabi
390 Davis
and Serpone [21] in an examination of flow through a coiled glass tube withan internal
coating of TiO,.
Minero et al. [36] noted that the PC0 rates of five different fluorophenols and difluorophe-
nols were very similar. Analogously, the rates of phenol, the three chlorophenol isomers, five
different dichlorophenols, and 2,4,6-trichlorophenol were all within about 30% [38]. Both of
these investigationsillustrate the nonselectivityof PC0 systems. However, in contrast, Tenian
et al. [43] found that the PC0 rate of m-cresol was about 2 112 times slower thanthat of either
0- or p-cresol under identical conditions.
Competitive interactions among 4-chlorophenol, 2,4-dichlorophenol, and 2,4,5-trichloro-
phenol were examined by Al-Ekabi et al. [42]. The PC0 rates of all three compounds were
slowed in a ternary mixture. However, the sum of the three individual rates was equal to that
for PC0 of a single compound, indicating thata fixed amount of oxidant was being produced
by the illuminated TiO, system.
Absolute comparisonof organic PC0 rates among various investigators is not possible due
to variations in substrate and catalyst loading, light intensity, and reactor configurations. Some
have based rates on target organic disappearance, whileothers have monitored the production
of CO, or Cl-. Batch and flow reactors using suspendedas well as immobilized photocatalyst
have been examined. Discussionson the effect of reactor dynamics onPC0 rates are presented
by Davis and Hao [76] and " c h i and Wolfrum [77].
D. Enhancement of ReactionRates
In order to utilize PC0 as a viable treatment process, the oxidation should be rapid and effi-
cient. Severalmethodologies havebeen examined, affecting boththeTiO,solidand the
makeup of the aqueous suspension, to enhance the effectiveness of K O .
An enhanced PC0 of organophosphorus insecticide by the addition of hydrogen peroxide
was reportedby Harada et al. [46]. Tanaka et al. [52,78] noted that low concentrationsof H,02
enhanced the photocatalytic oxidation of TCE and chloral hydrate,but rate inhibition occurred
at higher H202 additions. H202 can photolytically form OH. via reaction (8c) or it can act as
the electron scavenger as presented in reaction (8a). In either case, the hydroxyl radical con-
centration in the suspension shouldbe increased andthe corresponding oxidation reaction pro-
moted. Nevertheless, peroxide canalso promote hydroxyl radical recombination reactions [67]:
Overall: H202 + 2 OH* 4 2H20 +02 ( W
Several other reports of both enhancement and inhibition by hydrogen peroxide havebeen pub-
lished [22].
PC0 rates of several organic contaminantswere increased by the addition of inorganic ox-
idizing agentsto the suspension [22]. Peroxydisulfate(S2OS2-),periodate (IO4-), and chlorate
(ClO,-) enhanced oxidation rates by both scavenging electrons [analogous to reaction (6)] and
direct reaction with the substrate.
The photoactivityof the Ti02 solid can be modified by subjecting it to various physical and
chemical treatments. Abrahamset al. [1051 found an increased photocatalytic reductionrate by
heating theTiO, to 350°C, which was attributed to an improvementin the TiO, crystallinity by
annealing. Heller et al. [79] found that heating TiO, in the presence of oxygen or boiling it in
acid increasedthe reactivity; however, they used TiO,that originally had a passive surface coat-
ing, and any enhancement should primarily be induced by the removal of this coating. Heat
aminants
PC0 of Organic 391
treatments in air up to 500°C had a slight effect on toluene PC0 rates, but this process also
decreased the TiO, specific surface area [83]; overnight washingin strong acidor base did not
affect reactivity. The heatindannealing process eliminates imperfections and defects fromthe
TiO, solid state. These imperfectionscan act assites in which electron-hole recombination can
easily take place. As a result, the heating step increases photocatalytic reactivity. Mechanical
stressing of titanium dioxide particles by ball milling resulted in a decrease in photoactivity,
corresponding to the milling duration [79];this effectwas attributed to a disruption in the par-
ticle crystallinity.
Anpo et al. [80] foundenhancedphotoreactivityingas-phaseorganictransformations
when TiO, was coprecipitated with a fraction of A1,0,. Also, using laser flash photolysis, it
has been determinedthat iron-doped (0.5 wt %) TiO, is more photoreactive thanthe pure pho-
tocatalyst [81].It was suggested thatthe iron additionalters the photochemical behaviorof the
TiO,, allowing a longer e-/h+ lifetime andcurtailing recombination. However, dopings greater
than 1% apparently created an Fe2Ti05phase that decreases overall photoactivity. Another re-
cent study found that Ag+ ions (1%) impregnated into TiO, enhance chloride and CO2 pro-
duction from the photocatalytic degradation of chloroform and urea, respectively [82].
Davis and Espitallier [83]have completed a comprehensive investigation on the effect of
TiO,dopingwithmetals.Variousmetalshavebeenexamined,including V(V), Mn(VII),
Mn(IV), Mn(II), Fe(III), Al(III), Cu(II),Ni(II), and Ag(1); these metals were chosen to cover
a range of valences. Doping was accomplished usinga commercial TiO, mixed with a solution
of the metal, which was calcined at 500°C for 6 hr. Specific surface areas were quantified in all
cases. Initial PC0 rates of toluene were used to quantify doping effects.
In several cases specific reaction rates (rates per unit surface area) were increased by the
metal doping, but the calcining step concurrently decreased the specific surface area, resulting
in a decrease in the overall reaction rate. Only doping with Ag(1) resulted in a significant en-
hancement in the PC0 rate; initial rates were enhanced by a factor of up to 3. Unfortunately,
the reactivity of the silver-enhanced photocatalyst slightly decreases over the course of several
experimental runs, apparently due to the leaching of Ag+ from the TiO,, as also reported by
Kondo and Jardim [82].
While the cost of silver doping is certainly high, practical use of this technology may be
feasible because a significant rate enhancement results.If loss of leachable silver fromthe TiO,
can be averted andan efficient TiO, encapsulation processor capture processfor the suspended
TiO, particles is developed, silver losses fromthe treatment system canbe prevented and this
metal doping may be economically beneficial.
Another procedure that has received considerable attention for the enhancement of PC0
rates involves the supplemental addition of dissolved metals to theTiO, suspension. Addition
of dissolved transition metals has been observed to increase the rate of TiO, photocatalytic
oxidation by a factor of between 1 and 5 overthatin the absence ofanymetal ions
[6,10,24,50,51,60,84-871. For example, Pelizzetti et al. [lo]found that addition of Ag+ and
Fe3+ions to an illuminatedTiO,reactionsystemincreased the degradation rate of 2-
chlorodibenzo-p-dioxin. Sclafani et al. [87]and Wei et al. [86] found that added Fe3+ over
a range of 0 to 5 X lO-,/M increased the oxidation rate of phenol.Similarly, the initial
PC0 rates of phenol [24]and formic acid [50] were increased by the addition of dissolved
Cu2+. The copper co-anion slightly affected the reaction rate. In most cases the enhancement
was less at higher metal concentrations, and an optimum concentration of dissolved metals
was noted.
The observed rate increase resulting from the metal addition has been attributedto several
mechanistic phenomena.First, enhancement dueto electron trapping by the metal at the semi-
conductor surface is possible [10,24,501:
392 Davis
M"+ + e- + M(""')+ ( 17)
where M"+ represents Ag+, Cu2+, or Fe3+. This reaction prevents electron-hole recombina-
tion, correspondingly producingan increased rate of formation of OH- radicals through reac-
tion (2). Likewise, the detrimental effectsof high metal concentrationshave been attributed to
the reverse of reaction (17), i.e., oxidation of reduced metals by photogenerated holes, pro-
ceeding in competition with reaction (2) [6,84],
M("-')+ + h+ M"+ ( 18)
or by hydroxyl radicals. In order for reactions (17) and (18) to efficiently transpire, they must
be preceded by adsorption of the metal onto the TiO, surface.
A second mechanismto describe the enhancement assumesthat metal cations increase the
oxidation rate by participation in Fenton reactions to catalytically produce OH- radicals in an
alternative pathway to reactions (2a) and (2b) [20,24,87],
M("-')++ H202 + H+* M"' + OH. + H20 ( 19)
and/or to oxidize organic species or their radical intermediates [20].
The experimental results of Butler and Davis [88] indicate that dissolved Cu(II), Fe(III),
and Mn(I1) have both concentration- and pH-dependenteffects on the rate of toluene and chlo-
robenzene oxidation in TiO, photocatalytic systems. The initial reaction rate under the opti-
mum conditions [lo" M Cu(I1) at pH 31is double that without metals. There was negligible
adsorption of Cu(I1) onto the TiO, surface at the low metal concentrations and low pH values
at which the optimum rate was observed, indicating that metals enhance the removal rate
through a homogeneous reaction pathwayrather than through a TiO, surface reaction.A mech-
anism involvinga reactive complex betweenthe dissolved metal, the organicsubstrate, and an
oxygen-containing species such as H,02 or 0 ,
" was suggested.
In the presence of dissolved Cu(II), the PC0 kinetics can be described by a modified
Langmuir-Hinshelwood rate of the form (Figure 5 )
m
Rate = kk'KC
where kt represents the enhancement of the organic oxidationrate by a metal-catalyzed homo-
geneous reaction [88]. Using Equation (20), the values of k and K do not change appreciably
from thosein the absence of dissolved Cu(I1). Inthe presence of dissolved Fe(III), an additional
term is required to account for the absorption of UV light by the iron. At high metal ion con-
centrations, the detrimental effect on the reactionrate is likely due to absorbance of UV illu-
mination at high concentrations, in competition with absorption by the photocatalyst [87,88].
E. MechanismsandIntermediates
As a result of the current interest and investigative activity into various aspects of the PC0
process, some consistent mechanisms of oxidation are beginning to emerge, although many
conflicting ideas are still ubiquitous. As noted, PC0 demonstrates a Langmuir-Hinshelwood
relationship with respect to organic substrate concentration [Equation (ll)]. It has been as-
sumed that this dependence was directly due to a Langmuir isotherm dependence of the sub-
strate adsorption. For example, Matthews [56] investigated both the PC0 and dark adsorption
of methylene blueonto Ti02. Both were described using a Langmuir isotherm expression, sug-
gesting that adsorption of the substrate is a critical step in the oxidation. Several descriptions
of organic adsorption and competition from reactants and products such as 0 , and Cl- have
PC0 of Organic
aminants 393
30
6 20
"
'E
.-
E
E
IO
0
0.0 0.5 1.o 1.5 2.0
Initial TolueneConcentration (mM)
Figure 5 Enhancement of PC0 rates in the presence of dissolved copper (lo-' M)and iron ( M)
as a function of substrate concentration. (From Butler and Davis [88].)
been published. For example, Al-Ekabi and Serpone [21] studied the photocatalytic oxidation
of chlorinated phenols. They attempted to establish the role of organic adsorption in the PC0
process, although possible competitive effects of oxygen are ignored.
Kormann et al. [66] suggested that under properpH conditions, when the organic substrate
is favorably adsorbed, the reactions take place at the surface of the catalyst; a second-order
kinetic expression was presented based on adsorbedsubstrate and oxygen concentration, both
of which were quantified using Langmuir adsorption expressions. Conversely, CIR-FTIR ex-
amination of a photocatalyst suspension revealed no chemical bonding of 3,4-dichlorobiphenyl
to the TiOz [47].
Currently, the most widely accepted PC0 mechanism employs hydroxyl radicals as inter-
mediates in the oxidationprocess.Adsorption of the substrate is notrequired to produce
Langmuir-Hinshelwood kinetics if electron-hole and radical recombination reactionsare con-
sidered in the overall photocatalytic mechanism [7,89].
Evidence has consistently accrued implicating OH. radicalsthe in photocatalytic oxidation
of organics. Studyingthe role of OH. radicals in the oxidation of salicylic acid, Matthews [20]
found that the rate of degradation of the organic acid decreasedin proportion to the increase in
OH- radical scavenger concentration. ESR spectroscopy has confirmed an abundance of OH-
radicals produced upon the photoexcitation of TiO, [15,16]. As discussed earlier, Cunningham
and Srijaranai [l91 noted a photocatalytic kinetic isotope effect usingD20 instead of H20, but
not when an isotopic exchange was made on the organic substrate.
The OH. radicalsthat are produced at the catalyst surface may attack organic substrate that
is also adsorbedon the catalyst surface or theymay desorbandthenreactwith the or-
ganic in the bulk solution [7,43]. Recently Lawlesset al. [90] conducted studiesto identify the
role and importance of organic degradation by free versus Ti02 surface-bound OH. radicals.
394 Davis
Externally produced hydroxyl radicals were quickly adsorbed by TiO, particles, producing a
TiO, surface that had properties similar to those of the surface under PC0 conditions. This
suggests that surface-boundOH-radicals are formed during PCO. Their results also imply that
the organic oxidation occurs via these adsorbed OH. species.
Minero et al. [91] noted that decafluorobiphenyl (DFBP) that is strongly adsorbed onto
A1,03 is not photocatalytically oxidized when mixed with illuminated TiO,. However, degra-
dation of adsorbed DFBP does occur when hydroxyl radicals are supplied by H202in the pres-
ence of UV light. This evidencealso suggests thatthe organic substrate must be in close contact
with the Ti02 surface for degradation to occur and that the OH. radicalsthat are formed do not
travel far into the bulk solution.
Minero et al. [36] compared the diffusion rate of hydroxyl radicals in aqueous solution
with experimentally determined organic oxidation rates. Based on the assumption that these
rates are equal, it was shown thatthe OH. radicals could not diffusefar from the photocatalyst
into the bulk solution beforereacting, even at very low concentrations of the organicsubstrate.
Thus photocatalytic degradation processes occur either on or very near (within a few mono-
layers) the particle surface.
Others have proposed that OH. radicals formed by oxidation of surface water or hydroxo
groups eventually enter the solution to oxidize organics [16,92]. The formation of aqueous
H202 [through reactions (7b) and (7d)l and hydroxylated organic intermediates during photo-
catalysis provided the basis for their conclusion.
Peterson et al. [67] conducted a series of experiments using TiO, immobilized on a con-
ducting carbonpaste to study some of the reactions suggested to occurin a photoelectrochem-
ical slurry cell. If hydroxyl radicals were formed only at the TiO, surface, they would act as
recombination centers and form H202, producing an anodic photoresponse in their system.
However, if the OH- radicals were escaping into the bulk solution, a cathodic photoresponse
would be expected. A cathodic response was confirmed in the cell, leading to the conclusion
that OH.radicals do escape into the bulk solution.
Turchi and Ollis [7] have presented possible reaction mechanisms basedon four types of
interactions between photocatalytically formed OH. and the organic reactants:
1. The OH. radical species and the organic substrate are both adsorbed onthe catalyst surface.
2. The OH. radical migrates to the bulk solution (free OH- species) and reacts with the or-
ganic substrate in solution.
3. The adsorbed OH- radical reacts with the bulk solution organic substrate.
4. The free OH.radical reacts with the surface-adsorbed organic substrate.
Considering rates of recombination between holes and electrons, illumination intensity,
and additional information on catalyst physical properties, a mechanistic rate expression was
derived for the PC0 process. The resulting expression was in the form of Equation (11). The
rate parameter k was found to be constant for all four examined mechanisms and predictedto
be a function of the catalyst properties and reaction conditions;it was found to be essentially
independent of the organic substrate involved in the photocatalytic oxidation process. Exper-
imental results have confirmed this prediction of k being reactant-independent [7].
Turchiand Ollis proposed that, for the mechanisms inwhich the organic substrate is
present in the bulk solution, the parameter K is a function of the second-order reaction rate
constant for reaction of the OH- radical and the dissolved organicsubstrate. Conversely, if the
organic substrate is adsorbed on the catalyst surface, K is also proportional to the equilibrium
adsorption constant of the organic substrate.
Mechanisms of degradation by photocatalysis have been presented for several organic sub-
strates. Compounds such as hydroquinone, pyrocatechol, 1,2,4benzenetriol, pyragallol, and
PC0 of Organic
minants 395
2-hydroxy-l ,Cbenzoquinone have been isolatedas intermediates for the photocatalytic oxida-
tionofphenolusingTiO,[24].Suchhydroxylatedcompounds are suggestive of hydroxyl
radical attack. Catechol and quinone were also detected in the PC0 of phenol by Augugliaro
et al. [33]; hydroquinone and a phenol dimer were observed by Tseng and Huang [34]. A
mechanism involving hydroxyl radicals from illuminated TiO, 2,4,5-trichlorophenoxyacetic
for
acid and 2,4,5-trichlorophenol was postulated by Barbeni et al. [41]. Chlorinated quinones,
multihydroxylated chlorobenzenes, and other aldehyde and ketone chloroaromatics were iso-
lated. Final products were CO2 and HCl. Methyl catechol, methyl resorcinol, and methyl hy-
droquinone, all hydroxylated cresols, were isolated during the PC0 of o-, m- and p-cresols
[43]. A detailed examination of the PC0 of fluorinated phenols was presented by Minero
et al. [36].Stoichiometricproduction of CO, andF-wasfound; fluoride appearance
was much more rapid than that of CO2 and nearly coincides with the disappearance of the
parent compounds, suggesting that defluorination occurs early in the degradation process.
Intermediate products that were identified include mono- and dihydroxylated derivatives of the
parent compounds.
A plausible mechanism for phenol oxidationto catechol is that of reaction (21) [24]. Sim-
ilar mechanisms canbe invoked for the formation of hydroquinone from phenol and for reac-
tions of chlorinated and fluorinated phenols in which substituted catechol and hydroquinone
compounds have been detected. Continued hydroxyl radical attack should follow mechanisms
similar to those presented where OH. radicals are formed from sources other than photocatal-
ysis, i.e., high-pH ozone decomposition or radiolysis.
A detailed mechanism for the degradationof triazine herbicides has been published[45].
The primary degradation pathway is through alkyl chain oxidation. The final product for the
herbicide PC0 is cyanuric acid,
which is stable and not subject to further degradation [441. At this point, cyanuric acid is one
of only a few organic compounds that are photocatalytically unreactive.
Several publications have investigated the PC0 of other nitrogen-containing heterocyclic
organic compounds. Low et al. [S81 monitored the concentrations of ammonium, nitrate, and
carbon dioxide from several of these compounds. The appearance of ammonia was very rapid,
indicating quick cleavage of the ring to release the nitrogen. Rates of NO,- production sug-
gested that its formation was entirely due to the oxidation of previously synthesized ammo-
nium. Ammonium was also detected in the PC0 of nitrophenols[57],indicating a reduction of
the substrate nitro group.
As with all organic oxidation processes, there is concern over the formation of inter-
mediate compounds that may be more toxic than the parent material. Unknown intermediate
compounds from the partial PC0 of pentachlorophenol and 2,4-dichlorophenol demonstrated
an increase in toxicity to an activated sludge system over that of the parent compound [93].
396 Davis
Nevertheless, long-term PC0 of these compounds, as well as PC0 of methyl vinyl ketone,
decreased toxicity to activated sludge.
In summary, the mechanistic work withPC0 has demonstrated the formations of hydrox-
ylated intermediates, indicative of hydroxyl radical oxidative pathways. Less understood are
the formation and interaction of hydroxyl radicals and organic substrate, either at the photo-
catalyst surface or at some small distance into the solution. More studies are needed for com-
plete comprehension of these mechanisms.
111. LARGE-SCALEAPPLICATIONS
Pilot- and full-scale studies using solar illumination and reactor volumes of 100-300 gal have
been investigatedby the National Renewable Energy Laboratory (NREL) Golden, in Colorado.
PachecoandHolms [94] describe engineering-scale experiments for the detoxification of
solvent-contaminated groundwaters.' h 0 reactors were used: a parabolic concentrating trough
(7 ft by120 ft with a 51-fold concentration efficiency) and a falling film reactor. PC0 of a
model compound, salicylic acid, was examined. The light intensity ranged from 1032 to 484
W/m2 for clear to cloudy days, respectively. Resultsfor the two reactors are presented in Figure
6, where the exposure time is given as the total time multiplied by the ratio of light-exposed
water volumeto total water volume.Thus less than3 min exposure to illumination was required
for effective removal of this compound. The temperature of the suspension rose from7 to 53°C
as a result of the applied concentrated solar illumination, which may have enhanced the reac-
tion rate.
A field experiment using concentrating trough reactors is described by Mehos et al. [95]
and Tbrchi and Mehos [3]. W Osets of parabolic reactors, 120 ft long, were used for treating
deionized water spiked with TCEand, subsequently, contaminated groundwaterat Livermore,
California. A TiO, loading of 0.8-0.9 g/L was used. A flow rate of 4 gpm allowed a 10-min
exposure time and heated the water to 140°F. Results from the treatment of the contaminated
350 ?
4
U
.-
3 15
0
.- Falling Film:
3
- 10
220 w-w/I
d
5
0
0 1 2 3
Exposure Time (min)
Figure 6 Salicylic acid destruction using full-scale photocatalytic reactorwith solar illumination. (Re-
printed with permission from Pacheco and Holm [94]. Copyright 1990 American Chemical Society.)
aminants
PC0 of Organic 397
groundwater showed a decrease in TCE from 107 ppb to 10 ppb. However, by reducing the
water pH to 5.6 to decrease the effect of bicarbonate ions, the effluent TCE concentration was
reduced to < O S ppb.
Recent work at NREL [3,95] found that, on a basis normalizedby the photoreactor surface
area, PC0 employing nonconcentrating reactorsis more efficient than concentrating (i.e., par-
abolic) reactors. Thisis attributed to (1) the high light reflection losses in large-factor concen-
trating reactors; (2) the importance of capturing diffuse UV radiation, which is not collected in
concentrating reactors; and (3) the decrease in PC0 efficiency due to radical recombination
processes at high light intensities, as discussed in Section 1I.C.
"hrchi etal. [96] presenta detailed analysisfor the treatment of TCE-contaminated ground-
water usinga full-scale photocatalytic reactor. Modelsof solar irradiation are used in conjunc-
tionwith calculations of weather conditions to estimate available solar flux for the PC0
reaction. Incases where bicarbonateconcentrations are high, pre- and post-treatmentsteps con-
sisting of, respectively, a lowering and neutralizingof pH must be employed in the system for
efficient PCO. A strainer and filter areused to remove any particulate matter that may inhibit
light transmission through the contaminated water.
For a 100,OOO-gpd PC0 treatment system, land use for solar reactors ranges from 0.7 to
1.5 acres [96]. Solar sensors are used to adjust flow rates through the reactor system; higher
flow rates are used during periods of high solar intensity. The photocatalytic reactor would
operate at its maximum rate during midday, slow downas solar intensity decreases during the
evening, and shut off completely overnight. Surge tankswould be used to store the water both
before and after the phototreatment. This would allow continuous operation of groundwater
pumping wells as well as the pre- and post-treatment processes.
PC0 reactor schemes evaluated include parabolic reflector flow reactors as well as se-
quencing batch reactors and a continuous serpentine reactor, each approximately 1 m deep.
A detailed cost analysis usingPC0 reactors for a 100,OOO-gpd contaminated groundwater
cleanup facility in Livermore, California yields costs of $5.00-$6.00 per 1OOO gal treated. In
comparison, activated carbon treatment wasestimated at $6.20/1OOO gal and UV/H,02 oxida-
tion as $4.40/1OOO gal, thus indicating that PC0 can economically compete with these other
common groundwater remediation processesin an area that has a favorable solar flux.
A major concern in full-scale PC0 processes is the separation of the photocatalyst from
the water stream after the completion of the reaction. Most commercially availableTiO, par-
ticles are on the order of 1-10 pm in diameter, making efficient removal difficult. An active
research area incorporates the fixation of TiO, particles on various supports to allow easy sep-
aration. For example, the PC0 of several organic dyes using Ti0,-coated sand has been dem-
onstrated [97]. However, rates are apparently limited by mass transfer of the substrate to the
immobilized photocatalyst.
IV. OTHERENVIRONMENTALAPPLICATIONS
The success of organic PC0 processes has led to investigations into the application of photo-
catalysis to manage other environmental concerns. The catalytic redox properties of illumi-
nated Ti0, have recently been exploitedfor the treatment of inorganic contaminants. Pollema
et al. [98] present results from a detailed examination of the PC0 of cyanide. Langmuir-
Hinshelwood kinetics with respect to CN- concentration were found, and varying TiO, con-
centrations had negligible effects on the rate. Cyanate accumulated from the initial cyanide
oxidation; eventually the cyanate was converted to nitrite and finally to nitrate. Tennakone et
al. [99] also demonstrated that nitrite can be photocatalytically oxidized to nitrate. Cyanide
removal from a copper cyanide solution viaPC0 was investigated using TiO, and ZnO [loo];
398 Davis
TiO, was more efficient. The presence of copper enhanced the removal of CN- over that of a
simple KCN solution. Bhakta et al. [loll found that ferricyanide can be efficiently degraded
using PCO.
Another application of photocatalysis involves the use of reduction mechanism to treat
metals. For examples, hexavalent chromium can be reduced to the trivalent species. Also, dis-
solved metals can be completely reduced to the metallic form. Both Hg(I1) and CH,Hg(II) were
reduced to metallic mercury from 100-ppm solutions using TiO, [102]. Gold(II1) is reduced to
the metal by anatase titanium dioxide [103]:
3 e- + Au(II1)-+ Au(s) (22)
In both cases, oxygen production from water oxidation may be the hole scavenger; however,
adding methanol or ethanol increases the rate. Adsorption onto the TiO, and aqueous com-
plexation of the metal ion control the reaction rate.
V. SUMMARY
Photocatalytic oxidation has unlimited potential as a watedwastewater treatment process. PCO
has its greatest potential for use in areas of high solar irradiation where sunlight can provide the
TiO, excitation. A recent economic analysis suggests that PCO is competitive with common
organic treatment systems in areas of high solar flux, with current costs estimated at $5-$6 per
1000 gal treated [96]. Also the oxidation typically proceeds to CO,, water, and inorganic com-
pounds (Cl-, F-, PO,,-, NO,-, NH4+). The reaction is rapid and efficient. Therefore the
accumulation of possible toxic intermediates is avoided. Oxidation provides chemical treat-
ment of organic contaminants as opposed to phase separation processes, which transfer the pol-
lutant to a different waste stream.
Some of the present concerns of PCO include the separation of the TiO, from the efflu-
ent after the reaction and possible long oxidation times for large molecules or under nonopti-
mum conditions.
As with all oxidation processes, a major wastewater application may involve pretreatment
with PCO, followed by a traditional biological treatment. The partial photocatalytic oxidation
would convert difficult-to-treat compounds to substances that are much more amenable to bio-
degradation. Photocatalytic oxidation is a promising waste treatment technology and has the
potential to exert a significant impact in the field. Recently the use of PCO has been extended
to the treatment of organic-contaminated soils [ 1041.
ACKNOWLEDGMENTS
Support for some of this work came from the National Science Foundation, grant number BCS-
90 10434. Appreciation goes to Elizabeth Butler, Sonal Sanghavi, Phil Espitallier, and Muham-
mad Shariq Vohra. I also thank Oliver J. Hao and C. F? Huang for reviewing this chapter.
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57. Low, G . K.-C., McEvoy, S. R., and Matthews, R. W., Formation of nitrate and ammonium ions in
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58. Low, G . K.-C., McEvoy, S. R., and Matthews, R. W., Formation of ammonium and nitrate ions
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Water Res., 24, 653-660 (1990).
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65. Matthews,R. W,, Carbondioxideformationfromorganicsolutesinaqueoussuspensions of
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66. Kormann, C., Bahnemann, D. W., and Hoffmann, M. R., Photolysis of chloroform and other or-
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402 Davis
67. Peterson, M. W., lbrner, J. A., and Nozik, A. J., Mechanistic studies of the photocatalytic behav-
ior of TiO, particles in a photoelectrochemical slurry cell and the relevance to photodetoxification
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71. Sclafani, A., Palmisano, L., and Davi, E., Photocatalytic degradationof phenol by TiO, aqueous
dispersions: rutile and anatase activity, New J. Chem., 14, 256-268 (1990).
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l8
Biodegradation of Organic
Pollutants in Soil
Paul D.Kuhlmeier
Consulting Environmental Engineer
Boise, Idaho
1. OVERVIEW
Soil that is accidentally contaminatedby releases of hazardous chemicalsmay be classified as
hazardous waste under state or federal environmental statutes.When the amounts of contam-
inated soil are sufficiently large, themost often used methods of disposal, incineration or land
disposal, can become prohibitively expensive. In addition, soil pollutants act as a secondary
source for groundwater contamination. The U.S. Environmental Protection Agency has re-
cently implemented a strategy to address the complex problems associatedwith soil pollution
through the application of innovative technologies [l]. One of the most frequently studied al-
ternatives of late for the treatment of several classes of organics, notably petroleum hydrocar-
bons, is bioremediation.
Long maligned as a technology that simply uses pollutants to attack other pollutants, the
method was revived by Lee Thomas, former EPA administrator, and its use has spread to 130
contaminated sites throughout the country. Out of these 130 sites, 85 are targeted to treatsoils,
55 groundwater, and to a much lesser extent sediments, sludge, and surface water (Figure 1).
Of the two classical methods for bioremediation, ex situ and in situ, fully 75% are using the ex
situ method via some form of bioreactor, landfarming, static pile, or aerated lagoon. The vast
majority of sites undergoing bioremediation use aerobicas opposed to anaerobic methods[l].
Although considered a new “innovative” technology by the EPA, bioremediationis any-
thing but new. The mechanisms from which bioremediation research and application were de-
rived are deeply rootedin biological wastewater treatment. Groundwater is routinely extracted
and treated in on-site bioreactors that behave much like activated sludge systems, with three
unique differences: groundwater influentis more dilute than wastewater, groundwater influent
can containa single or select few substrate types, and if bioremediation is properly performed,
substrate levels continuously decline. A similar analogy can be drawn between soil treatment
and fixed-film wastewater reactors. Kinetic equations for activated sludge and trickling filter
reactors have been applied since at least the 1930s. R. L. Raymond was the first researcher to
405
406 Kuhlmeier
"
80-
70 -
60-
50-
40-
30-
20 -
10 -
08
SOIL GROUND SEDIMENTS SWDGE
2 SURFACE
l
WATER WATER
Figure 1 'Qpes of media treated by bioremediator. (After U.S. EPA [l].)
patent the applicationof subsurface microorganisms to degradea variety of groundwater con-

taminants as early as the 1970s [2-41.
The process of degrading hazardous organicsin shallow soils to be discussed here usually
involves stimulating the indigenous subsurface microflora to enhancethe decomposition rate.
Although engineered microorganisms with specialized metabolic capabilities have been devel-
oped andapplied, indigenous organism stimulation is being used at three outof every foursites
[l]. Irrespective of the microorganism selection, the goal of biodegradation is to convert or-
ganic wastes into biomass and harmless by-products of microbial metabolism such as HzO,
COz, CH4, and inorganic salts. To investigate the abilities of this remedial alternative, one
must understand the waste characteristics and microbial ecology unique to each site, the lim-
itations of the method, and the mechanisms by which its effectiveness can be optimized.
II. STRUCTUREANDBIODEGRADABILITY
A. Structure Relationships
There is no clear and consistent way by which to predict biodegradationof a specific compound
in soil absent specific site-related experiments. Thereare rules of thumb, however, that can be
applied when assessing the potential for a compound to be significantly degraded. These gen-
eral theories are rooted in chemical class or type, solubility, and chemical structure.
The following rules of thumb can generally be applied within classes of chemicals:
e
Water-soluble compoundsare usually degraded faster than less soluble compounds.

Branching from the main chain decreases the biodegradation rate.
Hydroxylandcarboxyl functional groups onbenzeneringsusuallyincreasebiodegrada-
tion rates.
Halogen, nitro, and sulfonate functional groups on benzene rings usually decrease biodegra-
dation rates.
Biodegradation of Organic Pollutants in Soil 407
Table 1 Degradability by OrganicClass

Contaminant groups Biodegradability lfeatment range (%)
~ ~~
Halogenated volatiles Effective 50- 100

Halogenated semivolatiles Effective 75-100
Nonhalogenated volatiles Potential effectiveness 20-95
Nonhalogenated semivolatiles Effective 20-85
PCBs Potential effectivenesdeffective <Aroclor 1242, 25-80
BArochlor 242,O-30
Pesticides Effective 35-100
Dioxinslfurans Not effective <30
Organic cyanides Potential effectiveness 10-70
Organic corrosives not effective <30
As the number of halogen atoms, e.g., chlorine, within the molecule increases the biodegra-
dation rate decreases.
Biodegradation rates are very slow for condensedor fused aromatic and cycloparaffinic mol-
ecules with four or more rings.
The number and positions of substituents on an organic molecule will affect loss rates. Alco-
hols and acids are more susceptible to biological decomposition than corresponding al-
kanes and ketones. Substituents on aromatic rings at the paraposition appear to be more
readily available to bacteria than those at the ortho or meta positions.
Unsaturated aliphatics degrade more readily than similar saturated hydrocarbons. The avail-
ability of various enzymes has been suggested as the cause for this observation.
n-Alkanes, n-alkylaromatics, and aromatic hydrocarbons in the C d , range are biodegrad-
able, but in most environments volatilization proceeds faster than biodegradation.
A synopsis of compound groups and their relative biodegradability is shown on Table
1.
B. General Pathways for Degradation

All microorganisms need a source of energy for maintenance of cell viability and growth. The
manner in which energy is obtained varies, and bacteria can be classified according to the
source of their energy requirement. Phototrophs such as cyanobacteria use light directly in a
photosynthetic process. Chemotrophs oxidize organicor inorganic compounds.
The most common method of gaining energy is through oxidation reactions, which are
normally coupled to the formation of ATP and other high-energy molecules. Many different
kinds of substrates can be oxidized, but eventually the substratesare modified to metabolites
that can enter one of only a few pathways for carbon dissimilation. These pathways can be
divided intotwo categories: fermentation pathways in which organic compounds serve as both
the electron donor and electron acceptor, and respiratory pathways in which oxygen or an in-
organic compound or ion serves as the terminal electron acceptor.
Aerobes utilize a respiratory pathway knownas the tricarboxylic acid cycle. The interme-
diates in the cycle are precursors to important cell macromolecules and may be used to fulfill
other needs. Other metabolic reactions act to replace the intermediates in order to maintain
functioning of the cycle.
A wide varietyof microbial species can degrade organic pollutants; there is a rather limited
series of sequences or pathways by which any particular class of organic may degrade [5,6].
Noteworthy study in this area was performed by Dagley [7],who critically reviewed several
common soluble organic wastes, coming to the conclusion that direct insertion of oxygen is
408 Kuhlmeier
required very early in the catabolic process. Either of two types of enzymes is associated with
this reaction, a monooxygenase or dioxygenase. The reaction is
RH + 0 2 + [H-] + ROH + H20 (1)
where R denotes an organic carbon chain.This reaction is usually dependenton nicotinamide

adenine dinucleotide (NADH).The second is a coenzyme-independent dioxygenase:
RH2 + 0 2 + R(OH)2 (2)

Some evidence suggests that these reactions, although associated with a large A H , may
proceed without being coupled with adenine triphosphate (ATP)or NADH production [g].
Enzymes are proteins and are the most well-known catalysts for biochemical processes.
They serve to increase the rate of a reaction, often causing a reaction to occur under physio-
logical conditions that otherwise could occur only under extremes ofpH, temperature, or
concentration.
Degradation pathways tendto converge owinglow substrate specificity of enzymes early
in the decomposition pathway. This observation holds generallytrue for a wide variety of sol-
uble organics, with notable exceptions being classes of compounds subject to cometabolism
such as chlorinated ethenes or very stable branched organics such as PCBs. Genetic research
has also produced an explanation for pathway convergence. Studies [9] focusing on pathways
for two specific plasmids found that degradative pathwaysfor aromatics are plasmid encoded
and that the organisms appearto be similar because theyare coded by the same plasmids. From
a practical viewpoint, knowledgeof the intricacies of enzyme coding andits effect on degrad-
ability is in its infancy, and applications in the field may not be commonly understood and
utilized until well into the next century.
C. Degradability of Petroleum Hydrocarbons

To date, over 70% of biodegradation studies and applications have focused on petroleumhy-
drocarbons. This situation is perhapsan artifact of the vast number of gas stations and petro-
leum refining and storage locations that have released substantial amountsof petroleum over
decades of use, and the fact that compoundsof this class are among the most readily degraded.
The biodegradability and biodegradation pathways of petroleum hydrocarbons have been ex-
haustively reviewed [lo-121. More specific reviews based on compound class have also been
performed for alkanes [13,14], cycloalkanes [15], and aromatics [16-191. For unweathered pe-
troleum, the primary catalysts for biological attack are oxygenases, whichrequire the presence
of free oxygen. Monooxygenase attack results in alcohols from alkanesby typically attacking
at theterminal position. The resulting alcohol is oxidized further to an aldehyde and finally to
a fatty acid by beta-oxidation. Methyl branching decreases the rate of biodegradation by in-
terfering with the beta-oxidation [20].This problem is usually overcomeby the introductionof
a secondary substrate such as methanol, which appears to promote diterminal attack or other
bypass mechanisms on the aldehydes. A general rule can be derived here: n-alkanes will de-
grade on the order of twice as rapidly as isoalkanes. Cycloalkanes are degraded more slowly
than the isoakanes. They are transformed by a poorly understood oxidase system to cyclic al-
cohols, which are in turn dehydrogenated to ketones. A separate and unique monooxygenase
then lactonizesthe ring, which is slowly opened by a lactone hydrolase. Itis salient to note that
these two oxygenasesystems rarely occurin the same microorganisms,which supports the use
of heterogeneousindigenouspopulations or heterogeneousinoculainjection (i.e., sewage
sludge, manure) as opposed to engineered pure cultures.
Perhaps seeing the widest range of study are the aromatics. Procaryotic microorganisms
convert aromatic hydrocarbons, through an initial dioxygenase attack, to trans-dihydrodials
that are further oxidizedto dihydroxy products, catechol in thecase of benzene [21]. Catechol
is the key intermediate in aromatic biodegradation.The ring is openedby either ortho or meta
cleavage, resulting in muconic acidor 2-hydroxymuconic semialdehyde. Following the tricar-
boxylic acid cycle, both products are further reduced. Polycyclic hydrocarbons are degraded
one ring at a time. It has been demonstrated that compounds containing four or more rings,
such as pyrene and chrysene, cannot be used directly as substrates by microorganisms [22],
however, they have been successfully degraded through cometabolic transformations [23,24].
Observations by the author in remediating railyard contamination suggest that 2 weeks of ac-
climatization time mustbe added for effecting long-term polycyclic aromatic degradationper
ring from three to six, beyond which no relationship or degradability could be inferred.
111. BIOKINETICS
Once the physiochemical site conditions have been assessed and the biofeasibility of degrading
a target pollutanthas been determined through soil respirometry or other similar studies, a con-
ceptual model for estimating field reaction rates can be constructed. Several theoretical models
have been proposed for simulating bioremediationof contaminated soil and groundwater [26-
281. These models consider contaminant movement from the bulk liquid phase to adjacent par-
ticle surfaces. Baveye and Valocchi [29] considered several models critically in light of their
applicability to soil remediation, ultimately proposingnew a model roughly based on the theory
of attached growth on fine media. Kuhlmeier[30] found that empirically derived data applied
to slight modifications of classical Monod relationships [31] provide the best-fit results across
a wide spectrum of nonchlorinated organics.
A. Biomass-SubstrateRelationships
The Monod relationships for describing the growth and decay of microorganisms and consump-
tion of organic substrate takes the form
and
where X is the microbial concentration (mg/L), pmis the maximum specific utilization rate
Uday), Y is the microbial yield coefficient (g/g), S, is the amountof limiting substrate(mg/L),
kd is the microbial decayrate (Uday), and K, is the substrate half-saturation constant (mg/L).
Growth takes the form of a hyperbolic functionof a limiting nutrient, usually nitrogenor
phosphorus. The interreactivity of oxygen availability and biomass density often renders spe-
cific nutrient stress difficult to pinpoint, however. If bench-scale studies allow for sensitivity
analysis, Equation (1) can be expandedto a multiple-compound analysis in the form of
where Ciis the concentration of the ith limiting nutrient.

410 Kuhlmeier
If Ci greatly exceeds Ki, the term Ci/ (Ki + Ci) goes to 1.0 and as a result has no effect
on microbial growth. A practical limiting value for a multiple of Kiis approximately 3 for
short-chain aliphatics using landfarming, to as much as 10 in situations where inhibitory com-
pounds suchas chlorinated solventsare commingled inthe soil to be treated. Concentrations of
trichloroethylene as low as 50 pg/L can inhibit activity in a 0.2 mgd slurry bioreactor. Con-
versely, when Ci < Ki, the growth rate will be roughly proportional to the concentration of
nutrient i. A critical element to field monitoring of minimum nutrient loading (Cmin)can be
derived from this analysis. Cmincan be written as
Recognize that Equation (4) represents a one-substrate scenario and that in practice this
condition is rare. Thus, organic degradation is generally not limited to the implied boundary
condition. Using the example of petroleum degradation, growth rates tend to decline substan-
tially at pollutant concentrations below 100 mgkg soil. To offset these losses, secondary sol-
uble substrate additions in the form of dilute primary alcohols can be added to the nutrient-
water injection solution. This technique is particularly effective in landfarms.
To develop a more accurate model for expressing microbial kinetics, decay must also be
considered. The rate of biomass growth in the bulk liquid phase can then be described as
where COis the concentration of oxygen in the liquid phase. Here the first term on the right-
hand side of the equation represents growth, and the second term represents decay.
In soil, the immobile microcolonies can havea significant effect on removalrates; in fact,
in many cases it can exceed the effect of mobile colonies, particularly in fine-grained soils
(permeability less than c d s ) whereinsitutreatment is beingconducted.Exchange rates
are not controlled by transport within the bulk pore network because the microcolonies are
found attached at the interface between the liquid and solid phases. To account for this phe-
nomenon, local adsorption-desorption equilibrium shouldbe included in an overall massrate
expression. The simplest form is based on a linear relationship that can be expressed as
qb = Kdx (8)
where q6 is the effective concentration of biomass in the solid phase (g/g) and Kd is the par-
tition coefficient of the biomass (g/g).
The rate of biomass growth in the form of microcolonies at the solid-liquid interface can
be expressed as
For simplicity, it is assumed that the concentrations of substrate and oxygen extracted by
the microcolonies are equal to those in the bulk liquid phase, which, in reality, is rarely true.
The rate of substrate degradation in the bulk phase can be estimated by
Similarly, the rate of substrate degradation by the microcolonies at the immobile interface is
Pollutants in Soil 411
To calculate the oxygen consumption required to keep population growthat a minimum,

the yield coefficient for oxygen(Yo) is substituted for Y in Equation (10).
B. Inhibitory Wastes
Discussion of kinetics to this point has assumed thatone or more soluble substrates are avail-
able to the resident microbial population. The existenceof inhibitory or toxic chemicals,how-
ever, more adequately reflects reality. Inhibitory waste is any waste
that, when introduced, can
effect a reduced respirationrate or a reduced growth rate.A compound's inhibitory actionmay
be membrane mediated or cytoplasmically mediated. Membrane mediation has been linked to
lipophilicity, particularly at low concentrations [32]. Research in this area has advanced rapidly
within the wastewater treatment industry. Extensions of this research to hazardous waste biore-
mediation is now being investigated. Existing theory in the wastewater regime suggests that
process dynamics.A sim-
operational difficulties associated with inhibitory wastes arise todue
ilar paradigm canbe demonstrated in soil remediation; landfarming systemsare more effective
than in situ systems. The primary reason is the ability
to control operating dynamics to a greater
extent with the ex situ method.
Substrate-inhibited growthmay be described by a variation of Monod theoryas expressed
by the Haldane equation [33]
where p is the actual specific growth rate and

KI is the inhibition constant.
Quantification of 1.1and KI is typically accomplished through respirometric studies. It is
interesting to notethatevenwhentreated as anempiricalequationdescribingsubstrate-
inhibitedgrowth,theHaldaneequationsuggeststhatperformanceenhancementscan be
achieved through stringent process control.
W. PRACTICALLIMITATIONS
Given the complexity of the bioremediation process, it is often as critical to know the limita-
tions of the site-specific scenarioas it is toknow how to apply the technology. Bioremediation
is not unlike a golf swing; to play well, good mechanicsare everything. Yet, recognizing flaws
and adjusting them seems to be an insurmountable task. Environmental factors may stunt or
preclude biodegradation even in the presence of engineered organisms. Biodegradationat re-
sidual concentrations of the target substrate frequently is a function
of the presenceof toxicants
[34]. During acclimatization and log growth phase, insufficient oxygen and nutrient are the
dominant constraintsto growth rate. As a target substrate is reduced to levels below 200 mgkg
soil, substrate concentrationand substrate inaccessibility may reduce the microbial population
to maintenance levels.If the applicationis being attempted in situ, the transport of oxygen and
nutrients to the contaminated zone and the extractability of the affected pore water present yet
another set of constraints.
The challenge of effectively introducing nutrients and oxygen to the subsurface can be
daunting. Bioslime buildup adjacent to injection wells or drains is a common problem. Sub-
surface heterogeneitiesand sorption of nutrients lead to preferential flow pathways for oxygen
412 Kuhlmeier
and nutrient transport, leaving pocketsof the contaminated zone virtually untouched. Field ex-
perience acquired from responses to tanker and railroadcar spills indicates that a practical limit
to the size of an in situ treatment system ranges from3 acres in fine-grained soils (sandy silt)
to perhaps 20 acres in porous sands and gravels with native organic contents greater than 3%.
Bioremediation in situ for contaminated soil over5 acres or contaminated groundwater greater
than 20 acres in size is not recommended as a sole treatment but may be included in a com-
bination system with such technologies as soil venting, in situ air sparging, or hydraulic con-
tainment with above-grade treatment.
Recall that in Section I1 it was noted that sufficient oxygen was requiredto commence the
catabolism process. Alexander [34] found that operating a system in an oxygen-deficient en-
vironment inhibited the metabolism of simple carbohydrates. Aromaticdegradation may cease
at oxygen concentrations less than 50% of optimum [35]. Lee and Ward [36] confirmed these
findings by observing a large decay rate for naphthalene, dibenzofuran, and phenanthrene in
oxygenated groundwater in comparison to oxygen-depleted water.
Aerobic degradation is not the only pathway for aromatic degradation, however. Miner-
alization of xylenes in river alluvium under denitrifyingconditions has been reported by Kuhn
et al. [37]. Benzene, toluene, and alkylbenzenes detectedin landfill leachate were mineralized
by methanotropic bacteria in a study by Wilson and Rees [38]. Anaerobic decomposition has
not been the subject of significant research efforts to date and currently is not being proposed
at any of the 80 soil remediation sites under the purview of the EPA [l].
Macronutrient levels should be maintained in excess of optimum whenever practical. In
order of importance to growth rate sensitivity, the major macronutrients are nitrogen, phos-
phorus, potassium, sodium, and calcium.
The effect of declining substrate concentration on biodegradationhas been documented in
soil and groundwater[39,40]. Kuhlmeier [39] postulated that a threshold may exist for degrad-
ing petroleum hydrocarbonsin landfarms at 30-70 mg/kg. Functional thresholdsfor numerous
other contaminants such as acetone, bromodichloromethane, and phenolshave been raised by
others [41-431.
Tbming once again to experience acquired fromthe wastewater industry, another limiting
factor can be the amount of inoculum introduced. The theoryis that the low cell densitythat is
introduced intosoil may not replicate enough to promote effective bioremediation. The effects
of predators (protozoa) on the growth of a strain of Pseudomonas bacteria in a sandy loam
injected with 50 mg/L methanol was tested. At a cell density of 520 cells/mL, the bacteria
declined when protozoa were not inhibited. However, when the protozoa were inhibitedby cy-
cloheximide and nystatin, the inoculated bacterium multiplied after a 30-h lag period to over
1.7 X lo4 cells/mL (Figure 2).
Other factors such as soil permeability,native organic content, sorption, pH, and temper-
ature also play a role in limiting biological degradation rates. Soils exhibiting a permeability
greater than 1 x cmls and a total organiccontent of 3% are moreamenable to bioresto-
ration. Free product in the subsurface should be removed prior to commencement of biofeasi-
bility studies. Sorption has the tendency to concentrate nutrients and canalso render the target
substrate unavailable to the microbial population. Solubilization techniques such as the addi-
tion of surfactants can aid in minimizing this problem.
Soil pH plays a key role in sorption phenomena of ionizable compounds and affects en-
zyme activity. Several strains of microorganisms known to degrade aromatic hydrocarbons are
inhibited at pH values less than 6 [44],and activity approaches zero at soil pH below 5.5. In
some cases it is preferable to adjust soil pH where possible to slightly basic. Hambrick et al.
1451 observed that mineralization of naphthalene in sediment was faster at pH 8 than at pH 5.
m
0
d. l0,Ooo
lOm0
7500
7w
j
-
-
m-
40 80 80 100
Figure 2 Effects of predator organismsoninoculumgrowth (soil amendedwith 50 mglL and 100

mg / L methanol).
A comparison was not madeat the less acidic conditions ofpH 6 or 6.5, so true optimization
could not be determined.
Temperature has a profound effect on microbial activity, particularly in landfarm appli-
cations. Several researchers have reported direct relationships between degradation and tem-
perature[39,46,47].Fungitend to be moretemperature-tolerantthanbacteria.Ageneral
benchmark for temperature thresholds is 55°F for inhibition and 42°F for cell die-off.
V. APPLICATIONS IN PRACTICE
A. Oxygen
Hydrogen peroxide is often usedto increase the amountof oxygen availableto microbes when
applying in situ techniques. Hydrogen peroxide may use be beneficial in landfarming situations
as well. Although it is an excellent alternative oxygen source, hydrogen peroxide is toxic at
concentrated levels. Lee et al. [48] suggested that 200 ppm can be toxic to microorganisms.
Their work, unfortunately, was limited to published literature. Introduction of stepwise in-
creases of hydrogen peroxide is possible up to at least 2 %.If added immediately after wetting
a landfarm where hydrophobic compoundsare of interest, concentrations of 4% have proved
successful in enhancing biodegradation rates. The combination of surfactants and hydrogen
peroxide injection in the waterstream is also showing promise in degrading hydrocarbons ad-
sorbed to the clay fraction in a fine-grained soil matrix. Hydrogen peroxide, if introduced into
the subsurface, should be added after nutrient addition to aid in controlling biofouling of in-
jection points.
B. Nutrients
Certain nutrients are required by all cells. Carbon is the most important, and those cells that
obtain it from organic substratesare referred to as heterotrophs. Autotrophs canfix carbon from
414 Kuhlmeier
carbon dioxide.A few specialized groups can use other substrates; methylotrophs,for example,
can oxidize methane at aerobic-anaerobic interfaces. Other essential nutrients include phos-
phorus, usually derived from phosphates, and nitrogen, usually obtained from nitrate or am-
monia. These three elementsare the most common nutrientsthat limit growth. Other necessary
growth factors include sulfur, magnesium, potassium, calcium, and other metallic elements.
While some bacteria synthesize all their required vitamins and growth factors, other bacteria
must obtain some from the environment. Water is also a specific requirement in cellular me-
tabolism. The bacterial cell is about 80% water, and water is both the solvent and a specific
cofactor in many biochemical reactions.
Nitrogen and phosphorus are the nutrients that typically limit microbial growth and me-
tabolism. Although other macro- and micronutrients are essential, soil and groundwater contain
sufficient levels of these to sustain unlimited microbial growth. Therefore, the quantitative
analysis of nutrients other than nitrogen and phosphorus is not typically necessary. Industrial
wastewater is a possible exception where other nutrientsmay become limiting.
Ammonia is the preferred nitrogen sourcefor bacteria. Soils, groundwater, or process wa-
ter are tested for residual levelsof ammoniacal nitrogen. Sincethe total amount of organic car-
bon is usually determinedat some point during the site assessment, the proper nitrogen addition
rate can be calculated based on the size of the site and the estimated total mass of organic
material that needs to be biodegraded.
The residual level of orthophosphate in a sample is also determined. Based on the total
organic carbon content of the sample, estimates can be made regarding the amount of phos-
phorus needed to bioremediate a site or waste stream. Based on the concentration of calcium
and magnesium in aqueous systems, phosphate in excess of that needed to remediate the site
may be required to prevent precipitate formation.
The availability of nutrients and the ability to move nutrients througha matrix such as soil
are important considerations when evaluating a site for in situ treatment. The aqueous phase
interaction of phosphorus, calcium,and magnesium should be considered. Soil itself poses an-
other potential problem. Ions tend to interact with soil particles byionic interactions. The
strength and magnitude of suchinteractions can influence themovement of nutrients through an
in situ treatmentarea. In order to determine thecorrect nutrient additionrate, the ability of the
soil to adsorb ammonia and phosphorus should be known. Adsorption immobilizes nutrients so
that their movement through the soil is seriously impeded. This effect can usually be counter-
acted by adjusting the nutrient addition rate to account for adsorption.
Although often not considered inorganic nutrients, trace levels of many metals, e.g., cal-
cium, magnesium, manganese, copper, cobalt, zinc, iron, and molybdenum, are essential for
microbial growth and metabolism. However, high concentrations of the heavy metals, espe-
cially mercury, lead, and cadmium, can be toxic to microorganisms. Interestingly, areas that
have been contaminated with heavy metals often have microbial populations that have become
resistant to heavy metals. Therefore,the presence of heavy metals at a site or in a waste stream
does not preclude bioremediation. The presence of high concentrations of calcium and mag-
nesium in variably saturated soil may seriously interfere with the physical process of trans-
porting nutrients and oxygen through a subsurface system. Both calcium and magnesiumwill
combine with phosphate to form an insoluble precipitate. Precipitation of calcium and mag-
nesium phosphates can clog geological formations during in situ soil and groundwater treat-
ments, thus preventing proper circulation of nutrients and oxygen throughthe treatment area.
In order to avoid practically irreversible clogging, the calcium and magnesium concentrations
must be determined when the in situ flushing technique is under consideration. The amountof
phosphorus added for in situ treatment can usuallybe adjusted to prevent precipitate formation
even in situations where high concentrationsof calcium or magnesium are present.
Soil
Biodegradation
in Pollutants
of Organic 415
Divalent cation chelators appear at first to be useful amendments for binding calcium and
magnesium. This makes the ions unavailable for interaction with phosphorus. Citric acid and
EDTA (ethylenediaminetetracetic acid) are both effective chelators for calcium and magnesium
ions. However, both compounds are organic, and both are easily biodegraded. The usual result
of adding citric acid or EDTA is that these compounds serve as alternative and preferred sub-
strates for the bacteria. Insteadof biodegrading the compounds of interest, the bacteria degrade
the chelator. Therefore, the benefits and effects of these chelators shouldbe thoroughly defined
prior to application.
C.SurfactantEnhancement
A persistent and often frustrating constraint on biodegradation effectiveness is the adsorption
of target substrates onto fine-grained soils and within the immobile liquid phase[49,50]. Be-
cause of the persistence and sorption of hydrophobic chemicals, it is probable that sorption acts
as a limiting mechanism for biodegradation. Solubilization of chemicals through the applica-
tion of surfactants has received increased attention [5 l]. The effect of various anionic and
nonionic surfactants on the solubilization of petroleum hydrocarbons including anthracene,
phenanthrene, and pyrene has been demonstrated in soil-water suspensions [52]. Theory on the
subject to date implies that if a surfactant solubilizesthe sorbed compound, the molecule will
then become readily available in the bulk fluid phase for microbial attack [53]. A similar notion
advanced by Kuhlmeier [54] found that surfactants can also promote immobile-phase extraction
of trace chlorinatedaliphatics, rendering them more amenable for vapor-phase extraction. Ben-
eficial uses of these productshave also been reported in soil-washing and pump-and-treat tech-
nologies [55,56].
What makesa surfactant molecule effectiveis its amphophilic nature, as it has two distinct
structure moieties, one polar andthe other nonpolar. The polar moietyof the molecule has an
affinity for water and many other polar substances. Conversely, the nonpolar moietyis hydro-
phobic. A surfactant molecule can dissolvein water as a monomer, adsorb to a solid surface,
or be incorporated with other surfactant molecules as part of a micelle. Critical micelle con-
centration (CMC)is the surfactant concentrationat which monomers begin to assemble incol-
loidal aggregates[57]. At surfactant concentrationsgreater than the CMC, additional surfactant
is incorporated intothe bulk solution through micelleformation. CMC values for a number of
surfactant solutions have been compiled by Mukerjee and Mysels [58]. Solubilization of pe-
troleum hydrocarbons and other hydrophobic substances starts at the CMC and followsa linear
function of surfactant concentration overa wide range of concentrations [57].
Evaluation of a surfactant for its ability to solubilize
a given chemicalmay be accomplished
using the molar solubilization ratio (MSR). The MSR is defined as the number of moles of
organic compound solubilized per mole of surfactant added to solution [59]. The increase in
solubilizate concentration per unit increase in micellar surfactant concentrationis equivalent to
the MSR. It is represented by the slope of a curve plotting solubilizate concentration against
surfactant concentration. The MSR for aromatic hydrocarbons can be calculated as
where S, is the total apparent solubilityof a chemical in micellar solution (moYL);

Sapp,the apparent solubility of a chemical at the CMC (mol/L); and
CS"*, the surfactant concentration at which S, is evaluated (mol/L).
Liu et al. [52] presented an alternative solution thatstill relies on batch column test design
theory. This theory attempts to partition the organic compound between micelles and mono-
meric solution with a mole fraction micelle phase/aqueous phase partition coefficient. The
416 Kuhlmeier
Table 2 AromaticSolubilityApplyingSurfactants
Aromatic solubility (mollL)
Compound No.Without
rings
surfactant
CMC (X l0-q MSR log K m
Naphthalene 2 3X 10-4 2.5-5.0 0.2-0.5 4.2-5.8

Phenanthrene 3 I X 10-4 0.1-0.4 0.1-0.2 5.4-6.5
Pyrene 8 4 X IO” 0.001-0.005 0.01-0.08 6.0-7.0
micelle phase/aqueous phasepartition coefficient, K,, is the ratio of the mole fraction of the
compound in the micellar phase, X,, to the mole fraction of the compound in the aqueous
phase, X,. Using batch tests, K, can be calculated as
and
X, = MSW(1 + MSR) (15)
The mole fraction of aromatic compound in the aqueous phasein dilute solutions(<0.5%) can
be approximated by
x, = S,, v, (16)
where V, is the molar volume of water (Umol). K , can then be expressed as
Experimental observations have been reported for only a sparingly few compounds. Re-
sults will also be specific to surfactant type. Nonionic surfactantsare preferred over anionicor
cationic surfactants becauseof differences in surfactant toxicity, biodegradability, and change.
Polyoxyethylene (POE) compounds comprise over 75% of nonionic surfactants produced in
America. From this majorclass, two octylphenol-POE andnonylphenol-FQE types are recom-
mended. Representative ranges for C,,, (CMC), MSR, andK , are given in Table 2 for two- to
four-ring aromatic hydrocarbons.
VI. CASE HISTORIES

Results fromfour independently performed petroleum landfarm sites are compared in an effort
to quantify the significance of several limiting growth parameters previously discussed andto
determine a threshold concentration below which biological activity ceases. At lower concen-
trations, it was expected that the microbial mix would change from predominantly eutrophic
species to oligotrophic species.The oligotroph is able to grow at low substrate levels, whereas
the eutrophic species multiplies at high concentrations. Consider that a single organism must
use up a certain amount of organic macronutrientsand substrate to provide enough energy to
maintain the cell. Therefore, whenthe nutrient concentration is quite high, diffusion will pro-
vide molecules to the cell surface at a rate that is rapid enough to meet the energy needs for
maintenance and growth. As substrate declines, growth ceases, and, finally, at a critical sub-
strate concentration, even maintenance cannot be satisfied.
Biodegradation
Pollutants
of Organic in Soil 417
A. Selection of Test Systems

In this reviewwe consider exclusively land treatment systems. Land treatment, or landfarming,
is a method by which contaminated soilsor sludges are excavated and placed in a lined treat-
ment cell. This technique has several distinct advantages over in situ treatment.
As previously
mentioned, it allows for better control of the system by controlling the depth of soil and the
surface area exposed. In turn,one is able to more accurately control soil temperature, nutrient
concentrations, moisture content, and oxygen availability. Placing a liner with a leachate col-
lection system beneath the soil column prevents any additional contamination potential and
provides for recovery and recyclingof water and nutrient. An added benefit of landfarming is
found in the ease of sampling and hence cleanup verification. Zones of slow degradation can
be readily identified and targeted for enhancement. This method allows for system optimization
in a manner in which other techniques do not.
Drawbacks to landfarming are primarily those of economics. Excavation and construction
of the treatment cellmay be costly, but the cost of off-site excavation and disposal exceeds that
of landfarming by a factor of 2 or more. Available space to operate is the other significant
constraint. Soil depthsare maintained between6 and 10 in. to accommodate complete tillingby
a disk or chisel plow. Therefore, the total surface area required mayexceed 2 acres for a
medium-size tank farm remediation project.
The four landfarms chosen for this review represent varying climatic conditions and initial
chemical concentrations. In addition, discrete parameter sensitivity analyses were performedat
one or more of the treatment sitesso that data could be presented both independently and col-
lectively. Each of the four locations (Ohio, California, Michigan, and Texas) contained petro-
leum hydrocarbon-contaminated soils.
B. Discussion
A synopsis of significant sitedata is presented in Table3. The maximum initial concentration
encountered was approximately 5100 mg/kg, and the lowest initial concentration was 3940
mgkg. The minimum concentration achievedat any site was74 mg/kg of total petroleumhy-
drocarbons (TPH). Values less than 100 mg/kg represented less than 10% of the total number
50
of observations, thereby suggesting that a threshold for effective biodegradation is between
and 125 mg/kg, accounting for measurement accuracy and precision.
Biodegradation flux or loss rates were calculated for the four sites collectively
and parti-
tioned by concentration incrementsas shown in Table4. Loss rate declines generally fit a first-
orderdecayfunction,withacclimatedsoilscontainingover 3000 mg/kg TPHdegrading
-
substrate at a mean rate of 95 mg (kg day). Dispersivity of data at concentrations above
500 mg/kg was low, typically less than10%of the mean.As substrate declines and competition
Table 3 LandfarmingPetroleum-Contaminated SoilsSummary Statistics for Four Sites

~~
Initial conc. TPH (mgkg) Final conc. TPH (mgkg)

Duration
Plot size Depth
No. Avg
Location
Max. . Min.
Avg.
Max. (weeks) (acres) (in.)
1 Ohio 5 100 3800 194 158 107 8 14-23' 2
2 California 4650 2611 96 87 74 10-42
8 1.4
3 Michigan 2150 1875 147 112 93 16-38
7 1.5
4 Texas 3940 18 17 133 106 89 18 0.5 12
TPH = total petroleum hydrocarbons.
'Activity ceased at point where cleanup criteria were exceeded.
418 Kuhlrneier
Table 4 Petroleum Loss Rates

~ ~ ~~
Loss rate (mg/kg)
Concentration*C,, (mgkg) Max. Avg . Min.

~4OOo 157 95 74
1000-4OOO 71 53 40
500-1000 57 38 26
250-500 23 9.5 4.0
100-250 8.0 5.4 1.9
<100 1.3 0.8 0
'Lowest observed value, 74 mg/kg.
sites disappear, pockets of viable and inviable activity form, and dispersivity increases to as
much as 80% of the mean value at concentrations less than 200 mglkg. The effects of the
several individual parameters contributing to this phenomenon are discussed in turn below.
Specific observations were made with respect to threshold values and inhibition points for
four parameters-oxygen, biological population enhancement,soil moisture, and temperature.
As noted previously, these factors do not constitute all of the potential constraints on biodeg-
radation of petroleum in soils; however, they representcritical elements that can often be con-
trolled in a applications environment.
1. OxygenLimitations
The primary purpose of tilling in a landfarm is to optimize the contact of soil microbes with
atmospheric oxygen. In soils, aeration depends on the total amount of air-filled pore space.
Elimination of air-filled porosity through excess wateringor compaction reduces oxygen trans-
fer between the microbial colonies and the substrate. Large amountsof biodegradable organics
in the top layer of soilwill deplete oxygen reservesin the soil and slow down oxygen diffusion
to the deeper layers.
Oxygen levels were measured at selected points in each of the four tests at l-week inter-
vals. More frequent oxygen monitoring was performed in the first 2-3 weeks for purposes of
evaluating tilling and moisture requirements.At three s i t e s d h i o , California, and Michigan-
tilling biweekly was optimal. At the Texas site, where temperatures were significantly higher,
oxygen transferwas more efficient and frequent; weeklytilling produced markedly higher deg-
radation rates. This observation is somewhat contrary to that expected. The maximum oxygen
content measured in soil water was 6.5 mg/L, which is approximately 80% of saturation. The
minimum amount of oxygen measured,0.9 mg/L, was at 6 in. below the surface in a soil that
had not been tilled for 4 weeks. Microbial growth was foundto be inhibited at concentrations
below 2.5 mg/L, and total cell loss was detected at oxygen concentrations below 1.4 mg/L,
which were found in plots with very low soil moisture.
2. MicrobialDensityEnhancement
One way to enhance biodegradation of organic compounds is to inoculate the soil or ground-
water (as appropriate) with microorganisms known to metabolize the chemical readily. This
concept has been roundly debated for its performance by various researchers and commercial
vendors of inoculum [m]. Both successes and failures have been notedin the literature. It has
been my experience that commercial bacteria cannot be relied upon as a sole source as their
populations tend to die off quickly, thus requiring numerous reapplications. In the natural en-
'h..
1oC
.... .".. Control (Tilled)
.".""".
",; T-
I \ \
% TPH
Remaining 50
\
\
""*
".". -......
40-
30-
20-
10 -
0 1 2 3 4 5 6 7 8 Q 1 0 1 1 1 2 1 3 1 4 1 5
Time (Weeks)
Figure 3 Effects of a proprietary inoculum to degrade TPH compared to a horse manure as a bacteria
additive over time.
vironment the hybrid species face competition, predation, or parasitism. Any of these inter-
actions could account for the inability of introduced microbes to survive [61].
The potential of hydrocarbon mixtures to be eliminated at a higher rate from soil when
hydrocarbon-degrading bacteria are added to the soil is also a much disputed matter. A general
criticism of the seeding approach is that the use of an allochthonous microbial population may
not be necessary or effective in most cases. Also, most isolates implicated in petroleum hy-
drocarbon biodegradationare gramnegative, non-spore-forming bacteria. These are difficultto
store in large quantities in a manner that preserves their viability.
Bioaugmentation was usedat the landfarm in Ohio.The ability of a proprietary inoculum
to degrade TPH was compared to horse manureas a bacteria additive and the simple addition
of sufficient macronutrients (fertilizer). Resultsof this evaluation are given in Figure 3. Inoc-
ulum was applied on a biweekly basis as population density levels were found difficultto main-
tain. Manure was found to lastat least 4 weeks before a reapplication was needed. While the
commercial additiveneeded substantially less acclimatization time in the soil-4 days as com-
pared to 3 weeks for the manure-its effectiveness diminished rapidly after the first month of
testing. After 15 weeks of activity the horse manure subplot performed the best, followed by the
commercial additive subplot and then the subplot with only macronutrient additions. Although
the performance difference between horse manure and commercial organisms is statistically
insignificant, the test indicated that continuous use of commercial bacteria was not beneficial.
It was determined, however, that initial injection of commercial bacteria decreased acclimati-
zation time, and ongoing injection of 5-15% of such bacteria with fertilization probably is
valuable and economically sound.
3. MoistureEffects
Moisture is essential to the growth of soil microorganisms. Water provides the mechanism for
the exchange of reactants and food absorption through the cell walls. Excessive amounts of
moisture can be disruptive. Commensurately, when soil moisture drops to near the point of
420 Kuhlmeier
o
lo -
90-
80-
70 -
96 TPH
60- m 85+% Saturation
Remaining 50 - B4 5 % Saturation
l1
40-
M
lo
0’
At 4 Weeks At 8 Weeks At 12 Weeks
Figure 4 Effects of moisture on petroleum degradation, plot 3.
specific retention, usually corresponding to 10% by volume or less, metabolic activity ceases.
Bossert and Bartha [62] suggested that moisture contents be maintained in the range of 20-
80%. Biodegradation studies performedat the site in Michigan sought to define a more accu-
rate or narrow range where moisture content is optimum.
Moisture data from three different subplots are shown on Figure 4. All other parameters
such as temperature, soil type, and nutrient loadings were kept as constant as possible; only
moisture content was deliberately varied. Values of 15%, 50%, and 85% of saturation were
chosen for the test. These levels were checked once a day for a total test period of 12 weeks.
Losses from the 15% moisture subplot were minor over the entire duration of the test. TPH
loss that was observed is believed to be due almost exclusively to volatilization, not biodeg-
radation. It was thus confirmed that moisture contents below 20% are threshold limiting to
biodegradation.
Biodegradation was observed in the 85% subplot but was only about one-third the loss
observed in the 50% moisture subplot. This evidence suggests that indeed inhibition 80% above
is present but is not a threshold condition.It is further offered, basedon the performance of this
test, that optimum moisture levels are probably in the range of 4040% of saturation. Addi-
tional study in this area is warranted.
4. TemperatureEffects
Temperature affects the respiration rates of microorganisms, and, through controlling respira-
tion, temperature affects metabolism. It also affects the solubility of the host hydrocarbons.
Temperature is directly related to the amount of evaporation and volatilization from the soil,
which in turn impacts microbial populations. Mesophilic organisms in general perform bestat
about 95°F. Huddleston and Cresswell [63] reported petroleum degradationat temperatures as
low as 30T.Kuhlmeier and Sunderland [M] found that inhibition became easilydetectable at
temperatures below 55T.
Temperature was closely monitored at each of the four test locations. Mean TPHloss rates
were calculated across a wide range of temperatures. Results of this analysis are presented in
Figure 5 . Beginning and ending TPH concentrations for a given period in which the average .
Biodegradation of Organic Pollutantsin Soil 421
90
70
%Loss 50-
TPH
40-
30-
20-
lo]
0
40 50 60 70 80
Tmperahrre (4)
Figure 5 Effects of temperature on microbial activity, plots 1-4.
daily temperature was in a designated temperature bracket (i.e.,OS, OS, etc.) were summed,
and the mean loss was derived from data in all tests. There was virtually no biodegradation
associated with observations at temperatures under 50°F. Losses shown in Figure 5 represent
volatilization losses and measurement inconsistencies.
There was a significant difference between degradation rates below 80°F from those above
this reference value. Interestingly, biologically attributable losses above 95°F did not prove to
be significantly greater than thoseat 85". Although less than 2%of the total observations were
at temperatures above 100"F, there was a noticeable difference from the balance of the data
points. When ambient temperatures exceeded 100°F the mean percent TPH loss was observed
to be 92%. The slight dropoff from the80s-90s bracket is postulatedto be attributable to high
due to heat stress, rapid moisture loss,
initial volatilization losses but subsequent cell mortality
or nutrient constraints or possibly some combination of these factors.
VI. CONCLUSIONS
A reviewof data collected at four independent petroleum landfarming operations has suggested
that biodegradation of contaminated soils may be kinetically limited at concentrations below
50 mg/kg. Loss rates decline dramatically when remaining substrate dips below 150 mg/kg.
Oxygen levels become criticalat 2 mg/L asmeasured in soil moisture. Ideally, soil mois-
ture should be maintained in the 4 0 4 0 % of saturation range. Ambient temperature hits a
threshold limit for degradation at approximately 50°F and reduces microbes to cell maintenance
levels once temperatures drop to 45".
The addition of commercial microorganisms was not found to be highly beneficial. Natural
additives such as sewage sludge or horse manure do enhance microbial activity by introduc-
ing large quantities (and diverse types) of microbes. Macronutrients, although not detailed
specificallyinthediscussion, are importantforcellactivity.Acarbordnitrogen ratio of
160: 1 as suggested by the American Petroleum Institute appears to be overly conservative.
422 Kuhlmeier
Carbodnitrogen ratiosof 6 0 : 1 to 160: 1 were used at the various sites, with little evidence that
the lower concentration of fertilizer was inhibiting growth.
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19
Siallon: The Microencapsulation of
Hydrocarbons Within a Silica Cell
Tom McDowell
Siallon Corporation
Laguna Niguel, California
1. INTRODUCTION
The magnitude of the effort required for remediation of hazardous waste sites throughout the
country is staggering. The number of underground storage tanks that are registered with the
U.S. Environmental Protection Agency (EPA) alone is estimatedat between 1.8 million and 2
million, of which25% are assumed to be leaking [l]. The costs associated with cleanupof our
hazardous waste problems are even more appalling. The remediation of underground storage
tanks (USTs) alone is estimated to cost $67 billion, assuming that current regulatory policies
do not get any more stringent. The cost of cleaning up all hazardous waste sites could reach
$1.7 trillion by the year2020 [2]. Numbersof this magnitude will make the remediation of haz-
ardous wastesone of the most pressing and vital matters for the next several decades. Cost/benefit
analysis will become the driving force in the environmental community; no longer will webe
able to pay exorbitant prices for soil remediation, nor will we have to. The responsible party
(RP) isnow more educated, more cost-conscious, more aware of the available options, and much
more receptive to new and innovative methods. Such willbe the focus of the next generation,
a move away from the “dig and haul” mentalityto treatment and eliminationof the problem.
One of the low-cost soil and sludge remediation methods that has been widely used for
many years is the solidification or’stabilizationof heavy metals. These techniquesare generally
based on the addition of a cementitious materialto the contaminated soil and the formation of
a solid monolith. Due to the multitude of reactions that take place both within the cementitious
material and between theheavy metals and the cement,this process can work well, with a few
drawbacks. The most significant downsideof well-solidified heavy metal-contaminated soil is
the large volume increase requiredto provide an adequate degree of nonleachability. This vol-
ume increase can be as little as 15% or as much as 150% of the original contaminated soil
volume [3,4]. The advantages ofsolidificatiodstabilization,however, most often far outweigh
these disadvantages. High volume throughput (100 yd3/hr is common) and low cost makethis
an attractive process for heavy metal solidification.
425
426 McDowell
It is these distinct advantages that have led many people to consider and actuallyuse this
type of process for the remediation of hydrocarboncontaminated soils. These attempts have
met with varying degrees of success, from outright failure [5] to some measure of solidifica-
tion that is usually contaminant-dependent [6]. These inconsistent results haveled EPA to
state that “immobilization of organics is uncertain” [7,8] and that the most stringent tests
for total hydrocarbons should be used in assessing the results of any organic solidification/
stabilization process.
The main reason for poor success is the fact that all of the conventional solidification,
. stabilization, or fixation processes use some type of cementitiousor pozzolanic material as the
mainstay of the process. Materials such as portland cement, fly ash, kiln dust, and lime (the
four major cementitiousor pozzolanic materials used) all undergo hydration reactions as part
of the curing process. It is well known within the concrete industrythat the setting of concrete
can be retarded by adding a small amount of diesel fuel prior to pouring the concrete. The
hydrophobic diesel fuel absorbsonto the crystal faces of the pozzolanics and effectively blocks
the infusion of water and subsequent hydration and thus the curing of the cement. This dichot-
omy of trying to solidify something that inherently prevents solidification has given solidifi-
cation of organics its “uncertain” reputation and more recently has ledto vendors looking at
additives such as carbon and clays to improve the retention of hydrocarbons within a solidified
matrix [9].
The Siallon processfor the microencapsulation of organics and hydrocarbonsis a unique
approach that does not use any cementitious or pozzolanic materials. It is a simple two-step
chemical reaction that results in the hydrocarbon being encapsulated within a micrometer-sized
particle of silica [10,11]. As there are no large amounts of pozzolanics used, there is no large
volume increase with treated soil and no attenuated cure time, and results are always deter-
mined using total concentration analysis.
II. THE SIALLON PROCESS

A.
Overview
The chemistry of the patented [l21 Siallon process is simple in that it is a two-stage reaction
involving two water-based products. The first step uses a water-based emulsifier that first de-
sorbs the hydrocarbon from the soil and then emulsifies it within a water phase. The second
stage is the addition of the Siallon reactivesilicate solution tothe mixture of soil and emulsified
hydrocarbon. The silicate undergoes an acid-base reaction with the emulsifier micelle and is
neutralized, forming a micrometer-sized particle of silica around the droplet of hydrocarbon.
As the essential reaction, the neutralization of the silica, is a simple acid-base reaction, it is
virtually instantaneous.The speed of this reaction leads to very high volume throughput during
soil remediation; depending upon site-specific conditions, throughput ranges from 25 to 200
tonshr.
The only limitation on the process is that the hydrocarbon or organic contaminant has to
be emulsifiable. This means thata wide variety of contaminants such as gasoline, dieselfuel,
jet fuel, motor oil, crude oil, greases and lube oils, coal tars, PCBs, chlorinated solvents, and
many others can all be successfully treated withina soil or sludge matrix. Similarly,the phys-
ical nature of the host material plays little part in the final remediation results. All types of
soils, from sand to clay, sludges, and tars, respond well to treatment, with the only modifica-
tions being to the actual processing or mixing equipment utilized. Pug mills, ribbon blenders,
Bomags, and modified soil composting equipment have been usedfor the application and mix-
ing of the Siallon reagents.
Siallon: 427
Applications of this process range from remediation of gasoline-contaminated soil from

a UST location to in situ remediation of PCB-contaminated soil at a transformer manufactur-
ing plant. Encapsulation efficiencies for benzene, ethylbenzene, toluene, and xylenes (BETX)
99.97%
and total petroleum hydrocarbons (TPH) in the gasoline-contaminated soil ranged from
to 100%. Encapsulation efficiencies for the in situ PCB remediation ranged from 99.9991%
to 99.9999%.
B. Siallon Chemistry
As mentioned previously, the Siallon process of microencapsulation is a simple two-step pro-
cedure. The first step, the emulsification of the hydrocarbon, is the heart of the process. Sur-
factant chemistry shows that when a hydrophobic materialis emulsified it forms a micelle[l31
within the aqueous phase. This micelle is composed of a droplet of hydrocarbon surrounded by
surfactant or emulsifier. The reason for this is the molecular structure of the surfactant. Mo-
lecularly all surfactants, emulsifiers, wetting agents,and detergents have a common structure,
a hydrophobicor oil-loving “tail” that is oil-soluble and a terminal hydrophilic or water-loving
portion or “head” that is water-soluble. The hydrophobic tail will attach itself to the hydro-
carbon particle, with the hydrophilic head conferring water solubility on the entire molecule.
As emulsion proceeds, moreand more surfactant molecules attachto the hydrocarbon particle
in the same orientation. Such extremely close packing of the surfactant molecules occurs that
the concentration of surfactant around the micellesin a given solution is much higher than the
concentration within the bulkof the solution. The final result is a spherical form of hydrocar-
bon surrounded by close-packedsurfactantmoleculeswithinthewaterphase.Theactual
amount of surfactant requiredto first produce desorption from soil and subsequently emulsify
the hydrocarbon is extremely small in relation to the mass of soil. Consider that the clothes
washing done in the average home is with an aqueous solution containing less than O.OOO1
mol% surfactant for removal of body oils and grease[141. This very high rateof activity allows
the Siallon process to remediate contaminated soil with relatively small amounts of additives
and no volume increase between the untreated soil and the treated soil.
The Siallon emulsifier differs from conventional surfactants or other emulsifiers in thatit
contains an acidic moiety as part of the hydrophilic end or head of the molecule. The acidic
moiety will orient itself along with the hydrophilic end toward the aqueous phase, in essence
producing a hydrocarbon microdroplet surrounded by and attached to the oil-loving portion,
surrounded in turnby the water-loving portion and thenby the acidic moiety. In essence there
are a series of spheres or shells around the hydrocarbon, ending with a shell that has acidic
reactive sites on its surface. The average diameter of these shellsor micelles is less than2 pm.
The small size of the micelles results in a very stable emulsion with or no
littletendency to split
or revert.
All individual hydrocarbon compounds are susceptible to emulsification, and each com-
pound responds to a very specific ratio between the size of the hydrophobic and hydrophilic
portions of the emulsifier molecule. A product such as crude oil is composed of hundreds of
individual compounds, each emulsifying best at a specific hydrophobic/hydrophilic ratio. To
overcome this problem and produce the smallest possible micelle and most stablepos- emulsion
sible for the various hydrocarbon products requires a range of emulsifiers, each covering a
range of hydrophobichydrophilic ratios. Each of the Siallon emulsifiers is a water-based, non-
toxic product having a pH in the 4.2-5.5 range.
The second step of the Siallon process is the addition of a water-based silicate that is
slightly alkaline with pHa of 9.5. The silicate undergoes an acid-base reaction with the acidic
sites on the emulsifier, which neutralizes the silicate. This reaction forms silica, water, and a
428 McDowell
trace amount of salt. As the acidic sites are formed in a sphere around the emulsified micelle
ofhydrocarbon, the silica in turn forms a cell around the micelle. The final product is a
micrometer-sized particle of silica containing bothemulsifier and the drop of hydrocarbon.
Extensive characterization of the morphology and chemical nature of the silica cell was
undertaken. Chemical analysis of the bulk material by both X-ray spectrometry and energy-
dispersive X-ray analysis (EDXA)showed that the material formed was more than 98% SiO,,
with a trace of salts. These results were consistent with the neutralizationof silicates in which
the reaction products are normally silica, water, and simple salts.
C. Siallon Cell Morphology

The evaluation of the physical characteristics of the Siallon silica cellwas aimed at answering
two questions: How durable is the cell? and How is the hydrocarbon held within the interior?
In most cases at least two different analytical or instrumental techniques were employed for
each step in order to confirm the answers by separate methods. Samples of motor oil that had
been encapsulated withthe Siallon process were usedas the basis sample formost of the eval-
uations of morphology.
The first item consideredwas the exactcrystalline structure of the silica cell. The generally
accepted structures of silica are crystalline forms of quartz, cristobalite, and tridymite, of
which only the quartz is thermodynamicallystable [U].Amorphous silica canbe formed by the
very slow cooling of molten silica, resulting in a random array of three-dimensional units or
chains of SiO,. When the Siallon silica cells are examined with a microscope under plane-
polarized light, the cells appear to be highly colored. Under plane-polarized light, crystalline
materials transmit the light without distortion and appear as bright or white areas. It was ob-
vious that the Siallon cells were amorphous silica.This was reaffirmed by the use of selected
area electron diffraction, where allof the samples show an amorphous haze, with the exception
of the trace of a salt formed as a by-product of the reaction that was confumed to be sylvite,
a common form of NaCl.
The next step was evaluation of the surface characteristics of single silica cells. Both scan-
ning electron microscopy (SEM) and transmission electron microscopy (TEM) were employed.
The SEM micrographs show the surface to be fairly regularin appearance, nonporous, and with
a solid monolithic character. The TEM micrographs show that the silica cell is essentially a
solid particle rather than a hollow sphere. This left the question of how the hydrocarbon was
held within the silica cell. It was obvious fromthe SEM work that there was encapsulation of
the hydrocarbon rather than adsorption, as the surface was nonporous, and also obvious that it
was not a zeolite typeof open-lattice structure thatwould lead toabsorption. Thenext step then
became the cutting of thin sections of single silica cells using a diamond knife in an ultrami-
crotome. The sections were first evaluated with SEM at 15,OOOX, 30,OOOX, and 60,OOOX
magnification and shown to be a random mix of solid matter and void space. They were then
analyzed by EDXA, which showed that the solid matter on the interior of the cell was essen-
tially pure SiO,. To further evaluate the configuration of the interior, the SEM micrographsof
the thin sections were computer-enhanced; the results show a three-dimensional, mazelike, ran-
dom honeycomb structure very much like a closed-cell urethane foam.
The results of the chemical and morphologicalinvestigations can be summarized as fol-
lows:
The Siallon reaction productis essentially pure silica-this provides a material with negligible
water solubility, extreme hardness and durability, and resistance to acids and alkali.
The silica is a stable amorphous form and as such is not prone to fracture or cleavage along
crystal planes.
Siallon: 429
The surface is solid and nonporous and will thus preventor retard leaching out of the encap-
sulated hydrocarbon.
The interior of the micrometer-sized silica cell is a mazelike configuration of almost infinite
tortuosity within which the hydrocarbon is firmly embedded.
1 -. .
.,,
.*,
*A.
:’
111. LEACHABILITYSTUDIES wsw P*’
A. Waste Leaching Tests-An Overview

In general a leaching test involves contacting the waste material with a liquid, the leachant, to
determine how much Contaminant is released or dissolved into the liquid. There are two basic
types of leach tests, the extraction tests suchas EPA’s Toxicity Characteristics Leaching Pro-
cedure (TCLP), inwhich the leachate is not renewed during the test, and dynamic testsassuch
the column leach tests used in this study, in which the leachant is periodically replaced or re-
newed. Extraction tests can be further categorized according to whether the sample is agitated
or nonagitated and whether only one extraction is run or multiple or sequential extractionsare
used. Dynamic tests can be further categorized according to how the waste and leachant are
brought into contact.
Serial tests involve the use of a granular or crushed sample that is leached by periodic
leachant renewal. Flow-through and flow-around tests are dynamic tests in which the sample
is a porousor solid configuration, respectively. Flow-through tests are typically used for a va-
riety of soil samples. Procedures such ‘as column or lysimeter studies are typical of flow-
through tests.
With any leach test there areat least five variables that canbe manipulated to ensure that
the test represents either a real-life situation, a worst-case scenario, or equilibrium conditions.
Sample preparation can involve simple grinding, aging, curing, compaction, or surface wash-
ing of monolithic samples. Leachant composition can be varied from simple distilled waterto
actual site leachate or to a variety of acidic or alkaline synthetic solutions, each designed to
provide specific contaminant-release information. The method of contact of the waste and the
leach solution canbe agitated or nonagitated, open to the atmosphereor a closed system.The
amount of leachate used relative to the amount of sample defines the liquidkolid ratio for
the procedure. Thisratio should be low enough to allow analysis of the contaminant and high
enough that solubility of the contaminant is not a limiting factor. The fifth variable is the
amount of time a sampleand the leach solution are in contact. For extraction tests using ground
samples, contact time is usually24-48 hr, however, for the same test for monolithic samples,
the time requiredto reach equilibrium conditions couldbe weeks or months. In dynamic tests
such as column extraction tests, contact time is simply a function of the flow rate of the leach
solution and the amountof leach solution passed through the column.
The data generated from a properly designed leaching protocol can be used to predict the
mechanism by whichaparticularcontaminantisreleasedfromawaste(e.g.,diffusion-
controlled), to predict relationships between time and contaminant release, or to simulate real-
life conditions and the resultant flux or release of contaminant per unit area.
B.Column LeachTest-Description
When hydrocarbon-contaminated soil that has beenmated by the Siallon process is analyzed,
the appropriate total concentration analysis is used. These methods will generally involve sol-
vent extraction followedby gas chromatographic analysis, which gives a result that is indicative
of the sample as it stands or at a fixed point in time. To assess the effects of both time and
groundwater intrusion on Siallon-treated soils an extensive leachability study was undertaken.
430 McDoweLL
The studyinvolvedmorethan 80 samplesandmorethan 600 separate analyses ofboth

gasoline- and diesel-contaminated sandy soil, silty sand soil, and clayey soil.
The soil samples used forthis study were prepared in the laboratory by spiking the appro-
priate soil type with approximately 10,OOO mgkg of gasoline or diesel fuel. The spiking was
done in a side-rolling, airtight mixer with theappropriate amount of gasoline or diesel sprayed
into a mixing chamber, containing approximately70 lbof soil, over a 6-hr period, and then the
soil was homogenized by continued mixing for a further 6 hr. The samples were treated by
adding the Siallon reagents while mixingin a laboratory-scale pug mill capable of processing
12 lb of soil per minute. Each treatment required35-40 Ib of contaminated soil, and the treat-
ments were each done in triplicate for each contaminant (gasoline anddiesel) and for each of
the three types of soils [16,17]. The samples were then analyzed for TPH using EPA Method’
8015 as modified by the California Departmentof Health Services (DHS). Thisparticular vari-
ation of Method 8015 used methylenechloride and sonication to extract the hydrocarbons from
the soil, followed by gas chromatographic analysis of the extract.
Table 1 shows the results of the treatment of gasoline-contaminated sandy soil anddiesel-
contaminated sandy soil. The average difference between the treated and untreated samples
equates to a 99.9% encapsulation efficiency.To ensure that the leaching study results were not
all “non-detect” results, the treated samples with the highest residualTPH-in other words,
the samples with the lowest encapsulation efficiency-were used for the balance of the study.
These worst-case resultsof the treated samplesam listed in Table2, showing the initial soil
analysis andthe treated sample analysis.All analyses were run with EPA Method 8015 as mod-
ified by California DHS. The 12 samples from Table2 were used for both phases of the leach-
ing study.
Phase 1 of the study involved column leachability studiesat ambient pressure on both com-
pacted and uncompacted samples. Phase2 consisted of column leachability studies similar to
those in Phase 1 but in a closed system at pressures of 500-1800 pounds per square inch (psi).
The leaching solution used for all samples was 0.1 M sodium acetate at pH 4.9, and analysis
of the leachate was with EPA Method 8015 as modified by California DHS. Each of the 12
samples was run through the Phase 1 and Phase 2 procedures both in an “as is” state and after
being compacted to 100% compaction.
C.ColumnDesign
For the Phase 1 ambient pressure study, graduated glass chromatography columns,5 cm in di-
ameter and 70 cm in length and equipped witha stopcock, were used. The columns were first
Table 1 Comparison of TreatedandUntreated SamplesSandy Soil

~~~~~ ~ ~
Initial
untreated
Siallon-treated
Contaminant
Sample
Sample ID. TPH (mg/kg) TPH (mg/kg)
Gasoline Control S- 16-6 7400
Gasoline Run 1 S- 16-1 c0.05
Gasoline Run 2 S-16-2 5.4
Gasoline Run 3 S- 16-3 0.9
Diesel Control S- 14-6 lo400
Diesel Run 1 S-14-1 6.6
Diesel Run 2 S- 14-2 12.2
Diesel Run 3 S- 14-3 13.4
TPH = total petroleum hydrocarbons.
Siallon: 431
Table 2 Summary of Relevant 'Ihxtability Results for Gasoline- and Diesel-Contaminated Soils
Initial untreated Siallon-treated
t.D. Sample Soil type "W-I pH
S-16-6 Gasoline Sandy 7400
S-16-2 Gasoline Sandy 5.4
S- 16-12 Gasoline Silty sand 8350
S-16-8 Gasoline Silty sand 34.1
S-16-18 Gasoline Clay 9150
S-16-13 Gasoline Clay 78.4
S-14-6 Diesel Sandy lo400
S- 14-3 Diesel Sandy 13.4
S-14-10 Diesel Silty sand 10700
S-14-8 Diesel Silty sand 78.2
S- 14- l6 Diesel Clay 9200
S-14-13 Diesel Clay 412.5
charged with3 cm of glass wool followed by 30 g of clean sand and another3 cm of glass wool.
The soil, compactedor uncompacted, was then added in three lifts totaling 250 Theg. soil was
then gently tamped with a 1 in. aluminum rod to remove air voids and channels. Each column
was equipped with a gravity feed systemto provide a constant volumeof 600 mL of leachant
above the top of the soil column. As the columns were allowed to run, the leachate was col-
lected in 250-mL volumes, equivalent to one pore volume of the soil. A total of six pore vol-
umes was collected from each column, the diesel collected at ambient temperature and the
gasoline collected into VOC containers in ice baths set at -5°C. Each of the Siallon-treated
samples was runin triplicate with one run of the untreated control sample, requiring four col-
umns for each sample run, a totalof 24 columns for the compacted samples and 24 columns for
the uncompacted samples.
The Phase 2 high pressure study required construction of a stainless steel column, by 2 in.
12 in. stainless steel tube equipped with threaded endsand sealed with caps. The interior was
fitted with a 3/8-in. (179-mm) porous glass frit and No. 4 Whatman filter paper. The column
was equipped with two pressure gauges, one within the soil area to measure the soil pressure
and one above the soil leachant interfaceto measure the solvent pressure. Inlet and exit valves
were installed in the sealed caps. The same mass of soil as in the Phase l study, 250 g, was
added to the open column, followedby 500 mL of leachant. The chamber was then sealed and
hydraulic pressure was applied. The leachate was collected in 200-mL increments, equal to one
pore volume of the soil, for a total of six pore volumes.
D. Leachability Results
There are three key analyses from this study, total concentration analyses
by EPA Method 8015
as modified by California DHS of the untreated and treated samples and the cumulative total
of the amount of TPH released over the six pore volumes in the column leaching. As shown in
Table 3, the Siallon encapsulationof the diesel-contaminated soils isso confining or tight that
even the aggressive solvent extractionof Method 8015 Modified cannot extract the contaminant
in the treated samples.However, as is also shownin Table 3, the total amount of contaminant
leached out of the treated samples is much less than is shown as available for leaching or as
unencapsulated by the TCA method. This held for all of the samples, with the total amount
leached ranging from only10.2% to 67.6% of the available TPHas determined by TCA. Ob-
viously, when the TCA type of analysis is used on Siallon-treated samples, it will detect not
432 McDowell
Table 3 Comparison of TCA and Total Leachate Release for Sandy Soil Samples
EPA Method 8015 Modified Total mg leached
After Before After Before
Contaminant treatment mg. treatment (mg) treatment (mg) treatment (mg)
Diesel 2600 3.35 2605 1.9
only the unencapsulated hydrocarbon but also the partially or poorly encapsulated hydrocar-
bon. In essence, the TCA methods overstate the impact on the environment.
As was mentioned previously, all of the samples were subjected to the column leach pro-
cedure in triplicate, resulting in more than75 samples being analyzed for each pore volume of
leachate. A portion of the mass of data generated is summarizedand averaged for the ambient
pressure study in Table 4.
As can be seen in Table 4, regardless of soil type, contaminant type, compacted or un-
compacted, the decrease in TPH leached over the six pore volumes follows the same rapid
decline for both treated and untreated samples. When the cumulative releaseof TPH is plotted
against the number of pore volumes (and each pore volume hasa time and flowrate factor), the
Table 4 ColumnLeachateStudyResults-AmbientPressure
Total petroleum hydrocarbon (m&)
Pore volume
Soil type Contaminant
Sample
Compaction
condition
1 2 3 4 5 6
Sandy Gasoline Untreated Uncompacted 2350 &Q0 5
60 ND ND
Sandy Gasoline Treated Uncompacted 1.77 0.37 ND ND ND ND
Sandy Gasoline Untreated Compacted 1450 360 110 40 10 5
Sandy Gasoline Treated Compacted 1.25 0.13 ND ND ND ND
Sandy silt Gasoline Untreated Uncompacted 2100 900 650 120 80 20
Sandy silt Gasoline Treated Uncompacted 7.1 1.3 0.4 ND ND ND
Sandy silt Gasoline Untreated Compacted 1650 1040 450 150 60 20
Sandy silt Gasoline Treated Compacted 2.6 0.65 0.2 ND M) ND
Clay Gasoline Untreated Uncompacted 1250 1100 950 600 400 250
Clay Gasoline Treated Uncompacted 9.9 5.3 3.6 1.9 0.65 0.2
Clay Gasoline Untreated Compacted 875 950 700 650 300 120
Clay Gasoline Treated Compacted 7.9 4.8 3.4 2.2 1 0.4
Sandy Diesel Untreated Uncompacted 5600 3100 1150 420 100 50
Sandy Diesel Treated Uncompacted 6.2 1.3 0.3 ND ND ND
Sandy Diesel Untreated Compacted 4400 2300 600 300 80 20
Sandy Diesel Treated Compacted 3.2 0.6 0.1 ND ND ND
Sandy silt Diesel Untreated Uncompacted 4200 1800 750 120 50 10
Sandy silt Diesel Treated Uncompacted 27.8 8.9 4.3 1.3 0.5 0.2
Sandy silt Diesel Untreated Compacted 3600 1400 600 100 80 20
Sandy silt Diesel Treated Compacted 17.3 6.3 1.5 0.6 ND ND
Clay Diesel Untreated Uncompacted 3350 1150 420 60 5 1
Clay Diesel Treated Uncompacted 148.6 68 33.4 19 6.1 2.1
Clay Diesel Untreated Compacted 2400 850 450 100 20 5
Clay Diesel Treated Compacted 73.3 27.1 9.2 4 1.3 0.6
Siallon: Hydrocarbon Encapsulation 433
INCREASINGPOREVOLUME
Figure 1 Cumulative releaseof TPH gasoline vs. increasing pore volume.(.) Sandy treated; (D) sandy
untreated; (+) silty sand treated; (0) silty sand untreated; (A) clay treated; (A) clay untreated.
resultant curves shown as Figure 1 have identical shapes for both treated and untreated samples.
The releaseof TPH fromthe untreated samplesis due to simple washoff or desorption from the
soil surface. There obviously has been no treatment of these samples, since diffusion and ad-
vection do not play a part in contaminant release. As the Siallon-treated samples show iden-
tically shaped release versus pore volume curves, the method of contaminant removalmust be
very similar to that in the untreated samples-a simple washoff of the unencapsulated TPH.
The differences lie in the amounts of TPH released.
One of the uses of leach tests is to determine the actual kinetics of contaminant leaching
from within treated wastes. There are several mechanisms for leaching contaminants from en-
capsulated or solidified materials.
At the particle-leachate interface, both dissolution and desorption can occur.
The contaminant can diffise out of the encapsulated or solidified matrix.
Dissolution of the encapsulant or solidified material will leadto steadily increasing cumulative
release results.
Chemical reaction can occur between the leachant used and either the encapsulation or solid-
ifying material or between the leachant and the contaminant.
According tothe Godbee and Joy [l81 model, a linear relationship between the cumulative
fraction of TPH leached and the square root of time for the leaching is a consequence of dif-
fusion control. When the results from Table 4 are plotted this way, the resulting curve shows
a rapid rise followed by a straight line of zero slope. Since the slope is equivalent to D,' (the
apparent diffision coefficient), it holds that followingthe rapid washoff of the unencapsulated
TPH, there is no detectable diffusion from within the Siallon silica cell. This was to be ex-
pected because the Siallon silicacell is resistant to the extraction effectsof even an aggressive
solvent suchas methylene chloride. This resistanceto extraction meansthat the solvent cannot
penetrate the silica cell to extract the hydrocarbon; similarly,the hydrocarbon cannot diffuse out
of the cell in any leaching protocol.This is clearly shown in Figure 2 and is especially evident
in the clay soil sample, where thereis a rapid washoff of the unencapsulated TPH followedby
a straight line with zero slope, indicating no diffusion from within the Siallon silica cell.
434 McDowell
O L -
*
I
*
-
z -- *
m
019 13.4 23.2 26.8 30 32.9
-
Square R o o t Time
Figure 2 Cumulativefractionleached vs. square mot of time-siallon-treated diesel-contaminated

soil. (M) Sandy; (A) silty sand; (4)clay.
E. LeachabilityConclusions
This intensive study of the leachability of hydrocarbons encapsulated with the Siallon process
is only a small part of the ongoing researchinto the durability, integrity, and life span of pro-
cessed materials.This study did, however, provide a number of significant conclusionsas to the
behavior of the Siallon silicacell.
1. The Siallon process was effective in encapsulating both diesel fuel and gasoline in sandy
soil, sandy silt soil, and clayey soil.
2. The Siallon silica cell is not affected by compaction or the tamping pressure of compac-
tion.
3. The Siallon silica cell is not affected by pressures up to 1500 psi.
4. Hydrocarbons that are encapsulated within the silica cell will not diffuse out of the cell or
leach into the environment.
5 . The limiting criterion for the long-term effectiveness of Siallon-encapsulated material is
not soil type, contaminant type, or the volume of leachant; rather it is the efficacy of the
initial Siallon treatment.
One of the main results of these conclusionsis that the Siallon process can easily
be mon-
itored for effectiveness by simple total concentration analysis methods such as EPA Method
8015 as modified by California DHS. Along with this conclusion isthe fact that when Siallon
treatment is used at a contaminated site and is required to meet state cleanup levels, the ac-
tual effect of the treatment on the environment will be even less than that expected from the
set levels.
IV. SIALLON APPLICATIONS AND MIXING EQUIPMENT

The Siallon microencapsulation process is applicable to the treatment of a wide varietyof waste
materials. The hydrocarbonsthat have been successfully treated and foundto be amenable to
treatment by microencapsulation include crude oil, gasoline, coal tars, creosote, lubricants,
diesel fuel, jet fuel, PCBs, and refinery wastes.
The differencesbetween many types of wastes are related not so much to the type of con-
taminant as to the physical form of the waste matrix. The treatments of pure crude oil, crude
Siallon: 435
oil-contaminated soil, and crude oil sludgeare all chemically similar; the differences lie in the
physical form of the material to be treated and in how it is handled during treatment. The most
important aspect of any Siallon treatment is that adequate mixing of the host material must be
obtained during the application of the reagents. For materials differing in physical character-
istics, it is obvious that different mixing equipmentor methods are required.
For remediation of normal contaminated soil,pug a mill has been found to meet all of the
requirements for efficient application of the Siallon process. Apug mill is simply a continuous
mixer with twin side-by-side helical mixing blades. The pug mill is used in many industries for
a variety of mixing and blending operations. The concrete industry and the mining industry are
large users of pug mills. For the processing of Siallon-treated soil, the large throughput of a pug
mill combined with the instantaneous reaction of the Siallon reagents makes the pug mill an
ideal tool for remediation of small to large quantities of soil. Pug mills for soil remediation
range in size from15 tonshr up to 200 tonshr. At these rates the Siallon process becomes one
of the most cost-effective remediation methods available.
Processing contaminated soil through puga mill is a relatively simple operation.The soil
is added to the pug mill hopper via a conveyor or auger system. As the soil enters the hopper,
the Siallon emulsifier is appliedby spray. Approximately halfway down the pug mill, the Sial-
lon reactive silicate is added. The soil exits the pug mill after a 90-sec residence time and is
ready for final disposition.
The pug mill is adjustable for mixing speed and residence time as well as flow rate and
pressure of the spray-applied reagents. This allows a pug mill to easily be configured to treat
many different contaminants, soil types, levels of contaminant, and various site conditions with
the Siallon process.
For sludges or heavy clays of high moisture content, a ribbon blender is the most appro-
priate mixing equipment. Ribbon blenders are used in a wide variety of industries for mixing
and blending everything from powdersto pastes. The food, chemical, detergent, pharmaceu-
tical, and paint industries all make use of this versatile mixer. These mixers come in watertight
configurations for mixing pastesor fluids, which makes them ideal for use as a mixing system
for sludges, tars, or other high water content materials.
The use of ribbon blenders for soil or sludge remediation with the Siallon process is a
batch-type production. The mixer is charged with known
a quantity of sludge and is then turned
on. After 30 sec of mixing to ensure homogeneity of the mixture, the Siallon emulsifier is au-
tomatically sprayed into themixer. This is mixed in for 2 min, after which the Siallon reactive
silicate is automatically added. Afurther 2 min of mixing ensures that total reaction has taken
place, and the treated soil is dumped through a bottom valveto a conveyor.
Ribbon blenders come in sizes ranging from 1 to 30 yd3 capacity,so processing 100 tonshr
of sludge is a simple matter. The watertight nature of the blender ensures that everything that
comes out of the system is treated and encapsulated.
The useof these blenders provides for excellent QNQCprocedures as all of the processing
parameters can be easily monitoredor adjusted.
For soil remediation on specific sites where the contaminant has little or no volatile com-
ponent, there is a large amount of debrisor cobble in the soil, and there is sufficient space to
lay out the contaminated soil in windrows, a tractor-driven soil-mixing machine has found ap-
plication. The Dirt Witch is similarto equipment used for composting soil in its overall design.
The differences are in the mixing blades, the spray system, and the control system. Theequip
ment used for the application of Siallon reagents is modified to provide intimate soil mixing
rather than the simple blending accomplished with cornposting machines. The mixing blades
are L-shaped to provide maximum turbulence in the soil. Reagent is added from a bulk storage
tank controlledby pressure settings and flow rate to provide the proper spray pattern and force
436 McDowell
of impingement on the soil particles. A tachometer is used to ensure constant mixing speeds,
and a low-speed speedometeris used to ensure a constant mixing timeon any given soil block.
There are several advantages to the use of this equipment for ex situ remediation. Only
debris larger than 10 in. has to be removed from the soil. Processing rates are upwards of 100
tonslhr, depending uponsite conditions. The equipmentis simple and inexpensive, working off
the power take-off of a standard tractor.
To remediate soil with the Dirt Witch, the soil is laid out in windrows on a plastic liner.
The windrows are generally 6 ft high and 8 ft wide, the lengthof the windrow being governed
by the site. The Dirt Witch moves through the windrow, mixing and adding the reagents in a
sequential manner. In other words, it will makea complete pass mixingand applying the Sial-
lon emulsifier and then a second complete pass mixing and applying the Siallon reactive sili-
cate.
For on-surface or shallowdepth soil remediation, the use of a Bomag or similar type of
mixing equipmenthas beem found to be the most practical. These mixersare generally used for
soil or sludge solidification, and the only modifications necessary are the addition of the re-
agent flow control and spray system. Their mixing depthis usually limited to 18 in., and their
speed in applying Siallon materials is 1 mph on an 8-ft-wide path. This makestheir use one of
the most cost-effective and efficient methods of remediating large sites where the contamina-
tion is all within the top foot of surface.
V. SITE REMEDIATION OF GASOLINE-CONTAMINATED SOIL

The actual remediation of a site is always the true test of whether or not a process has appli-
cability within the environmental industry, and whetheror not it will find acceptability among
the regulatory agencies and clients.’The following documents the remediation of gasoline-
impacted soilat a UST site in Los Angeles, California.As with the majority of service stations,
speed is of the essence when it comes to soil remediation and tank replacement. If a service
station is shut down for tank replacement and the associated soil remediation, is not
it pumping
gas, and in the case of some of the large stations in the Los Angeles area this can representthe
loss of sales of tens of thousands of gallons. With speed ofremediation in mind, the client chose
the Siallon process for remediation of the soil at this particular site.
A.SiteCharacteristics
The site is in Los Angeles and is located about 1.5 mi east of the Pacific Ocean. It lies at an
of a silty sandt
elevation only slightly above sea level. The soil was ype,with fair permeability.
Approximately 700 yd3 of contaminated soil had been excavated and stockpiled on site and
covered with plastic during sampling, analysis, permitting, and work plan preparation.
The soil contamination at this site resulted from spillage as well as leaking underground
storage tanks (USTs) and their associate piping. It had an average TPH of 6700 ppm and an
average BTXE contamination of 320 ppm. The “hot spots” ranged as high as 67,000 ppm
TPH and 2300 ppm xylenes. All the soil had to be remediated as part of the work plan.
Outside the “hot spots,” the TPH levels ranged from nondetectable up to 5200 ppm, with
an average TPH of 1920 ppm. The BTXE components range from nondetectableto 190 ppm
xylenes, with an average BTXE of 79 ppm.
B. RegulatoryAffairs
Siallon Corporation provided a pug mill, fully permitted as a transportable treatment unit
(“U) capable of processing 20 tons of soil per hour. Siallon Corporation sampled the heated
Siallon: 437
material and had an on-site mobile, state-certified laboratory perform EPA 8015 as modified
by California DHS and EPA 8020 analyses on all appropriate samples.
The soil was to be remediated on-site with the TTU-permitted pug mill. At present the
operation of a TTU for remediation is allowed under Permitby Rule (PBR), which requires all
appropriate regulatory agenciesto be notified prior to each site remediation. As the movement
of contaminated soilprior to remediation may lead to some air release of volatile hydrocarbons,
approval by South Coast Air Quality Management District (SCAQMD) to operate was also re-
quired through their Rule 1166 permitting procedure. The regulatory agencies that were re-
quired to be notified were SCAQMD, Los Angeles Fire Department, Los Angeles County
Department of Public Works, California Department of Health Services, and the Regional Wa-
ter Quality Control Board.
C. AnalyticalandSampling Methods
All analyses were performed by a state-certified laboratory in accordance with the following
methods:
Analyte Analytical procedure

Total petroleum hydrocarbons EPA Method 8015, Modified
Total recoverable petroleum EPA Method 418.1
hydrocarbons (TRPH)
Benzene, toluene, ethylbenzene. and EPA Method 8020
total xylenes (BETX)
Organic lead California DHS-LUFT Method
Sampling of the Siallon-treated material was done with the aid of an automatic samplerat
the exit to the pug mill. The sampler retrieveda sample every6 min and placed it in a sealable
container for cornpositing prior to analysis. The regulatory requirements for analysis required
one sample for every 75 yd3 of soil processed.
D. SiallonTreatment
Siallon Corporation provided a fully permitted pug mill capable of processing 20 tons of soil
per hour, two experienced operator/technicians, and the labor and equipment required to load
the contaminated soil into the pug mill and stockpile the clean material on-site. Siallon Cor-
poration also regularly sampled the treated material and had a certified laboratory perform
EPA 8015 and 8020 analyses on all appropriate samples.
The pug mill used for the encapsulation of the gasoline-contaminated soil entails several
preparatory steps: setupof the unit, prescreening of the soil, and pretreatmentof the soil. In this
case the pretreatment step required that the contaminated soil be sprayed with a dilute (1 part
Siallon emulsifier to 10 parts water) Siallon emulsifier solutionto minimize the possibility of
any volatile emissions duringthe soil prescreeningstep. The treatment unitwas transported to
the site via a 45-ft trailer.
The soil that had been excavated previously was analyzed for TPH by the client’s consul-
tant, thus allowing forthe calculation of the appropriate dose rates for the Siallon reagents. The
choice of dose rate was sufficient to encapsulatethe hydrocarbons at the highest contamination
levels. The actual dose rate used was 0.007% by weight of soil of both the Siallon emulsifier
and the Siallon reactive silicate.This would equate to 14 lb of emulsifier and 14 lb of reactive
silicate per ton of soil.
438 McDavell
The influent soilwas continuously monitoredfor volatization of hydrocarbons with a por-

table organic vapor analyzer(OVA), because exceeding 50 ppm of volatile organics in the air
would have required a major interruption of the remediation. There wasno major interruption
in the remediation of the soil stockpile.
After being wet withthe dilute emulsifier solution to control VOC emissions, the contam-
inated soilwas loaded into a feed hopper that was equipped witha shaker screen.The soil was
then automatically conveyedto the back portion of the twin-screw pug mill for mixing. There
the emulsifier blend was sprayed on the soil in thefirst portion of the mixing chamber. The soil
was mixed and moved downthe pug mill and approximately halfway along the Siallon reactive
silicate solution was spray-applied. The treated soil was then discharged to a stockpile until
analysis was completed. After effective Siallon remediation, the treated soil was transported
for use as day cover at a designated Class I11 landfill as the client had used a mixture of sand
and pea gravel to backfill the excavated tank cavity.
E. Remediation Results
The client was concerned about the time requiredfor remediation, and thesite was cleaned in
less than 7 working days.A summary of results is presented as Table 5 . The summary clearly
shows the efficacy of the Siallon process in remediation of contaminated soils. An encapsula-
tion efficiency of greater than 99.9% and essentially nondetect results for all contaminants
was two orders of magnitude lower than the required regulatory cleanup levels of 100 mg/kg as
TPH gasoline.
Clearly, a significant amount of contaminated soil had been promptly and effectively re-
mediated with the Siallon microencapsulation process, yielding a soil that easily met the reg-
ulatory target. Following the Siallon soil treatment, the regulatory agencies allowed the soil to
be used in a Class I11 landfill and the facility to be delisted. The environment had been pro-
tected quickly and completely, with no expectation of any further impact from the contami-
nated soil.
VI. CONCLUSIONS
This chapter has shown how the Siallon process for the microencapsulation of hydrocarbons
differs from conventionalsolidification or stabilization processes. Its simple two-step chemical
process avoidsmany of the pitfalls inherent inother processes. It has clearly shown itself to be
another tool in the remediation of contaminated soil, and as such its advantage of speed and
efficiency can be teamed with other remediation methods to provide the client with the best
possible alternatives at the lowest costs. The Siallon process can be used to remediate the
source area of the highest contamination ona site where biodegradation is being used for re-
mediation of the plume area. At a site where vapor extractionis operating in a plume area, the
Table 5 Gasoline-ContaminatedSoil-RemediationResultsSummary
Highest before Avg before Avg after Encapsulation
Contaminant
treatment (mag) treatment (mgkg) treatment (mg/kg) percentage
~~~~ ~~ ~ ~
TPH gasoline 67O

,OO 6670 <OS >99.99
Benzene 120 12 CO.01 >99.9
Toluene 420 48 0.04 99.9
Ethylbenzene 350 36 <0.01 >99.9
Xylenes 2,300 220 0.19 99.9
Siallon: Hydrocarbon Encapsulation 439
Siallon process can quickly clean up the heavy source contamination to prevent any further
migration into the plume or groundwater.
The Siallon microencapsulation process is designed to reduceor eliminate the mobility and
toxicity of the contaminant and thereby lessen or eliminate the contaminant's impact on the
environment andhuman health. This reduction in toxicity and mobility is a function of the ef-
ficiency of the Siallon treatment, the rate of leaching of any untreated or unencapsulated ma-
terial, and the lifespanof the silica cell.Whenthesefactors are optimized, aninformed
decision as to the safety and reliability of the encapsulation can be made.
REFERENCES
1. The Jennings Group, Underground Storage Tank Markets, 1991-1995, Chatham, N.J., 1991.
2. M. Russel et al.,Hazardous Waste Remediation: The Task Ahead, Univ. Tennessee Waste Manage-
ment Research and Education Institute, December 1991.
3. U.S. EPA, Guide to the Disposal of Chemically Stabilized and Solidfied Waste, US.Environmental
Protection Agency Publ. SW-872, Washington, D.C., September 1980.
4. Solidtech Inc. SolidificationlStabilization Process-Applications Analysis Report, U.S. EPA Publ.
EPA/54OIA5-891005, Risk Reduction Engineering Laboratory.
5. Quicklime PCB treatment, Hazardous Waste Consultant, SeptemberlOctober 1991.
6. Caldwell, R. J., and Cote, F? L., Investigation of solidificationfor the immobilization of trace or-
ganic contaminants, Hazardous Waste Hazardous Mat., 7, 3 (1990).
7. Office of Solid Waste and Emergency Response, Immobilization as Treatment, U.S.EPAPubl.
9380.3-07FS, 1991.
8. Funderbruk, R., EPA still doubtjkl about organic immobilization, Hazmat World, February 1991.
9. StabilizationlSolidification of CERCLA and RCRA Wastes, U.S. EPA Publ. EPA/625/6-89/022,
May1989.
10. McDowell, T. K.,Microencapsulationof hydrocarbons in soil using reactive silicate technology, in
Hydrocarbon Contaminated Soils and Groundwater, Vol. 2 (Calabrese and Kostecki,eds.), Lewis,
Chelsea, Mich., 1991.
11. Siallon Technical Manual, Siallon Corp., Laguna Niguel, Calif., 1992.
12. Noonan,W.R.,andMcDowell,T. K.,Oil treatment method, U.S. Patent 5,076,938 (December
1991).
13. Shwartz, A. M., and Perry, J. M., Surface Active Agents, 3rd ed., Interscience-Wiley, New York,
1949.
14. Considine, D. M., ChemicalandProcessTechnologyEncyclopedia, McGraw-Hill,NewYork,
1974.
15. Cotton, F. S., and Wilkinson, G., Advanced Inorganic Chemistry, Interscience, New York, 1962.
16. Gasoline Fuel Contaminated Soils, Siallon Corp. Rep. B102A. September 1991.
17. Diesel Fuel Contaminated Soils, Siallon Corp. Rep. BlOlB, August 1991.
18. Godbee, H.W., and Joy, D. S., Assessment of theLoss of Radioactive Isotopes from Waste Solids
to the Environment, Part 1: Background and Theory, Oak Ridge National Laboratory, Oak Ridge,
Tenn., Publ. No. T"4333, 1974.
20
Remediation of Heavy Metal
Contaminated Solids Using Polysilicates
George J. Trezek
Greenfield Environmental
Carlsbad, California
and Universiq of California at Berkeley
Berkeley, California
1. INTRODUCTION
The polysilicate technologyfor the remediation of heavy metals in solidor semisolid matrices
is a commercial process capable of cost-effectively treating materials at rates on the order of
100 tonsihr. This process is known in the industry as the STS technology. The process evolved
through a series of laboratory bench-scale studies, pilot field tests, and the construction of
commercial-scale mobile systems.
The development of the process began inearnest in early 1985 as a project to ascertain the
technical and economic feasibilityof treating the heavy metals containedin automobile shred-
der residue. The California Departmentof Health Services (DHS) requiredthat this material be
managed as a hazardous waste because it failed to pass the California wet extraction test(CAM
test) for certain metals such as lead, cadmium, and zinc. After the successful development of
a treatment protocol on the laboratory scale, a pilot system was installed as part of the shred-
ding plant process line. A full-scale permanent on-line treatment system was installed toward
the end of 1985.
Following the initial success with auto shredder residue,the treatment was applied to mit-
igating heavy metals in other types of materials. These have included heavy metal-contami-
nated soil, bag house dust, electric arc furnace dust, incinerator ash, filter press cake, foundry
sand, wastewaster treatment sludges, and sludges from a variety of other manufacturing oper-
ations. Thus far, the majority of experience with the technology has been through its applica-
tion of remediating heavy metals contained in soil-like substrates such as soil, clay, sand,
sludges, and residues as well as mixtures of these materials. Depending upon the particular
circumstance or site, thequantities of treated material range from several thousandto several
hundred thousand tons. The nature of the metals also varied fromone predominant constituent
to a material containing five or more elevated metal concentrations.
Consideration will be givento the nature of the technology, the development of treatment
protocols, the delivery of the technology for site remediation includingcase studies, and a de-
441
442 Trezek
scription of the governing parametersthat encompasses hydration andcuring, compactability,

final particle size distribution, and long-term effects.
11. NATURE OF THE TECHNOLOGY

The plysilicatetreatment technologyis a chemical treatment that uses commercially available
soluble silicate solutions and various cementitious materials such as cement, lime, pozzalime,
and fly ash [1,2]. Relatively small amountsof polysilicates andcementitious materials are used
to change the chemical characteristics of heavy metals containedin solid or semisolid matrices.
Consequently, this chemical treatmentdiffers significantly fromthe so-called solidificationhta-
bilization technologies, requiring as much as a 100% addition of reagents. Three principal steps
are involved in delivering the treatment: (1) thorough wetting of the material containing the
heavy metals with a silicate-water blend, (2) the addition of appropriate cementitious mate-
rials, and (3) curing of the mixed material into a friable form suitable for backfilling.The fol-
lowing discussion deals with the chemistry associated with these steps [3].
Typically, the common metallic compounds found in materials requiring treatment are a
mixture of free metallic ions and other metallic ions resulting from metal chlorides, sulfates,
carbonates, etc., and metallic oxides and hydroxides as shown below.
Free Metallic Ions
2 H20 r"-H3O+ + OH-
M'"*M' + a e- + (6G - S@)
Other Metallic Ions
MCl, F+ + a Cl-
M"+
Mb(S04&C- b Ma+ + c S042-
Mb(C03)ce- b M" + c C q 2 -
Metallic Oxides/Hydroxides
In field applications, the free metallic ions are usually present in small quantities. The
actual concentrations of these ions and of the other metallic ions resulting fromsalts, oxides,
and bases are determined by the equilibrium Gibbsfree energy of the constituents of the mix-
ture. These concentrations are also influenced by various kinetic factors relatedto the presence
of catalysts and particle size distributions. On the other hand, theconcentrationsof the metallic
oxides and hydroxides are also typically related to the material generation source and influ-
enced by historical temperature, chemical medium, moisturecontent, and age. These metallic
substances can be contained in a wide variety of substrates such as various soils, clays, soil-
clay mixtures, amorphous silica containing a broad spectrum of grain sizes, sludges generated
as a by-product of industrial processes, and combinations of these materials.The following lead
and zinc reactions are typical of metallic constituents requiring treatment:
H20 + 2 e- + ZnO C - ZnO2 + H2C- Zn(0H)z

Remediation
Solids of Heavy
Contaminated
Metal 443
As previously mentioned, the first element in the treatment involves wetting with the pol-
ysilicate-water blend that is created priorto its introduction into the mixing process. The most
effective treatments have used potassium silicates, which are a family of chemicals with a wide
range of physical and chemical properties. They are clear, highly viscous liquids having a pH
in the range of11.3-1 1.7. The viscosity is affected by the Si0,/K20 ratio, concentration, and
temperature. For example, the lower theratio and the more alkaline at a given solids content,
the lower the viscosity. When the silicate is mixed with water it quickly forms a solution whose
viscosity approaches that of water. Also, relatively small temperature increases, on the order of
10°C, can cause a fivefold decrease in viscosity.
The formation of the liquid silicate polymerbecan represented by the following equations.
Water
Liquid Silicate
As shown, the liquid silicates depolymerize when mixed with water, revealing their active
negatively charged oxygen sites. Further, the silicon backbones themselves go into smaller, ion-
ically charged clusters.
The following shows the nature of the reactionthat occurs between the active metallic el-
ements, divalent in this case, in the material and the liquid silicate polymer.'
2x K+ + 2x OH- + 2u KOH
' This balance considers the active metals. not the silicates, to be the limiting reactants.
444 Trezek
OH
H0
Here, ionically active metallic compounds react with the liquid silicates to form stable
metal silicate chelates. The formation of these metal silicates is kinetically relatedto a number
of factors suchas themetal ionizationstate, particle size,reaction temperature, andactivation
energy. Further, when a combination of heavy metalsare present in a material requiring treat-
ment, reaction priority is given to the more electropositive heavy metal. Thermodynamically,
the reaction progresses toward a minimum potential energy equilibrium state.
After the material has been thoroughly wettedby the polysilicate-water blend, a cemen-
titious material is introduced into the process. The metal polysilicate chelates, and other me-
tallic compounds are incorporatedinto a crystalline cementitious matrix. The following
example illustrates the hydration of cement and lime, which are two commonly used cemen-
titious materials.
Portland Cement (In cement chemistrynotation2)
2C3.S + 6H + 3C.2S.3H + 3(CH)
2C2.S + 4H + 3C.2S.3H + CH
4C-A-F + 1OH + 2(CH) + 6C-A.F.12H
3C-A + 12H + CH + 3C.ACH.12H
3C-A + 10H + CS.2H + 3C.A.CS-12H
Lime
+
2CaO + 2H20 + CaOeH20 + Ca(OH)2 27.5 kBN(lb-mo1)
Ca(OH)2+ C a 2 + + 2 OH-
+
a Ca2+ a OH- + Ma+ + M(OH), a Ca2' +
+
CaCO3 + 78 kBtu/(lb.mol) + CaO CO, (gas)
Remediation
Contaminated
Solids
Metal
of Heavy 445
During the hydration of portland cement, active ionic bonds begin to transform into co-
valent bonds of greater stability. As the metal polysilicate chelates are incorporated into the
cementitious structure, the size and stability of the usual 7-10-silicon backbone crystalline
structure is increased. In addition, the metal polysilicates, along withactive metal oxides and
hydroxides, tend to chelate the cementitious silicate chains by providing the necessary elec-
tronic bonding clouds. Again, the relatively weak ionic bonds are transformed into strong co-
valent bonds linking metal to oxide or hydroxide and the oxide or hydroxide to the silicon
backbone.
Typically, lime is used in combination with cement. Whenisitapplied separatelyto multi-
metallic materials, highly soluble metal hydroxidechelates can form. However, in combination
with cement, it can provide the heat necessary to activate and accelerate metal oxidation and
cement hydration reactions, thereby yieldinga stronger structure. The resulting configuration
is a three-dimensional, low potentialenergy crystalline cementitiousmatrix that has
orderly passivated metallic elements integrated into itsstructure. An example of the transfor-
mation of this structure from the ionic to the covalent state is shown below.
I I I I I I I
0 0 0 0 0 0 0
0 0 0 0 0 0 0
I I
I I I
I I
Si-0-Si- 0-Si-0-Si-0-Si-0-Si-0-Si
I
I I I I l I
OH OH OH
' M OH). ' M
o/c" '0 0 '0 0
I I l
I I I I
Si-O~i-O-~i-~-~i-O--Si~-Si-O-si
I I
I I I I I
0 0 '0 0 0 0 0
111. DEVELOPMENT OF TREATMENT PROTOCOLS

A series of bench-scale treatability studies are commonly used to establish aninitial treatment
protocol. Typically,a series of samples taken from representative areas in the field, particularly
those having the highest concentrations, are evaluated in the laboratory and then subjectedto
a range of treatment protocols.Thus, the treatability studies providethe initial data that validate
the applicability of the process for the associated metals. These testsalso give an indication of
the effectiveness of the reagents, that is, the polysilicate blend, and the quantity and compo-
sition of the cementitious materials. After a basic protocol is developed and optimized, the
treatability studies provide an initial estimate of the treatment costs.
The treatment protocolsused in the application of the STS technology are sensitive to the
nature, type,and combination of metals present, the material substrate, and the overall physical
446 Trezek
characteristics of the material. These featuresare organized into a database (Table 1) contain-
ing the following principal information:
Laboratory identification for internal tracking
Generator information
Waste classification
Physical characteristics
Treatment reagents
Extraction information
Pre- and posttreatment soluble and total metalconcentrations
The database is designed to include other nonsilicate reagents thatmay be applicable tothe
use of the STS technology in conjunction withother procedures suchas metal extraction, trans-
formation of metal states, and the combined treatment of hydrocarbon- and metal-contaminated
materials. Provisions are also made for the evaluation of both the STLC and TCLP extraction
methods. (The STLC procedure is the so-called California test based on sodium citrate as the
leaching agent.) Further, information on metals other than those regulated is included because
of their importancein the overall treatment dynamics termsin of metal-metal interactions and
matrix bonding stability. The results of approximately 800 treatability and commercial treat-
ment evaluations are currently stored in the database. In addition to providingthe information
necessary to quantify the chemical nature and validity of the treatment, the database offers
valuable insights intothe development of protocols for new materials requiring treatment.
Examples of the efficacy of the treatment are given in Table2 for five metal groups. With
the exceptionof group 4, these groups contain various concentrations of the same six metals-
arsenic, copper, lead, nickel, cadmium, and zinc. In each case, values are given for the total
metal concentration (TTLC) and the pre- and posttreatment soluble metal concentration as
measured by either the STLC or TCLP procedure. The important features are summarized as
follows.
Metal system 1. Here copper is the predominant metal as given by both the total and soluble
concentrations. The treatment resulted in a primary reduction in copper, a secondary re-
duction in lead, and minor ductions in the other metals.
Metal system 2. Based on total concentrations, arsenic and copper are the primary metals;
however,only the soluble concentration of arsenic exceeds regulatory limits. Here the
treatment resulted in a primary reduction in arsenic, secondary reductions in copper and
zinc, and essentially no detectable reductions in the other metals.
Metal system 3. This system is characterized by elevated levels ofcopper, lead, and zinc.
Arsenic is essentially not involved in this metal system. Here the treatment significantly
lowered the levels of all the metals.
MetaI system 4. The metals of principal concern in this system are copper, lead, cadmium,
andzinc.In this metalgroup,nickelremainedrelativelyunchangedwithtreatment,
whereas the other metals experienced significant reductions.
Metal system 5. This system exhibits elevated total concentrations of arsenic, copper, and
lead. Based only on totals, this would be classed as a three-metal system. However, this
group also exhibits elevated soluble levelsof nickel and cadmium,so it behaves as a five-
metal system. The treatment significantly reduced the soluble levelsof arsenic, copper, and
cadmium. The soluble levels of zinc and nickel were reduced to
a lesser extent, whereas the
level of lead remained essentially unchanged.
The reactions in these five metal groups are complex and often not exactly predictable.
Competing ions suchas calcium, magnesium, iron, and, to a lesser extent, sodium, potassium,
Remediation of Heavy
Contaminated
Solids
Metal 447
and cationic charged substances like clays, often occupy active sites within the developing ce-
ment-silicate matrix preferentially over the contaminant ion and can decrease the stability of
certain precipitants prior to the poyolanic reaction. Equilibrium between the metals present,
their oxidation states, and the competition exhibited during induced reactions are complicated
and are typically determinedby experimental processes. In this regard, the use the of database
allows treatment options to be predetermined, thereby permitting actual treatment protocols to
be expeditiously established.
IV.DELIVERY OF THE TECHNOLOGY

For site remediation applications, the technology is delivered by means of a mobile system that
can be operated under a TTU (Transportable Treatment Unit) permit. The equipment is versa-
tile and self-contained, requires a relatively small space, and can be made operational on a site
within two to three working days.
The principal elementsof the treatment system, shown schematically in Figure 1, consist
of the feeder, magnet, screen, pug mill mixing plant, and polysilicate blending unit. The actual
equipment used in the latter two elements is shown in Figure 2. These unit operations are op-
erated as an in-line continuous system with a throughput of 100-125 tonshr.
A brief description of the system (Figure 1) follows. Soil requiring treatment is taken from
stockpiled material with a front-end loader and fed into a variable-speed feeder equipped with
a set of grizzly bars to remove large tramp material. In some cases, to improve material han-
dling and eliminate certain objects that could fall through the grizzlies (which could cause tears
in the feeder belt or jams in the feeder, resulting in excessive equipment maintenance down-
time), stockpiled material is prescreened with a short residence time mobile screen. After the
material exits the feeder, it passes under a cross belt magnet to remove any ferrous material that
may be present. (This fraction is common in scrap yard remediations.) The material then enters
a triple-deck screen, where the large oversize fraction consisting of pieces of concrete, asphalt,
wood, etc., is removed on the top deck. After the middle fraction (i.e., smaller rocks, stones,
nonferrous metals, etc.) is removed, the remaining material is the undersize soil that is suitably
conditioned for treatment. The feedrate of the material entering the feed hopper on the treat-
ment unit is recorded by a certified belt scale.
The polysilicate additives and mixing process are configured into two mobile treatment
units. The mixing unit (Figure 2) consists of two feed hoppers, a twin-screw pug mill, a ce-
mentitious material storage silo, and a discharge conveyor. The silo, capable of storing ap-
proximately 50 tons of material, is hydraulically elevated after the unit arrives on the site.
Although a diesel engine generator system is mounted on the mixing trailer to provide a self-
contained source of power, the demands of the ancillary equipment may require the use of a
separate mobile generator on the site. The polysilicate delivery system is contained in a sep-
arate trailer. A 2OOO-gal buffer tank allows the polysilicate-containing water blend to be de-
livered to a spray nozzle system at the point where the soil enters the pug The mill.polysilicates
are added to the buffer tankby means of calibrated metering pumps connected to four 250-gal
tanks. Polysilicate in 55-gal drums can be directly pumped into these tanks from outside the
trailer. Typically, water enters the buffer tank directly from an on-site hydrant. Appropriate
instrumentation allows for the measurement of the flow rates of all water and chemicals en-
tering and exiting the chemical delivery system. Thus, along with the measurement of the soil
throughput, a complete mass balance can be performed on the system.
During operation, material requiring treatment enters the rear of the twin-screw pug mill.
The diluted polysilicate blend is sprayed onto the feed soil. Intensive wetting of the soil with
the polysilicates occurs in the first half-portion of the mixer. The cementitious material is
Table 1 Elements of the Metals Treatment Database
Generator Waste Physical 'Zteatment Extraction
Laboratory I.D. information classification characteristics reagents information Pre- and post-treatment concns.
E
Sample # Generator Waste type % Moisture. Silicate 1 (g) Ext. date (totals) Ag SIZC Ni STLC
Lab I.D. Address Waste code Density Silicate 2 (g) Ext. date (TCLP) Ag TCLP Ni TCLP
Site Location Character Comprehensive strength Cement (g) Ext. date (STLC) Ag TTLC Ni TTLC
Treatment date Size < 1/4 in. Cement type A1 STUJ PbsTLc
Size > '/4 in. Lime (g) Al TCLP Pb TCLP
Size > % in. Lime type AlTTLC P b m
Size > % in. Fly ash (g) AssLC Sb SIZC
Treated size Fly ash type As TCLP Sb TCLP
Waste m t e d (g) Kiln dust (g) A s m Sb TTLC
Kiln dust type Ba STLC Se STLC
Polysulfide (g) Ba TCLP Se TCLP
Y
Polysulfide type Ba TTLC
Phosphate (g) Be STLC
Se TTLC
T1 STLC
5%
Phosphate type
Acid (g)
Be TCLP
Be TIu3
T1 TCLP
TI TTLC F
r8
Acid type Cd sIu3 Vslzc B
Base (g) Cd TCLP V TCLP 5
Base type Cd TTLC V TTLC 3
Oxidant (g) c o STLC zn STLC %

Oxidant type Co TCLP Zn TCLP 2
Q
Reductant (g) c o TTLC ZnTTLC
Reductant type
Other 1 (g)
cam =
Cr(II1) TCLP
ca STLC
Ca TCLP
4
%
r8
Other 1 type Cr(1II) TTLC cam E.

Other 2 (g)
Other 2 type
cr(w =
Cr(VI) TCLP
c1 STLC
C1 TCLP
2
3
c r ( w TTLC CI TTLC 3
cu STu= F e r n
Cu TCLP Fe TCLP
c u TIu3 FeTTLc
FTTZC Mg STLC
FSlZC Mg TCLP
F TCLP Mg
Hg =
Hg !m-.c
Na STLC
Na TCLP
Hg TCLP Na TTLC
Mo sTu= Final dry wt.
Mo TCLP pH solid
Mo TTLC DHextract
Table 2 Total Metal and he-and Posttreatment Concentrations for Metal Gmum 1-5
~ ~~~
Extraction procedure Character Units Arsenic Copper Lead Nickel Cadmium Zinc
Metal system 1
Totals 3050 Initial 2 16,300 2 1.24 0.01 70
STLC initial mg/kg
m a 0.005 589 0.27 1S 2 0.01 0.01
STLC Treated m a 0.001 11.23 0.02 0.88 0.01 0.01
Metal system 2
Totals 3050 lnitial mgkg 3217 I359 21 29 2 398
TCLP #1 Initial mg/L 140 1.11 0.06 0.1 0.01 2.2
TCLP #2 Treated mg/L 0.09 0.12 0.05 0.1 0.01 0.003
Metal system 3
Totals 3050 Initial 0.001 3917 770 30 40 5400
STLC Initial mg/L o.OoO1 383 72 2.89 0.28 915
STLC Treated mglL O.OOO1 0.88 0.075 0.01 0.005 21 -0.5
Metal system 4
Totals 3050 Initial mag N/A 350 537 92 4.95 1,012
STLC Initial mg/L NIA 19.01 31.99 2.56 0.46 87.04
snc TEated mg/L NIA 7.28 0.62 1.64 0.005 0.84
Metal system 5
Totals 3050 Initial 2,759 1,627 1,550 470 48 325
TCLP #2 Initial m gn
mglkg 158.3 34.7 0.33 41.25 1.54 15.7
TCLP #2 Treated mpn 0.068 0.075 0.28 20.91 0.005 0.534
Remediation of Heavy Metal Contaminated Solids 451
?
.p!
8
W
5
B
1I
Fa
B
3.2
452 Trezek
Figure 2 Equipment used in the delivery of the STS technology.
introduced at the midpoint of the mixer. The feed rate canbe adjusted by controlling the
variable-speed drive on the silo rotary vane feeder.The residence timein the mixer is controlled
by the blade angles. For soil, a 22" blade angle is used in the first half of the mixer to enhance
retention (i.e., increase the contact timebetween the silicates and the material). In the section
after the cementitious material is added, the blade angles are set at approximately 45" to en-
hance mixing and removal of the treated material from the chamber. As the treated material
exits the pug mill unit, a radial stacking conveyor pilesthe material. The process is complete
after the material has cured in the stockpiles. The treated stockpiles typicallyare turned with
a front-end loader on a daily basis for several days. A Bomag unit can also be used to cure
treated material. Here, the material is arranged in 3-44? lifts. After the material has partially
set, the Bomag unit traverses the lift, creating suitably sized material.
The final aspect of the treatment includes the sampling and subsequent analytical evalua-
tion of the cured material. This involves obtaining representative samples from treated stock-
piles and subjectingthe material to an extraction test. If the EPA TCLP test is used, the treated
material (crystalline cementitious matrix) is extracted witha sodium acetate-acetic acid buffer
solution. In this process, metallic elements can be leached from the matrix to form metal ac-
etates. As shown below, the final extraction product is an equilibrium mixture of metal poly-
silicates, metal acetates, acetic acid, metal hydroxides, metal oxides, etc.
a CH3COO- + b H+ + c Na+ + d H20 + e M(OH), + fCa(OH)2
+ g metalpolysilicates + - - 4
h (CH3COO),M + i CH3COONa + j CH3COOH k H20 + + l M(OH), + m Ca(OH)2

+ + +
n NaOH o ca3(C~H&)~ p metal polysilicates
Remediation
Solids of Heavy
Contaminated
Metal 453
Thus, in order for a treatment to be successful with regard to the TCLP test, a stable matrix
must be created that resists the attackof the aggressive leachingfluid, i.e., one in which only
negligible quantities of soluble metallic elementsare present. Upon completion of the analyt-
ical data, the treatedfriable material can then be backfilled on thesite with conventionalearth-
moving equipment.
V. CASESTUDIES
Two examples of applying the technology to actual site remediations are given here. These par-
ticular case studies were selected becauseof their diversityin terms of both site conditions and
types of metals. The first case study involves a heavy metal-contaminated site in the Port of
Los Angeles where there had been an extensive metal salvaging operation dealing with a va-
riety of operations that included ship breaking. Asa result of these activities, the soil was con-
taminated with lead, zinc, cadmium, nickel,and copper. The treatmentoperations were carried
out on a clay pad constructed on site. The second case study is an example of “treatment in
tank” that requiredthe construction of an RCRA tank before treatmentoperations were begun.
In this case, arsenic was the principal metal of concern, and its remediation required a mod-
ification of the processing system to include an additionalsilo for the delivery of a second ce-
mentitious material.
A. Case Study I
This case study deals with the remediation of a 23.5-acre site located in the Terminal Island
District of the Portof Los Angeles [4]. The initialsite characterizationanalytical data indicated
that approximately 18-24 in. of top soil material, or about 60,OOO tons of soil, would require
treatment. In actuality, 106,700 tons of soil was treated in the overall project.
A clean areawas prepared onsite for the mobile equipment treatment operations. The con-
taminated layer was removed in a 300 ft by 300 ft area, stockpiled in an adjacent location on
the site, and replaced or backfilled with clean decomposed granite soil. This area provided a
working pad for the equipment and the curing of treated material.
The material requiring treatment was not typical soil. Because of the prior metal salvaging
activities, the material containeda variety of ferrous and nonferrousmetals, rocks and stones,
pieces of wood and asphalt, and other miscellaneous items. The size distribution of these ma-
terials spanned several orders of magnitude ranging from less than l in. to several feet. Occa-
sionally, various parts of ships (i.e., riveted and welded beams, parts of anchors, sections of
mechanical equipment, etc.) were uncovered in the excavation of the site and found their way
into the stockpile for treatment. Consequently, the heterogeneous natureof the material dictated
the type of preprocessing unit operations prior to mitigating the heavy metals.
Although the project was permitted to operate from 6:00 A.M. to 6:00 P.M. five days a
week, the South Coast Air Quality District imposed the added restriction that all operations
including operating rolling stock cease by 5 0 0 P.M. Consequently, the effective daily treatment
window was approximately 10 hr or less, depending upon downtime. A period of at least 1 hr
was required for cleanup, maintenance, moving piles, etc. at the end of each shift. Thus, in
order to meet the project schedule,a nominal 1OOO tons of material per day had to be processed
within these time constraints.
Material requiring treatmentwas arranged in 1000-ton stockpiles, 30 by 150 by 8 ft high,
on the site adjacent to the clean soil equipment zone. Samplesof this material for laboratory
analysis of heavy metals were taken as the piles were generated. Thesedata were used to s u p
plement the original site characterization data and provide guidance in establishing the daily
454 Trezek
treatment protocols.The sampling protocol also involved the collection of samples of untreated
and treated material at 15-min intervals during operation. These samples formeda daily com-
posite, which was split for independent certified laboratory analysis. After receiptof the lab-
oratory report and acceptance by the Port inspectors, the material was backfilled on the site.
Additional samples of the in-place material were also taken.
1. TreatmentLevels
Testing of the contaminated soil for all 17 metals revealed that only five had elevated levels
requiring treatment. The range of these metals in terms of both the soluble (STLC) and total
(TTLC) concentrations is summarized as follows: (1) lead, STLC 11-121 mg/L; TTLC 27-
1500 mg/kg; (2) zinc, STLC 14-320 mg/L; TTLC 242-3130 mgkg; (3) cadmium, STLC 0.1-
1.9 mg/L; TTLC 2-12 mgkg; (4) nickel, STLC 0.2-7 mg/L; TTLC 30-600 m a g ; and (5)
copper, STLC2-96 mgL; TTLC 70-2610 mgkg. The soluble concentrationswere determined
by the CAM wet extraction method, which involves milling to pass a No. 10 standard sieve
followed by 48 hr of extraction in a sodium citrate solution.
The relationship between the total and soluble concentrations summarized inFigure 3
shows the respective ranges for each metal. In effect, the treatment process must deal with
metals whose concentrations cover a range of four orders of magnitude. It should be noted that
the values of lead shown in Figure 3 are plotted as Pb/100 to aid in pattern recognition. Thus,
the concentrationsof lead are in the same general band as copper and the lower range of zinc.
2. TreatmentResults
The actual treatmentactivities began on October9, 1989 and terminated on April 12, 1990. The
treatment of the initial 60,OOO tons of material was completed by the contracted scheduledate
of January 15, 1990. The project period was then extended to treat the additional 47,000 tons
of soil. Approximately 16,000 tons of nonhazardous oversize material was removed in the
screening operation. With the exception of the ferrous metals, this fractionwas disposed of in
a Class 111 landfill.
The quantities of polysilicates and cementitious material were adjusted to coincide with
the concentrations of metals in the in-feed material. Because of a combination of logistical,
economic, andtreatability considerations, cement wasused as thecementitiousmaterial.
Throughout the course of the treatment, the additionof cement ranged from 10.14 to 11.08%.
Even with the wide range of STLCconcentrations of the various metals,the use of polysilicates
varied over a relatively narrow band, which ranged from 0.513 to 0.59 gaton of soil.
B. Case Study II
This study involves the remediation of 40,OOO tons of heavy metals-contaminated soil at the
Thompson-Isaacson site in 'hkwila, Washington. In this soil, arsenic was the principal metal
of concern. Theother metals thatwere evaluated were barium, chromium, copper, nickel,lead,
and zinc. The need for the remediation arose asa result of the planned developmentof the site,
which entailed the construction of an industrial structure necessitating substantial excavations
for foundations and pedestrian tunnels[5].
Elevated levelsof arsenic are believed to have occurredas a result of the dredging,filling,
and straighteningof the Duwamish channel beginning aroundthe turn of the century. Presently,
one of the site boundaries is the Duwamish Waterway, which once flowed through the approx-
imate center of the site before the channel was straightened and redirected. Various site inves-
tigations [6,7] indicated thatthe arsenic contaminationmay have resulted froma variety of fill
materials generated by smelting and other ore processing operations.
0
0
9
0
0
0
0
0
0
-
0
456 Trezek
A number of factors entered intothe decision to use on-site treatment forthe remediation
of the heavy metals. Basically, thisalternative allowed the site owner to maintain control in that
the treated material would remain on-site, thereby reducing the reliance on off-site hazardous
waste landfill disposal and its associated long-term liabilities. Further, the useof on-site treat-
ment at high processing rates (100 tons/hr) eliminates the excessive time associated with truck-
ing large quantities of material considerable distances to Class I disposal sites. Finally, in terms
of construction, since the characteristics of the backfilled STS-treated materialare suitable for
the placement of buildings, the need and costs associated with imported fill materials can be
significantly reduced or eliminated.
The conditions for theuse of on-site treatment were consistent with the treatment in tank
by generator regulations. Consequently,an RCRA tank was designed and constructed withthe
appropriatemembraneliner,asphaltconcretepavement,catchbasins, etc. Basically,this
RCRA tank was designed to not only contain the soil during treatment, but also to collect all
contact and noncontact liquids,which could be subsequently transferred toappropriate storage
tanks. A secondary containment system was also installed for the purpose of monitoring any
leakage ftom this system.
Normally, full-scale or commercial processing would follow the treatability study. How-
ever, in thisproject, the Washington State Department of Ecology, as part of the approval of the
Site Remediation Action Plan[g], requested a 4000-5000-ton pilot field test prior to full-scale
remediation for the purposeof verifying the treatability data and the effectiveness of the treat-
ment under actualfield conditions. It was necessary to first construct the previously mentioned
RCRA tank before the test could begin. The mobile treatment system was then erected in the
completed tank. This system consistedof the feed hopper, mixing unit, chemical delivery sys-
tem, and associated feed and discharge conveyors. In this project, the curing and subsequent
stockpiling of the treated material occurred in the tank.
Approximately 4500.tons of soil was treated at commercial processing rates of 80-100
tonskr during the 5-day pilottest; Material requiring treatmentwas excavated to the water ta-
ble (about 12 ft below the surface) using a standard backhoe machine. Prior to entering the
treatment unit, the excavated soil was screened to a 314 in. particle size through a two-step pro-
cess using grizzly bars and a trommel screen. Stockpilesof the screened material were sampled
and evaluatedfor heavy metals concentrations before treatment. Composite samples of the ma-
terial were also evaluated before and after treatment. Control of the treatment protocol was
accomplished through a mass balance, which entails continuous measurement of the rate at
which material and reagentsenter the treatment unit. The necessary instrumentation included
a certified belt scale on the material in-feed conveyor, calibrated and computer-controlled ro-
tary feeders for dry reagents, and in-line flow meters and calibrated delivery pumps for liquids.
After the successful completion of the pilot test program, the remaining 36,000 tons of material
was processed and subsequently backfilled into the excavation.
1. TreatmentLevels
In this particular soil, as in Case I, a comparison of the total (TTLC) and soluble concentra-
tions (TCLP) for arsenic, copper, and zinc (Figure 4) illustrates that the concentrationsof heavy
metals can vary over several orders of magnitude throughout the site. Arsenic is the principal
metal of concern; copper and zinc exhibitedthe next highest concentrations but did not exceed
TCLP limits. The data shown in Figure 4 were obtained during the pilot test program. During
the production phase, the evaluation of total concentration levelswas not included in the rou-
tine data collection.
An analysis of the data in Figure 4 indicates that the degreeof solubility is a function of
total concentration. In the case of arsenic, the soluble concentrations were about five times
Contaminated
SolidsMetal 457
Figure 4 Relationship between soluble and total concentration levels in untreated soil (Case Study 11).
greater at the highest TTLC levels. In other words, the TCLP levels range between 200 and
lo00 times less than the TTLC levels as they decrease from lO,o00 to 100. Copper exhibits
similar behavioreven though the ranges in TTLC and TCPL levels only span an order of mag-
nitude. On the other hand, the levels of zinc are clustered such thatthe TCLP levelis about 100
times less than the TTLC concentration. Itis interesting to comparethis soil with that of Case
I, which also exhibited concentration levelsof the aggregate or mixture of metals that spanned
several orders of magnitude (Figure 3). However, unlike the arsenic in this soil, the metals in
the Case I soil were grouped or clustered in relatively narrow ranges withinthe overall distri-
bution. Also, another notable exceptionwas zinc, which was not clustered. In these particular
arrangements (Figure 3), the average soluble concentrations (determined by the STLC proce-
dure) were about 20 times less than the total concentration. Extraction procedures will affect
the behavior of soluble concentrations in a mixture of metals. In terms of the above compar-
ison, this would involve differences inthe leaching characteristics between the previously dis-
cussed TCLP procedure and the STLC extraction, which uses a sodium citrate buffer with a
tenfold dilution factor.
2.TreatmentResults
The treatment protocol used two cementitious materials, cement and lime, in the ratios of 20:3
or 15:5, with polysilicate additionsof approximately 0.5 gaton. An example of the ability of
the process to reduce the soluble concentration is given for arsenic treatment (Figure 5) during
the production phase.It is important to notethat in this case the treatment standard for arsenic
was set at 1 ppmby the site owner instead of the regulated level of 5 ppm. The analytical
evaluation protocol was established at 0.2ppm, so values belowthis level were not determined.
458 Trezek
Number of Samples
figure 5 Comparison of untreated and treated TCLP levels of arsenic (Case Study 11).
In this project, a daily production goalof 750 tons of treated material was established as
being reasonable for the site conditions, which were constrained by the ability to deliver ma-
terial to the process (i.e., excavation, screening, sampling,etc.), the cycle time for curing and
stockpiling in the tank, and the subsequent backfilling. The ability of the system to meet the
processing goals is illustrated in Figure 6 in terms of daily tonnage and daily average tonnage
over the production phase of the project. At times it was not possible to meet the daily pro-
duction schedules, the reasons being (1) a mechanical failure in the lime delivery system on
days 3 and 4, (2) the unavailability of feed material on day 3 1, and (3) the reduced quantityof
feed material at the end of the major portion of the project during days 37 and 38.
An additional feature of this project concerned the contaminated water collected on-site in
the process. The RCRA tank allowed liquids to be collected from the processing areas that
included both the screening and treatment activities. Approximately 12,000 gal of water per day
was generated froma combination of spraying for dust controland rain. An on-site systemwas
implemented that allowed this water to be incorporated into the treatment process. The water
from the collection system was introduced into the first of a series of four Baker tanks. This
provided suitable capacity and time for the settling of suspended solids. The liquid from the
fourth tank was then returned to the polysilicate-water blending tank in the chemical mixing
portion of the treatment system. The concentration of arsenic in the liquid entering this tank,
as determined by EPA methods SW-846,3010, and 6010 was on theorder of 4 mg/L. Blending
this liquid with the process water at a ratio of 1:20 did not impact the treatment protocol. In
addition, the project benefited from a significant savings in off-site disposal costs.
VI. ANCILLARY TREATMENT PERFORMANCE PARAMETERS

In addition to the task of reducing metal solubility,other important featuresof this technology
are considered. These include (1) the nature of hydration and curing; (2) the compactability
of the treated material as related to on-site backfilling; (3) the effect of pre- and posttreat-
ment particle sizes, which influence metal concentrations in dispersed material; and (4) the
long-termviabilityof the treatment as measuredthroughmultipleextractionprocedures.
10 15 20 25 30 35
Days Running
Figure 6 h e s s i n g system throughput performance (Case Study II).
A. HydrationandCuring
As previously mentioned, curing the treated material is the final step in the process. In terms
of the field application of the technology, this basically amounts to liberating the moisture in
the treated material, i.e., allowing it to dry. However, this process has other fundamental and
serious impacts on the efficacy of the technology in terms of(1) the proper hydration of ce-
mentitious materials, which is relatedto the transformation of ionic bonds to covalent bonds,
and (2) the use of sampling procedures that ensure that the curing process has been completed
before the material is subjected to TCLP or other extraction protocols.
The following discussion
considers the interrelationship between hydration, curing, and sampling, which were exten-
sively evaluated for the soil treated in Case Study 11.
The treatment protocol developed for the remediation of the arsenic-contaminated soilof
Case Study I1 used cementnime ratios of either 20:3 or 15:5 on the basis of weight. The effect
of these mixtures on the hydration characteristics of the treated material is illustrated in Figure
7 for a bench-scale test using an initial 500-g sample of soil having a moisture content 12%. of
After the addition of reagents and water in the amounts of 85 and 100 mL, respectively, the
mixture weight was about 700 g for both cement-lime combinations. Here water essentially
behaves as a reaction catalyst. Based on prevailing accepted stoichiometric data, the amountof
water bound to cement and lime is on the order of 13% and 30% of their weight, respectively.
This would indicate that approximately 17-18 g of water would be retained in the matrix. In
460 Trezek
-
Time hours
Figure 7 Hydration characteristics of cement-lime mixtures.
other words, the dilution factor due to water would be approximately 3.5%. As expected, the
mixture with the higher percentage of lime begins to initially lose its free water at a faster
rate (Figure 7) due to the increased heat of hydration. After thisinitial period, a similar linear
rate of water loss occurs in both mixtures over a 72-h period. During this time, the samples
were subjected to a 70°F, 65% relative humidity environment and were broken at 8-hrintervals
to expose new surface. Between 72 and 75 hr into the test period, heat lamps were used to
accelerate the water loss. The samples were allowed to equilibrate to room conditions for 1 hr
before final weighing.
The data obtained fromthe above exerciseillustrate that (1) the majority of the free water
used as a catalyst will be liberated and(2) the retentionof water in the matrix appearsto be less
than that derived from conventional stoichiometry. However, more important in terms of op-
erations, using artificial means such as heat lamps to accelerate the loss of free water does not
alter the fundamentals of the treatment. In certain cases, a procedure of this nature, referred to
as a lab cure, is used to expedite the turnaround time of obtaining analytical laboratory TCLP
data. Operationally, this can allow naturally cured stockpiles to be backfilled at the time the
analytical data are available. A comparison of the lab and field cure TCLP arsenic data (Figure
8 ) illustrates that the two methods yield the same results with proper field curing. It shouldbe
noted that in Figure 8 , arsenic data are given for both the pilot test and the production phase
where the detection limits were 0.01 and 0.2 mg/L, respectively.The acceptable TCLP levelof
arsenic in the treated material was set at 1.0 mg/L. Basically, the elevated levels in the field
data shown in Figure8 indicate that the material was prematurely sampled.Sufficient free wa-
ter was still present; that is, the process shown in Figure 7 was not completed. The tendency
of the treated material to form monoliths is another ramification of improper field curing.
Stockpiled material must be turned, usually on a daily basis, to (1) enhance the rate of curing
through accelerated heat and mass transfer to the environment and(2) mechanically overcome
the tendency of cementitious mixtures to fuse or solidify into a continuous substance, which
would negate the desirable feature of a friable matrix structure.
Number of Samples
Figure 8 Comparison of laboratory and field curing on TCLP arsenic concentrations.
B. Compactability
An important feature of the process is the ability to backfill or recompact the treated material
into the excavation. Standard tests of treated material using ASTM Method D-l557 yield a
compaction of about 97%. The following procedure is typically used in the field to achieve this
compaction.
Stockpiled cured material is loaded into a dump truck and moved to the excavation. Here
the dumped pile is spread with a bulldozer into an 8-12-in. lift. The moisture content is ad-
justed according to the ASTM test data to be consistent with optimum compaction. A drum
vibrating compactor is then usedto complete the placementof the lift. The volume expansion
due to treatment is estimated to be on the order of 20%. Operationally, after the removal of the
oversize fraction, the backfilled treated material occupies the volumeof the excavation.
Several field observations indicate that the features of the backfilled treated material are
suitable for construction. For example, backhoe digging tests on material in place for 28 days
showed that it remained friable with sufficient structural stability for trenching; that is, sharp
vertical cuts couldbe made. The equipment operators indicated that the backfilled material was
similar to digging hardpan.
C. Effect of Particle Size

An additional featureof the STS polysilicate technology is its ability to indirectly mitigate total
metal concentrations through increased posttreatment particle The size.basic mechanism stems
from the fact that the emissionrate for total respiration particulate matter(E,,) has significant
E,, is illustrated through the work
particle size sensitivity. This effect on of Cowherd et al. [9]
and summarized in the California Site Mitigation Decision Tree F’rocess [lo]. The basic cal-
culational methodology follows.
1.ParticleSizeDistribution
The f m t step in the procedure involves the determination of the characteristic particle size.
This is typically accomplishedby subjecting representative samples of pre- and posttreated ma-
c
462 Trezek
Size mm
Figure 9 Size distribution of pre- andposttreated soil.
terial to a sieve analysis andarranging the results in terms of percent passing vs. size (Figure
9). It is interesting to note that the characteristics of the treated material (straight line on a
semilog plot) are representative of a Rosin Rammler distribution, which will have a charac-
teristic particle size (X,) corresponding to 63.2% passing. Consequently, for illustrative pur-
poses, the value of X, for the particular treated material shown in Figure 9 would be given by
a size of about 6.4 mm. The comparable size for the untreated material can thenbe taken as 0.8
mm. Thus, as illustrated in Figure 9, the agglomerative featuresof creating the metasilicate and
cementitious matrix during the treatment process hasthe effect of shifting the size distribution
of the treated materialto larger sizes. The increase inthe characteristic size is usually about an
order of magnitude. Here this increase is a factor of 8.
2.ThresholdFriction Velocity
As illustrated in the work of Cowherd [9], the threshold friction velocity (Uf)is logarithmically
related to the so-called aggregate size distribution mode. Basically, this parameter is intended
to be representative of the wind speed at ground level corresponding to the occurrence of soil
erosion. In termsof the characteristic particle size, the valueof Uffor the 0.8-mm and 6.4-mm
particles are 60 c d s e c and 140 cdsec, respectively. Thus, an eightfold increase in particle
size slightly more than doubles the threshold friction velocity.
3. Roughness Height
Roughness height is used to convert the value of U, at ground level to the wind speed at a
typical 7-m-high weatherstation. Values of roughness height(Z,) range from0.1 cm for natural
snow to IO00 cm for high-rise buildings. Similarly,plowed fields and grasslands are given by
Z, values of 1.O cm and 2.0-4.0 cm, respectively. A Z, value of 1 cm is typically used for soil
being remediated.
Contaminated
Solids
Metal 463
4.Threshold WindVelocity
The threshold wind velocity (Ur),i.e., the wind speed necessary to initiate soil erosion as de-
termined by 7-m-high weather station data, is given in terms of the value of Ufaccording to a
relation developed by Cowherd,
Ut = U, (13.1 - 2.5 In G)
The corresponding values of U,for the 0.8- and 6.4-mm particles are 7.86 and 18.34 m/
sec, respectively.
5. Respirable Particulate EmissionRate
The following relation developed by Cowherd was used to evaluatethe emission rate of respi-
rable particle matter from erodible surfaces:
El0 = 0.036 (1 - V ) ( I Y / U , )F(x)
~
where E,, is the emission rate for total respirable particular matter [g/(m 2.hr)]; V , the fraction
of exposed contaminated area thatis vegetated (V = 0 for bare soil); and U,the mean annual
wind speed (m/sec).
The parameter F(x) is given by the relation
F(x) = 0.18(82 + 12x)/8*

where
x = 0.886 (UJU)
Assuming a nominal 10 mph wind speed (4.47 m/sec), the value of E,, for the 0.8-mm
particle size is 5.15 X low3g/(m 2*hr).The corresponding value for the 6.4-mm particle is
7.3 X lo-* g/(m 2+r). Thus, an eightfold increasein particle size reduces the value of E,, by
7 X lo4. Alternatively, relatively small increases in threshold friction velocity due to increased
particle size result in large decreases in respirable emission rates.
The E,, behavior with wind speedfor 0.8-mm and 6.4-mm particles is illustrated in Figure
10. Each particle exhibits a characteristic steep rise in concentration at elevated wind speed.
Basically, the larger particles can sustain higher wind speeds for a given concentration. For
example, the 0.8-mm particle has an E , , value of 5.15 X g/(m2-hr)at 10 mph. A similar
value of E,, for the 6.4-mm particle would be reached at a 23 mph wind speed.
6. DownwindConcentrations
The effect of particle size on concentrations of specific constituents reachinga downwind re-
ceptor can be obtained from therelation
X = Q/n ayazU
where X is the concentration of the constituent in ambient air (pg/m); Q is the emission rate
(pg/sec); ayand a, are the standard deviationof horizontal and vertical dispersion, respectively
(m);and U is wind speed (m/sec).
The following assumptions are made to illustrate the effect of particle size on downwind
concentrations for a working area of IO00 m' and a length of 100 m to the receptor. Using the
data of lbrner in the Workbook of Atmospheric Dispersion Estimates[1l] and ClassC stability,
the values of ayand a, are 13 and 7 m, respectively, fora 100-m distance. Thus, for a 10 mph
wind speed, the valuesof X become 1.12 X IO3 and 1S 8 X ng/m3for the 0.8 and 6.4-
mm particles, respectively. Thus, an estimate of the downwind concentration of any specific
46.4 Trezek
A. 6.4 mm PARTICLE
3 0 _
X I- o.amm
_
PARTICLE
U
C
1.OOE-(
i
38
1.00E-07
Figure 10 Influence of wind speed on concentration.

E10 (gms/sqm.hr)
, l .OOE-
constituent can be calculated by multiplying the downwind concentration X by the mass frac-
1H
1 .OOE-0'
tion of that constituent. The results of this calculation are summarized in Table3 for the total
metal concentrations given in Table 2 for metal system5 . Basically, these results follow the
effect such that the downwind concentrations become negligible for the larger particle size.
E,,
1.00E+00
VII. MULTIPLEEXTRACTIONPROCEDURE
The standard extraction tests (TCLPor California STLC) provide a one-time equilibrium sol-
ubility valueof the heavy metal compounds in the extraction fluid do butnot give an indication
of the time-dependent stability of the residual matrix.The EPA multiple extraction procedure,
designed for evaluating the leachabilityof materials exposedto so-called acid rain conditions,
was used to test the stability of the polysilicate cementitious treatment protocol.
Table 3 Effect of Particle Size on Constituent Downwind Total Metal Concentrations for Metal
System 5"
Concn,
Mass Concn,
0.8 mm 6.4 mm
Compound fraction X particle (ng/m3) particle(ng/m3 X 10"~)
Arsenic 2.759 3.09 4.36
Copper 2.57
1.627 1 .S2
Lead S5
12.45 1.74
Nickel 0.174 0.47 0.526
Cadmium 0.076 0.048 0.054
0.364 Zinc 0.325
~ ~~
'Mean wind speed = IO mph.

Remediation
Contaminated
Solids
Metal
of Heavy 465
STLC Arl Ar3 Ar2

Ar4 Ar5 Ar7 Ar6 Ar8 Ar9 Arlo
STLC - Acid Rain Extractions
Figure 11 Effect of multiple extractions on soluble metal concentrations.
The evaluation consistedof an initial STLC extraction (as described in CCR title26, Ch22-
66261 Appendix 2) followed by 10 consecutive acid rain extractions (using 60/40 a solution of
sulfurichitric acid with apH of 3 as described inSW846 Volume C, Ch. 6,Method 1320).The
predominant metals in the sample being treated were copper, lead, and zinc with initial STLC
concentrations of 22, 110, and 106 ppm, respectively. Thus, in this sample the summed value
for the STLC soluble metal concentration would be 238 ppm. Following treatment, the summed
STLC concentration value was 11.7 ppm. The results of the subsequent acid rain extractions for
both the treated and untreated materials are shown in Figure 11. Basically, the stability of the
treated material is illustratedby the fact that the equilibrium leachable value was reached fol-
lowing the second acid rain extraction and remained unchanged. On the other hand, the me-
talliccompoundsintheuntreatedmaterialcontinuedtoionize andleachfollowingeach
additional extraction step.
VIII. CONCLUDING REMARKS

The STS polysilicate technology provides an effective and relatively low cost method of re-
mediating soils contaminated with heavy metals. In this system, the metals become partof a
covalent bonded matrix created through the action of the silicates and cementitious materials.
Reductioninheavymetalsolubleconcentrationlevels of severalorders of magnitude are
achievable. In terms of site remediation, the processing equipment can be configured in the
form of a mobile system capable of operatingat high throughput rates. When properly cured,
thetreatedmaterial is friableandcan be backfilledwitha 97% compaction. An order-
of-magnitude increase in the mean particle size of mated
the material significantly reduces the
466 Trezek
downwind total metal concentrationsof potentially airborne material. Finally, multiple extrac-
tion procedures validate the long-term survival
of treated material in an acid rain environment.
ACKNOWLEDGMENT
I wish to express my appreciation to Ms. Nancy Wright for her patience and competent assis-
tance in preparing the manuscript.
1. 'Ifezek, G . J., Polysilicate heavy metals mitigation technology, in PhysicallChernical Processes,In-

novative Hazardous Waste Treatment Technol. Ser., Vol. 2, Technomic, Lancaster, Penna., 1987,
pp.155-163.
2. Trezek, G . J., Polysilicate treatment of heavy metals in soil, Fifth Annual Hazardous Materials
Management Conf./West, November 1989.
3. Trezek, G . J., Raphael, G . , Wilber, J. S., and VanPelt, R. E., Remediation of arsenic contaminated
soil using polysilicates, HMCRI R&D '92 Conf., San Francisco, February 1992.
4. Trezek, G . J., Heavy metal contaminated soil remediation at high throughput, Proc. Superfund '90,
Washington, D.C., November 1990, pp 673-676.
5. Landau Associates, Inc., Edmonds, Wash., Thompson-Isaacson Site Soil Stabilization Pilot Test
Summary Report, Prepared for The Boeing Company, July 1991.
6. Wicks, F! H., Bothell. Wash., Proposed Remedial Action at Isaacson Corporation Property, Seattle,
Washington, Prepared for Isaacson Corporation, 1984.
7. Dames & Moore, Seattle, Wash., Report of Evaluation of Site Contamination, Isaacson Steel Prop-
erty, Prepared for the Boeing Company, 1983.
8. LandauAssociates,Inc.,Edmonds,Wash.,andParametrix, Inc.,Bellevue,Wash.,Thompson-
Isaacson Site Soil Remedial Action Plan, Prepared for The Boeing Company, 1990.
9. Cowherd, C. M., Muleski, G . E., Englehart, F! J., and Gillette. D. A. Rapid Assessment of Ex-
posure to Particulate Emissions from Surface Contamination Sites, Midwest Research Institute,
Kansas City, MO., 1984.
10. California Department of Health Services, Toxic Substances Control Division,The California Site
Mitigation Decision Tree Manual, Sacramento, Calif., 1986.
11. 'lbmer. D. B., Workbook ofArtnospheric Dispersion Estimates, HEW, Washington, D.C., 1970.
21
Fluidized Bed Combustion for
Waste Minimization: Emissions
and Ash Related Issues
E. J. Anthony and F. Preto

CANMET
Ottawa, Canada
1. INTRODUCTION
Fluidized bed combustion (FBC) is a versatile technology that can be used in burning a wide
variety of fuels. Fuels may range from conventional premium fuels (coal, oil, and natural gas)
to municipal solid wastes (MSW), refusederived fuels (RDF), coal rejects (up to 70% ash or
more than 50% moisture), biomass and biomass wastes, sludges, pitches, and tars [l-51.
Another advantage of FBC is that, due to lower combustion temperatures, NO, levels
are considerably lower than for conventional combustion systems. Furthermore, SO2emissions
can be reduced by using limestone as the bed material to capture sulfur (as CaSO,)[6-81.
Paradoxically,despitethelowercombustiontemperatures(typically800-950°Ccompared
to 1200-1400°C for conventional combustion), FBC also produces very low levels of poly-
aromatic hydrocarbons (PAH) and other volatile organic compounds(VOC), due to a number
of factors. First, the residence times of gases and solids in the combustion zone are rela-
tively long compared to conventional combustion; second, FBC systems provide excellent,
turbulentmixing;finally, it appearsthat at FBCcombustiontemperatures,limestone bed
particles act as a catalyst to destroy organics [9-131. In a study on both FBC and pulverized
fuel boilers burning coal, it was concluded that “in general, the levels for the limited poly-
chlorinated dibenzofurans and dioxins that have been detected in fly ashes from these power
stations are several orders of magnitude lower than levels reported in municipal incinerator
ashes” [Ill.
The use of sorbents as bed material results in the generation of ashes with unique prop-
erties. The management, i.e., disposal or utilization, of these ashes must be taken into account
as part of the overall waste minimization scheme. For high sulfur fuels as such
coal, petroleum
coke, and some pitches and tars, the ash produced has high calcium oxide content and be can
associated with exothermic reactions, dimensional instabilityin waste disposal sites, and high
pH leachate (typically pH 11-12). However, the alkaline nature of these ashes does confer the
benefit that leaching of heavy metals from such residues in minimal [14,15].
467
468 Anthony and Preto
CANMET (the research division of Energy, Mines and Resources Canada, the federal gov-
ernment department responsible for energy-related activities in Canada) has been investigating
fluidized bed combustion for coal, industrial wastes, and biomass since 1975. Research using
bench-scale and pilot-scale reactors throughout this period has shown that fluidized bed com-
bustion appears to be an ideal technology for efficiently burning a wide variety of fuels and
wastes while also achieving verylow emissions of pollutants. The only significant difficulties
have been related to feeding nonconventional fuels using pilot-scale equipment. These diffi-
culties are resolvable in full-scale units.
II. FLUIDIZEDBEDCOMBUSTIONPRIMER
A fluidized bed consist ofbed a of particles suspended above a grid (e.g., perforated plate) by
a fluid (air) moving upward through holes in the grid. The velocity of the fluid must be suf-
ficient to suspend the particlesso that they move freely in the bed region. If the velocityis too
low, the particles are immobile in a “fixed bed”; at velocities greater than the particle’s ter-
minal velocity, the particles are blown completely out of the bed, i.e., elutriated. In the flu-
idized bed regime, particles remain in the bed (hence good residence time) yet move about
freely (hence good mixing). These characteristics, i.e., good mixing and long residence time,
are the primary reasons for the numerous benefitsof using fluidized beds.
Fluidized bed combustion (FBC) is the technique whereby a fluidized bed of particles is
used as a medium for the combustion process. The bed particles themselves are not usually
consumed in the combustion process but may play important roles in emissions control, for
example, limestone particles are used to capture sulfur dioxide (forming calcium sulfate, i.e.,
anhydrite). The fuel particles typically comprise a very small fraction of the bed, e.g., less
1% for burning coal. Good particle mixing results in nearly uniform bed temperatures. This
together with high thermalinertia due to the considerable mass of particles in thebed allows
for virtually isothermal reaction
at the optimum operating temperature. This confers upon FBC
a number of advantages over conventional combustion systems. Some of FBC’s advantages ca
be summarized as follows.
Fuel particles are rapidly heated to stable combustion temperatures.
Almost any fuel can be handled, including nonhomogeneous fuels withlow volatility or high
moisture content.
The requirements for fuel preparation are minimal; washing, drying, and pulverization are gen-
erally unnecessary.
Judicious selection of bed material can result in the in-bed capture of gaseous pollutant sp
Low combustion temperatures (typically800-950°C) ensure that the formation of nitrogen ox-
ides from air nitrogen is negligible.
A schematic diagramof the FBC process is shown in Figure 1. A blower suppliesair to the
windbox, which then discharges it through the distributor plate into the bed. The particle bed
is traversed by heat exchanger tubes to provide for heat extraction from the bed. Above the
particle bed a “freeboard” region is providedto allow particles ejected fromthe bed to settle
back and to allow gas-phase reactionsto proceed to greater completion.The cyclone separator
removes all but the finest particles carried by the exhaust gases. The cyclone product can be
either recycled to the bed for further reaction or removed from the system. The gases leaving
the cyclone are passed through a fabric filter “baghouse” to remove fly ash.
The type of FBC unit shown in Figure1 is generally referred toas a bubbling bed because
bed through whichair in excessof that required for fluidization passesas
there exists a distinct
“bubbles.” Superfkial fluidizing velocities are typically 1-4 &sec. If the fluidizing velocity
.
Fluidized Bed Combustion
L +
STACK
469
I
I
I
1
CYCLONE
BAGHOUSE
f
COMBUSTOR
OVERBED
FUEL &
S
*O
RB
E
NT
+
*
"
-. I3
COOLIN1
WATER
-.
* UNDERBED
FUEL &
*BENT
AS
RECYCL -
- WINDBOX
?
AIR
V
CiYCLONE UNDERBED OVERBED BAGHOUSE
P'RODUCT
PRODUCT
PRODUCTPRODUCT
Figure 1 Schematic diagram of FBC process.
is increased substantially, i.e., to 4-8 d s e c , the bed particles become entrained and are car-
ried out of the combustor. These particles can, however, be captured by a "hot" cyclone and
returned to the bed. A hot particle circulation loop is thus established that allows particle re-
actions to continue throughout the complete cycle. This type of system offers some advantages
for capture of pollutant species and combustionof low-reactivity fuelsdue to the considerably
increased residence time of fine particles in the bed. The actionof this systemis referred to as
circulating fluidized bed combustion (CFBC).
This section is included only as a basic introduction toFBC.The literature on FBC is quite
voluminous, a recommended source beingthe American Society of Mechanical Engineers' se-
ries of conferences, themost recent of which is the 12th International Conference onFBC held
in San Diego in May 1993.
111. FBC FOR WASTE MINIMIZATION

Due to low organic emissions levels, FBC is a promising technology for disposal of organic
material-laden wastes. Donlee Technologies (USA) has developed a CFBC boilerto incinerate
infectious hospital wastes by cofiring with coal [16]. Based on pilot-scale testing, they report
that PAH, dioxin, and furan emissions were typically well below those achieved with other
typesofhospitalwasteincinerators. Furthermore, suppression ofHClofup to 50% was
achieved. Organic emissions metboth the Pennsylvania Department of Environmental Re-
sources and proposed California restrictions. FBC-based technology meeting all emission limits
for PAH, dioxins, and furans has also been offered by Ogden Environmental Services (USA)
for the successful destruction of a number of hazardous wastes, including PCB-contaminated
soil [17,18].
FBC is being examined in Italy for the combustion of organic material-laden industrial,
agricultural, and domestic wastes. Published results[l91 indicate emission levelsof dioxins and
furans much lower than proposed European legislated limits.The potential of FBC technology
as an inexpensive method for disposal of hazardous wastes is being examined in India by San-
doz (India) and Thermax [20,21]. Thermax also reports that there are now 200 FBC installa-
tions operating in India burninga wide rangeof fuels fromlow grade coals to agrowastes such
as rice hulls [21]. In India, FBC is overtaking rotary kilnsas the preferred technology for the
incineration of solid and liquid wastes [21].
The use of FBC (primarily bubbling bed technology) for incineration is strongly estab-
lished in Japan [22,23]. FBC is routinely used to burn MSW, plastics, and tires among other
materials (one supplier alone, EBARA Corp., has 40 FBC incinerators operating [23]). It has
been reported that there are currently 113 FBC incinerators operating in Japan [24].
In Europe there are over 50 FBC incineration plants [25]. Studies have also shown that
FBC can burn RDF and industrial waste plastics either directly or by cofiring with coal [26,27].
A particularly interesting design concept, the fast internally circulating bed [25], used FBC
technology to achieve “100%” elimination of all pollutants. The principal disadvantageof the
concept was that the payback periodin the Austrian contextwas inherently long, i.e., 15 years
for a 10 MW(th) unit.
In North America, the use of bubbling fluidized bed combustion is increasingly finding
more acceptanceas a means for the production of energy from the combustion of used tires and
municipal wastes [28]. In the UnitedStates, circulating fluidized bed combustion is being used
for disposal of hazardous wastes [17,18]. In Canada, a 10 MW(e) revolving fluidized bed unit
has recentlybeen built to cleanly burn residues fromtar ponds near Sydney,Nova Scotia [29].
Although the main thrust of this project is to clean up 700,000 tons of coke oven residues,the
energy production is not unimportant. This unit is due to become fully operational in 1993.
Cofiring involvesthe burning of a waste “fuel” in conjunction with a premium fuel(coal,
gas, or oil). Cofiring is used to supplement a waste fuel that may not be able to sustain com-
bustion on its own or as a topping fuel if insufficient waste fuel is available. Cofiring, also
known as “smart-burn,” does not prevent recycling programs,as any reduction inthe quantity
of waste (particularly MSW) can be made up with the premium fuel. Cofiring thus appears to
offer a palatable solution to the considerable municipal waste disposal problems now being
experienced across North America. Traditional resistance to incinerators is likely to be reduced
since as little or asmuch MSW canbe burned or recycled as desired, based on local economic
or legislative requirements.
Recently, the idea of cofiring coal and MSW or RDF has begun to find favorin the United
States [30]. This is especially true in California, where the use of such wastes allows positive
returns (extension of the lifetime of disposal sites; reduction in waste site emissions of green-
Fluidized 471
Table 1 BubblingFBCCombustion of Biomass

paper
husks
waste
basis
Corn
pellets
Rice
grass
Alfa
Dry cobs Wood pellets
% Volatiles 59.8
83.1 80.9 - -
% Fixed C 15.2 14.6 13.4 - -
% Sulfur 0.2 - - - -
% Ash 1.6 4.4 22.2 - -
HHV (MJkg) 18. l 18.8 14.1 - -
Particle size 40-50 mm 3-cm fragments 5 10-mmhusks l-cm pieces 2-3-cm pieces
diam, 150-
mm-long
cylinders
Feed rate 40-80 61 20-70 70 80-90
(kg/hr)
Fluidization 0.9-1.2.4 2 1.4 0.4-2.2 1.3
velocity
(dsec)
Combustion >98% 96%
>96% >97% >90%
efficiency
CO 100-400 ppm 1.9% >200(up
ppm 0.1-0.3% 0.6-1.0%
to 0.5 %)
NO, @Pm) 100-180
60-150 155 >450 60-80
so, (PPm) 100-200 - 50-150 - -
house gases and other toxic products; and generation of energy in the form of heat, process
stream, and/or electricity) while still meeting the strict state environmental guidelines[31]. El-
liot [31] quotes a figure of 3.6-4.1 cents/kWh for cofiring MSW compared with approximately
5.5 cents/kWh for a new coal-burning plant.Furthermore, these figures do not include a credit
for the extension of the lifetime of the waste disposal facility or reduced liability costs for
storage of potentially hazardous materials such as used tires. The economics of cofiring are
therefore very favorable, findings that have been reinforced by a recent detailed literature sur-
vey on application of FBC to MSW [32]. In Canada, a number of companies are evaluating
this technology and CANMET is also actively supporting FBC technology for biomass com-
bustion [33,34].
A. Firing of Waste Biomass

CANMET has tested a number of waste biomass fuels in pilot-scale bubbling fluidized bed
combustors (40cm X 4 cm units with a total height of 5 m) [35]. The fuels that have been
burned are paper waste pellets, alfa grass, wood chips, corncobs, and rice husks. Proximate
analyses of the fuels, where available, operating conditions, combustion performance, and
emission levels are given in Table 1. The only serious problem associated with burning these
fuels was feeding them into the bed. This was largely due to the pilot scale of the equipment;
the alfa grass and wood chips had a tendency to “bridge” in the fuel hopper; the cyclone was
overwhelmed by ash during the alfa grass trials. Both the alga grass and corncob exhibited
significant particle carryover.
Freeboard combustionwas found to be significantfor all biomassfuels, particularly if the
bed temperature was low. For instance, for the paper pellet tests, when the bed temperatures
were between 600 and 800”C, the freeboard temperatures were typically in the range of 1000-
1100°C. However, if the bed temperature was increased to 700-95OoC, the freeboard temper-
atures dropped to 650-950°C. In the case of this particular feedstock there were also some
problems associated with defluidization of the bed. This was theorized as being due to ag-
glomeration, possibly caused by the chlorine contentof the fuel. Scanning electron microscopic
examination of the bed material showed high levels of chlorine in the limestone particles.
Rice husks proved to be an ideal fuel for pilot-scale trails as their small uniformsize and
low compressibility allowed them to be easily screw-fed into the bed. Their combustion char-
acteristics were excellent (Table 1). The principal finding of this work was that the primary
challenge for FBC utilization of waste biomass fuels is that of feeding the fuel. Once this can
be done successfully, complete combustion and low emissions of both SO, and NO, can be
achieved. Reduction in CO emissions and particle carryover require only a longer residence
time, i.e., a substantial freeboard.
Combustion of wood waste (sawdust and hog fuel) has beencarried out at the University
of British Columbia using a 150-mm internal diameter circulating fluidized bed reactor [33].
NO, emissions were found to be low (<l00 ppm); however, the CO concentrationswere found
to be quite erratic and ranged from 10 to 2000 ppm. This variability was probably due to an
unsteady feed rate, again due to limitations in the equipment size. Gas chromatographic anal-
ysis indicated the presenceof higher molecular weight hydrocarbons, probably of phenolic or-
igin, but these could not be properly characterized by the analytical system used.
The worldwide number of FBC units burning industrial and biomass wastes, either alone
or cofired, lies in the hundreds. The exact numberis undetermined, partly because of the wide
range in unit size that can be built. Babcock & Wilcox have built 29 FBC units, of which ap-
proximately half operate as waste cofiring units [36]. Inthe United States, B&W has built three
CFBC/Studsvik-design boilersto burn wood and waste wood products [37]. Pyropower reports
that as of 1991, it had built over 90 CFBC units worldwide, of which 20 or so have been used
to burn wood or industrial waste [38,39] (some in the cofiiing mode). Other major suppliers
such as FosterWheeler,DeutscheBabcock,AseaBrownBoveri-Combustion Engineering/
Lurgi, and Tampella Power Corporation also offer proven CFBC designs for a wide range of
biomass and industrial wastes at both the industrial and utility scales.
On a smaller scale, FBC technology is also available for a wide range of wastes. For
example, JWP Energy Products of Idaho has built five successfully operating bubbling fluid-
izedbed boilers for the combustion of biomass in California [40]. The largest of these, a
27-MW(e) FBC boiler located in Delano, California burns agricultural wastes (orchard prun-
ings, secondarywood, almond shells, andcotton stalks). It has met Californiaemission
guidelines for sulfur compounds, oxidesof nitrogen, hydrocarbons, and carbon monoxide. No
significant problems have been reported for any of these units, although limestone addition was
necessary for somefuels to raise the ash softening point and reduce fouling the on heat transfer
surfaces. Ammonia injection has, where necessary, been used to meet California’s NO, emis-
sion guidelines.
Outokumpu Technology Inc. recently enteredthe North American market and boasts over
30 bubbling fluidized bed boilers worldwide burninga variety of “difficult” fuels, including
bark, wood chips, paper waste, waste sludges, and oil tank sludges. Outokumpu’s North Ame
ican subsidiary (Outokumpu EcoEnergy Inc.)is building a 25-MW(e) FBC plantto bum saw-
dust and high moisture (46%) wood waste [41].
This brief review of FBC facilities designed to bum industrial waste, biomass, and other
wastes is in no way intended to be exhaustive. It does, however, demonstrate that FBC tech-
nology can be regarded as a mature technology for burning theseclasses of fuels.
Fluidized 473
B. Cofiring of Pulp Mill Sludges

The Canadian pulp and paper industry produces on the order of 2200 tonnes/day of dry sludge
from wastewater treatment operations. These materials typically contain high moisture (>50%)
and have low heating values. Approximately half of this material is incinerated, and the re-
mainder is used as landfill. Increasing concerns about heavy metal contamination may make the
landfill option less attractive in the future.
A study has been directed by CANMET, using a 150-mm-diameter CFBC unit, to inves-
tigate the cofiring of these sludges with high sulfur bituminous coal [34]. Eight trails were per-
formed with coaYsludge mass ratios varying between 3:1 and 1 :3. Sludge moisture ranged
form 50 to 60%. One test, burning only sludge, quickly demonstrated that the sludge alone
could not sustain combustion. In general, combustion efficiencies of 93-98% were achieved
(based on carbon conversion). Emissions were low; NO, varied from 100 to 200 ppm, and CO
levels ranged from 30 to 700 ppm. The only significant problem was, once again, feeding due
to the fibrous nature of the sludges. To echo an earlier conclusion: If feed problems can be
resolved, there are no barriers to using FBC technologyfor minimization of pulp mill sludges.
The economics of sludge combustion would probably be significantly improved by better de-
watering techniques.
In a joint project, CANMET and Air Products and Chemicals, Inc. (USA) have used a 40
cm X 40 cm FBC pilot plant [35] to study the combustion performance of deinking sludges
cofired with propane. Again,once feed problemswere overcome, all of the combustion results
were successful. Due to low sulfur content anda high degree of sulfur capture inherentin the
sludge, SO, concentrations remained below 5 ppm. NO, and CO concentrations were easily
maintained below 150 ppm and 100 ppm, respectively. HCl levels were typically less than 15
ppm. At low temperatures (<850°C), N,O concentrations of approximately 10 ppm were re-
corded, dropping to a few ppm at higher temperatures. A complete set of organic analyses
showed that PAH, dioxins, andfurans were much lowerthan Canadian guidelinesfor municipal
incinerators. The ash leachate characteristicsas measured by the Toxicity Characteristic Leach-
ing Protocol (TCLP) were also well within limits.
W. GASEOUSEMISSIONS
A. Nitrogen-BasedSpecies
As indicated earlier, fluidized bed combustors operate at temperatures of 800-95OoC, several
hundred degrees below temperatures for suspension or pulverized fuel fired boilers. At these
lower temperatures, nitrogen inthe air is not fixed, and thereforethe majority of NO, (emitted
primarily as NO rather than NO,) originates from fuel-bound nitrogen. Conversion of fuel ni-
trogen to NO, is typically in the 10-25% range. The bulk of the fuel nitrogenis either directly
converted to N, or reduced to N, by reaction of NO, with the char present in the bed [42,43].
As a general rule, higher nitrogen content of the fuel leads to higher NO, emissions [42-441.
The volatile content of a fuel can also affect NO, emissions, with NO, increasing with
increasing volatile content. The following relationship hasbeen found to be hold for numerous
fuels [44,45]:
Nitrogen conversion a Vol(%) X N(%)
where nitrogen conversion can be either the percentage of fuel nitrogen convertedto NO, or the
actual NO, emission referenced toa constant oxygen level. Vol(%) is the percentage of volatiles
in the fuel, and N(%) is the percentage of nitrogen in the fuel.
As expected, higher temperatures leadto higher NO, emissions, with increases as high as
260 ppm being reported [42-441. Nevertheless, bubbling FBC systems can normally operate
with NO, concentrations lower than 250 ppm. Circulating FBC systems can usually operate
with NO, concentrations below 150 ppm due to an inherent staging capability in these units.
Biomass fuels typically have significantly less fuel nitrogen (<0.3%) than coal (typically
in the 0.8-1.5% range). NO, emissions are therefore not usually a concern for these types of
fuels. In cases whereNO, emissions are significant, NH, injection has been shown to bea very
successful technique for achieving extremely low NO, levels [46,47].
Leckner and Karlsson[48] studied the effect of cofiring wood chips and sawdust with coal
in an 8-MW(th) CFBC boiler. They concludedthat the conversion of fuel-bound nitrogen was
higher for wood (about 20%) than for coal (<lo%).However, due to the relatively low levels
of fuel nitrogen in the wood, NO, emissions were acceptably low. This work also showed ef-
fectively linear relationships for CO, SO2, and even N 2 0 emissions with the percentageof coal
fired for the cofiring of wood and coal.
Leckner and Karlsson also found that nitrogen emissions rosedisproportionatelyfor cofir-
ing wood with relatively small amountsof coal. NO, emissions peaked(greater than for either
100% coal or wood firing) when coal was used to supply approximately 20% of the total energy
input. Thiswas attributed to the increased nitrogen content from the coal without a correspond-
ing increase in the char content. Burning coal by itself results in higher char content in the
system, which normally helps to reduce the NO, to N,. The best strategy for low-NO, emis-
sions when cofiring waste thus appears to be to fire the less reactive fuel (such as coal) in
excess.
N 2 0 is a pollutant that has not hitherto received much attention and is not as yet con-
trolled. Nevertheless, it is a greenhouse gas, and its atmospheric concentrationis increasing at
a rate of about 0.2% per annum. N 2 0 is responsible for perhaps 6% of the greenhouse effect
(excluding H,O). N20 is also responsible for significantstratospheric ozone destruction, with
estimates ranging from 20 to 70% in the presence of stratospheric chlorine and bromine [49-
511.
It has recently been shown that FBC can produce relatively significant N20 emissions
when burning coal and petroleum coke(40-250 ppm at 6% 0,).This compares with less than
10 ppm for coal-fired pulverized fuel boilers for coal [49, 52-54]. N 2 0 emissions from FBC
decrease with increasing temperature. Control of N 2 0 emissions is thus feasible by creating
high-temperature zones through injection of small amounts of natural gas to the cyclone or
upper part of the combustor. Using these techniques, Gustavsson and Leckner [52] observed
N,O reductions on the order of 50%. N,O-reducing additives are also being investigated 1551.
Unlike coal, biomass fuels do not exhibit elevated N 2 0 levels under fluidized bed com-
bustion. As noted earlier, CANMET tests with deinking sludges showed N20 concentrations
below 10 ppm. Circulating fluidized bed combustion [0.8 MW(th) pilot plant] of wood pellets
showed values in the neighborhood of 1 ppm. Similar results were reported by Leckner and
Karlsson [48] [8 MW(th) CFBC] withN 2 0 emissions typicallyless than 10 ppm. Leckneret al.
report that for a 165-MW(th) CFBCunit, N 2 0 emissions were practically negligiblefor wood
firing [56].
B. Halogen Species
The principalCl-containing species producedin fluidized bed combustion of chlorine-
containing wastes is HC1 [57]. It has been frequently claimed that FBC systems with lime-
stone additionhave the potential to capture halidesin general andchlorine in particular via the
mechanism
Fluidized Bed Combustion 475
CaO + 2 HX e CaX2 + H20 (1)

where X is a halogen such as F, Cl, or Br. However, work on CaCl,, CaBr, and PVC addition
to both bubbling and circulating fluidized beds has shown that despite such claims, chlorine
and bromine are not effectively captured by limestone sorbents [57,58]. Except for CaF,, the
calcium halides tend to decompose under typical FBC conditions (800-950°C) and capture is
negligible above 850°C.
Experiments with additives containing Cl, Br, and I, either as the alkali metalsalts or in the
form of volatile halogen compounds (halons), have shown that the presence of halogens has a
pronounced effect on the CO concentration in the flue gases [59,60]. Massive addition of
chlorine-containing feedstocksto a fluidized bed combustor indicates that the conversion of CO
to CO, can be adversely affected [59-611. It has been suggested that these effects are due to
suppression (to equilibrium levels)of radical populations in the FBC environment, thus inhib-
iting reaction of CO with the OH radical [57, 59, 60, 621:
CO+OH=COz+H (2)
Other undesirable effects have also been noted, in particular an increase in NO, formation.
Anthony et al. [62] have speculated that this is due to modification of the limestone sorbent
surface.
Capture of chlorine in the baghouse is possible and has been reported by Itaya et al. [63],
who injected Ca(OH), into a bag filter to help control HCl emissions. Weinell et al. [M] have
also shown that the optimum temperatures for HCl capture with slaked lime [Ca(OH),] and
CaC03 is in the range of 500-600°C or below 150°C with Ca(OH), in the presence of H20
(which they ascribe to the presence of a liquid product phase). Such capturein an FBC boiler
or incinerator is thus somewhat limited unless conditions can be properly optimized.
In fact, significant chlorine capture by limestone sorbents in an FBC environment is not
even a particularly desirable phenomenon. CaCl, melts at about 782°C. Therefore, large ex-
cesses of such materials could lead to agglomeration of the bed material. Experience with
CANMET and Queen’s University bubbling fluidized bed pilot plants has shown significant
corrosion of metal internals, which can be traced to high levels of addition of PVC and CaC1,.
Equally, the presence of high levelsof CaC1, in electrostatic precipitators (ESPs)or baghouses
can be expectedto lead to problems. CaCl, is a potentially corrosive and deliquescent solid that
can be expected to cause corrosion in an ESP and caking and “blinding” of baghouse filters.
Although fluidized bed combustors have been showntobe able to burnmixed plastic
wastes, PCB-contaminated soil, and other chlorine-contaminated wastes [l ,17,18,26,27], it
seems likely that the use of some additional control technology suchas scrubbers and perhaps
combustion modificationof the FBC system itself (by additionof a premium fuel such as nat-
ural gas) is required for firing wastes containing very high levelsof chlorine.
C. Organic Species
In general, due to “low”-temperature operations, fluidized bed combustionhasnotbeen
thought of as appropriate for the destruction of hazardous organic wastes. Infact, FBC systems
can perform extremely wellas incinerators for almost all types of wastes. As mentioned earlier,
FBC can perform welldue to very good mixing, long residencetimes (up to hours for solids in
the combustor), and potential catalytic effects of bed particles. The proper combination of
these features allows FBCto be very effective in destroying organic species [12,13].
There are probably more elusive mechanismsat work in the destruction of organic species
by FBC. Classical “low”-temperature combustion such as occurs in “cool flames” involves
the formation of oxygenated species such as alcohols, aldehydes, and organic acids.At higher
476 and Anthony Preto
temperatures (>725”C), H, 0, and OH radicals become responsible for chain branching, and
this leads to a combustion process dominated by free radical processes [65]. High concentra-
tions of H and OH radicals canbe expected to destroy organics such asPAH provided that the
residence time and mixing (turbulence) are sufficient.
The importanceof radical processes for incineration was reexamined by Lyon [66] via the
oxidation kineticsof CHJCl, c6H6, and C6H,Cl (as representative of fuels thatare “difficult”
to incinerate). The conclusion was that besides the familiar lower flammabilitylimits there is
a second and “unrecognized” threshold for effective combustion “i.e., if a reaction is to occur
with the high rate a superequilibrium free radical concentration can provide, then the initial
concentration of the fuel must be sufficiently high to generate that superequilibrium concen-
tration” [66]. Furthermore, improvements in toxic organic material destructionby a factor of
up to 10,OOO achieved by the additionof a “clean” fuel were also reported. Similar results have
been reported by Banaszak, Miller, and coworkers, who studied improvements in the destruc-
tion efficiencyof organic species inan electrically heated gas stream by the addition of a small
“pilot” flame [67,68]. In these studies a temperature of approximately 1100 K was necessary
for the chain-branching reaction
H+02+OH+O (3)
to be faster than the reaction
H+O2M%H02+M
which otherwise served as a sink for the free radicals. Radicals multiplied rapidly at the loca-
tion where the gas streams mixed (i.e., waste gas and “pilot” flame), thus allowing attack of
the organic “wastes” [69].
It is well known that in flame combustion there exists a significant excess of radicals
(above the thermodynamically predicted concentrations) in the flame reaction zone [70]. It has
been demonstrated that radical concentrationsin FBC systems are also likely to be present at
above-equilibrium concentrations[57,59,60,62]. Thus, the low level oforganic emissions seen
from FBC systems is not particularly surprising, and from the point of view of emissions of
unburned hydrocarbons, FBC should be regarded as a high-temperature combustion technol-
ogy -
Another particularly important class of pollutants comprises dioxins and furans. Griffin
[71,72] speculated that the “Deacon reaction” is a source of elemental chlorine and hence
dioxins inthe combustion environment. He further suggested that the presenceof sulfur at S/Cl
ratios greater than 10 can completely suppress dioxin formationby removing the chlorine via
the reaction
Cl2 + SO2 + H20 4 SO3 + 2 HCl (5)
If this effect can be confirmed, then this might provide a new niche for high sulfur fuels for
cofiring with industrial wastes-a novel method for dioxin and furan control.
V. ASH MANAGEMENT
Fluidized bed combustion ashes can be classified into two distinct categories depending on
whether the fuel sulfur content is high enough to require limestone (or dolomite) addition (to
reduce SO2). If limestone addition is not required, then the property of the ashes is strongly
dependent on the natureof the waste being combusted and the material added to maintain par-
ticle bed inventory (e.g., sand). In that case very little of a general nature canbe said about the
ashes other than that FBC can reducethe massholume ratio of the waste being burnedby one
Fluidized 477
or two orders of magnitude. Even if the ashesare hazardous and must be disposed of in haz-
ardous waste disposal sites, the quantity of material is considerably reduced. FBC therefore
offers not only a net saving in terms of overall waste disposal, but also potential for the re-
covery of energy as steam or power. One of the few exceptions to this is combustion of coal
washery rejects, which can contain upto 70% or more of ash and for which any gains in net
reduction of materials are minimal. The potential energy from waste gain is still significant
enough to make thistype of project economically feasible.
A. SulfurCapture
For coals of moderateor high sulfur content, petroleum coke, and any high sulfur waste such
as pitch and tars from upgrading processes (all suitable FBC fuels [4,45]), sorbent (limestone
or dolomite) must be added to reduce SO, emissions. The properties of the ashesare strongly
affected by the presence of limestone. In an atmospheric fluidized bed combustor, limestone
calcines and then reacts via the reactions
CaCO3 e CaO + C02 (6)
and
CaO + SO;! + 3:1 0 2 e Cas04 (7)

Both of these reactions are reversible. However, the calcination reaction (6) normally goes to
near completion andat FBC temperatures canbe considered to be relatively rapid in compar-
ison to the sulfation reaction (7) [7,8,73]. Typically, when the ashes from FBC are examined
they are found to contain less than9%CaC03, and it is possible thatat least some of the car-
bonate may be due to recarbonization. On thermodynamic grounds, the sulfation reaction (7)
should go to completion; however, pore plugging normally prevents conversion (i.e., sorbent
utilization) from going beyond 50% (molar basis) [7,8]. Pore plugging occurs during sulfate
formation because the molar volume of the CaS04 product is greater than that of the original
CaCO,. Canada’sfirstindustrial-scale[22MW(e)]circulatingfluidized bed combustor at
Chatham, New Brunswick is able to achieve sorbent utilization of up to 51% [74]. The best
reported performance for a large bubblingbed facility is the Tennessee Valley Authority’s 20-
MW(e) unit with sorbent utilization up of to 45% [75]. In comparison,flue gas desulfurization
technologies suchas wet anddry scrubbing exhibit calcium utilization efficiencies on the order
of 85-92% [50].
As a result of below stoichiometric sorbent utilization, FBC systems produce a relatively
large amount of waste solids. For example, Minto or coal
Syncrude petroleum coke (both up to
8% sulfur) can produce 0.65 kg ofash for every kilogram of fuel fed, assuming a sorbent uti-
lization of 4596, 5% CaC03 in the final ash, and 90% SO2 removal. The significant ash pro-
duction quantities make it important that the ashbe well characterized and that disposal costs
be as low as possible, or alternatively that suitable applications be found for the ash.
B. Ash Disposal
Successful disposal of high-calcium FBC ashes is currently practiced throughout the world,
resulting in an increasing bodyof experience in this domain. In the United States thereare over
150 operating FBC units producing4.5 GW(e) [47] for which adequate ash management prac-
tices exist. Good overviews of ash disposal techniques are availablein the literature [76-781.
In Canada, Environment Canada, the federal government agency charged with developing en-
vironmental standards, has developed interim guidelines for dealing with CFBC ashes [79].
The disposal of FBC ash is complicated by the fact that such ashes show a tendency to react
with moisture in the atmosphere, leadingto expansion anddeterioration of the integrity of the
disposal site. Canadian experience witha number of test cells set up to study optimum hydra-
tion and compaction showed that the permeability of an optimally compacted test cell deteri-
orated from cndsec (equivalent to a clayliner) to c d s e c within 2 yearsofplacement
[80]. Work is proceeding to use a new patented hydration process (CERCHAR, France) to
selectivelyconverttheCaO component of Ca(OH),withouthydratingCaSO, or forming
aluminosulfates like ettringite or aluminosilicates [81,821. This process controls subsequent ex-
pansion and improvesthe behavior of the ashes for both disposal and utilization. Another tech-
nique for improvingthe behavior of ash is pelletization [83], which also offers the potential of
producing a commercial grade aggregate fromthe ash.
Canadian and Polish researchers (CANMET, Committee on Atlantic Coal, Environment
Canada, Canadian Electrical Association, Cracow University of Technology, Academy of Min-
ing and Metallurgy, Cracow, Poland) are jointly investigating ash disposal by mine backfill.
This technique produces ash water dense slurries (AWDS) that can be pumped over a kilometer
into abandoned mines.This technology is being used extensively in Poland for disposal of pul-
verized coal ashes. Such slurries have been shown to be able to set to a low strength material
with permeabilities of about cmlsec [84]. If successfully applied to FBC ashes, this tech-
nique will become a useful adjunct to existing disposal technologies.
C. Ash Utilization
As the scarcity and costsof landfill increase, utilizationof FBC ashes becomes moredesirable
and even necessary. Given that disposal costs for FBC residues approach $20/ton, there is a
major economic incentive to turn theashes into a salable product rather than a liability. In prin-
ciple, there are many potential uses for the high calcium residues from FBC [85,86]: agricul-
turaluse,lime substitute in acidicwaste neutralization, wastestabilizationagentinlime/
pozzolan systems, asphaltic concrete, synthetic aggregate, low-strength backfill applications
(with and without portland cement), and roller-compacted concrete.
Agricultural use of the ash as a lime substitute represents an obvious method of taking
advantage of the high CaO content and is already being applied [87]. Agricultural useis, how-
ever, limited by a number of factors. Obtaining the necessary license may be a lengthy and
costly undertaking. The lime component may be only a third of the ashes by weight, and the
ashes must therefore be used at twice the agricultural lime rate. Transportation costs for this
lower value product are significant, and in practice it is seldom economic to transport these
ashes beyond 150 km.
Acid neutralization is a very promising if restricted use for FBC-derived residues. Petro-
leum coke, which often hasa very high sulfur content (leading to the use of considerable quan-
tities of limestone for sulfur capture) and a low fuel ash component, is particularly suited to
such applications. This, in fact, is the method of disposal employed for two coke-fired [l00
MW(e)] CFBC units operated by NISCO in Lake Charles, Louisiana [88].
Ultimately, construction material applications may represent the most promising methods
for dealing with FBC-derived ashes. Unfortunately, some of the most technically promising
applications such as asphaltic concretes use only small amounts of FBC-derived materials, and
the economic benefits of such useare at best marginal [76,85]. FBC-derived residues have been
shown to beable to react with pozzolans to produce materials withcementitiousproperties, and
there are already a number of demonstrations of the use of such residues: low-strength backfill
applications, roadbase materials, mortars, masonry blocks, etc. [86]. Nevertheless, before
such uses can become widespread, considerable effort will be required to better understand the
cementitious reactions further, to reduce setting times, to improve the freeze-thaw behavior,
and also to resolve problems causedby destructive expansion often seenin FBC-derived prod-
ucts. Furthermore, the variability in such residues is likely to delay their widespread use. Fi-
nally, obtaining market acceptance for such products remains a major obstacle that must be
overcome before their use can become commonplace.
VI. SORBENTUTILIZATIONISSUES
An alternative to attemptingto use large quantities of ashes fromfluidized bed combustion of
high sulfur fuels is to improve the efficiency of the sulfur capture process. FBC sorbent utili-
low and can range from30 to 45% [7,8]. Given that both
zation for sulfur capture is relatively
sorbent transportation costs and disposal costare often on the order of $20/ton, major savings
can be realized if near-stoichiometric utilizations canbe achieved. For example, consider the
165-MW(e) CFBC unit being constructed in Point Aconi, Nova Scotia, which will burn a high
sulfur coal. This unit is expected to generate up to 1000 tonnes of ash per day [89]. Near-
stoichiometric utilization of the limestone could produce savingsof up to $20,000 a day.
Research on reactivation or enhancement of sorbent performance has a long history. Ar-
gonne National Laboratories have used both halide salts and sodium carbonate addition [90]to
enhance sorbent performance anda direct hydration technique using steamin a fluidized bed
hydrator to reactivate spent sorbent for reinjection and reuse [91,92]. The first process works
by surface modification of the limestone in the combustor allowing moderate sintering of the
sorbent pores so that they become available for further reaction with SO,. In the hydration
process, the spent sorbent is reactedwithwater,whichbreaks the sulfate shell that forms
around spent sorbent particles, thus allowing unreacted limestone to be used on subsequent
reinjection intothe combustor. In principle, hydration can be repeated several times until near-
stoichiometric utilization of the sorbent is achieved. These methods have been duplicated by
other researchers with similar success[60,93], however, the use of additives is not promising
because of the corrosion and fouling problems likely to be experienced if such salts were in-
troduced into a boiler.
CANMET has also developed a technique for reactivation that involves fine grinding and
pelletization of limestone to produce a sorbent with enhanced porosity[7,8]. Improvements in
sulfur capture of up to a factor of 5 have been obtained. This work was aimed at bubbling
fluidized beds; the advent of circulating fluidized beds has raised concerns about the physical
strength of such “artificial” sorbents in the more vigorous CFBC environment. European re-
search intothe use of synthetic reusable sorbents [94] hasbeen somewhat successful; however,
the approach does not appear to be economically viable.
Currently, itwould appear that thereare two promising approaches to improve sorbent per-
formance: an improved hydration technology(e.g., CERCHAR process), which delivers a dry
product with complete hydrationof the CaO componentof the ash, and injectionof spent sor-
bent in a slurry form either into the combustor or into the back end of the boiler. These pro-
cesses are different from the hydration techniquesin that they rely on reactions with the fuel
ash componentsto form high-surface-area silicate and aluminosilicate products,which are then
capable of secondary reaction withSOz. The most noticeable of these processes is perhaps the
proprietary (ABB-CE) ADVACATE process [95]. These types of processes are of limited val-
ues for use with petroleum cokeor pitches or tars that have very low ashes, in that these fuels
do not provide the required silica products in the fuel ash. For these types of fuels, hydration
process may well offer the best hope for ash reactivation.
A Canadian study [96] on CFBC bottomash from Elmtree limestone found that the degree
of hydration of the spend ashes was directly proportional to the degree of reutilization of the
sorbent. The results were correlated by
Z Utilization = 0.23 X (% degree of hydration) + 38 (8)
This suggests that a process that achieves effectively complete hydration (e.g., CERCHAR
process [82]) may be particularly suitable for reactivation. The highest CaO contents are typ-
ically foundin bed ashes; therefore,a promising strategy may be to take the bed ashes, hydrate
them for reactivation, and reinject them. This would also ensure that only one ash stream is
produced for disposal.
VII. CONCLUSIONS
Research on bench-scale and pilot-scale reactors throughout the last two decades has shown that
fluidized bed combustion appearsto be an ideal technology for efficiently burninga wide va-
riety of fuels and wastes whilealso achieving very low emissions of pollutants. The only sig-
nificant difficulties havebeenrelated to feedingnonconventionalfuelsusingpilot-scale
equipment. These difficulties are resolvable in full-scale units. A number of large-scale [>20
MW(e)] unitshave recently begun operating, successfully burninga wide variety of industrial
and agricultural wastes.
FBC cofiring is increasingly being adopted to burn a waste fuel that may not be able to
sustain combustion onits own or as a topping fuelif insufficient waste fuelis available. Cofir-
ing does not discourage recycling programs,as any reduction in the quantity of waste (partic-
ularly MSW) can be made up with the premium fuel. Cofiring thus appears to offer a palatable
solution to the considerable municipal waste disposal problems now being experienced across
North America.
In terms of emissions, the application of FBC for waste minimizationis characterized by
the following statements:
NO, levels are much lower thanfor conventional systems, due primarily to lower combustion
temperatures.
SO, levels can be reduced by using limestone or dolomite as bed material for in situ sulfur
capture.
FBC’s turbulent mixing and increased residence times result in excellent organic compound
destruction, and FBCshould therefore be regarded as a high-temperature combustiontech-
nology.
N,O concentrationsfor fluidized bed combustion of biomass fuels are typically below 10 ppm.
Although fluidized bed combustors have been shown to be able to burn mixed plastic wastes,
PCB-contaminated soil, and other chlorine-contaminated wastes, it seems likely that the
use of some additionalcontrol technology is required forfiring wastes containing very high
levels of chlorine.
Fluidized bed combustion ash management must be addressed in anyconsideration of com-

bustion of waste fuels. In some cases ashes canbe used as agricultural or construction material
additives, thus further minimizing the amount of waste that must be discarded. Even if the
ashes cannot be used, FBC offersa considerable reduction in the mass of material over thatof
the waste fuel. FBC’s fuel versatility makes it an ideal
candidate for combining energy recovery
and waste minimization.
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with lime and limestone: kinetics and sorption capacity,Ind. Eng. Chem. Res., 31,164-171 (1992).
65. Haynes, B. S., Soot and hydrocarbons in combustion, in Fossil Fuel Combustion-A Source Book
(W. Bartok and A. F. Sarofim. 4s.). Wiley, New York, 1991.
66. Lyon, R. K.,The existence of a second threshold for combustion and its implication to incineration,
Proc. Twenty-third Symp. (hr.) Combustion, Orltans, France, 1990, pp. 902-908.
67. Banaszak, T.,Miller, R., and Zembrzuski, M,,The influence of flame-generated free radicals on
the thermal oxidation of waste gases, JAPC, 37, 1434-1438 (1987).
68. Banaszak, T., Miller, R., Rybak, W., and Zieba, A., Thermal-catalytic incineration of waste gases,
First Int. Conf. Combustion Technologies for a Clean Environment, Vilamoura (Algarve), Portugal,
Sept.3-6,1991.
69.Bulewicz,E. M., Cracow Univ. Technology, Poland, Private communication, November 1992.
70. Gaydon and Wolfhard, Flames: Their Structure and Radiution, Chapman and Hall, 1979.
71. Griffin, R. D., A new theory of dioxin formationin municipal solid waste combustion, 78th Annual
Meeting of the Air Pollution Control Assoc., Detroit, MichJ, June 16-21, 1985.
72. Griffin, R. D., A new theory of dioxin formation in municipal solid waste combustion, Chemo-
sphere, 15, 1987-1990 (1986).
73.
Couturier,M. F., Sulphur DioxideRemoval in
Fluidized
Bed
Combustors,
Tech.
Rep.
QFBC.TR.86.1 to Energy, Mines and Resources, Canada, 1986.
74. W. H. Richards et al., ChathamCFB test bum of Nova Scotia coal and limestone, Tenth Int. Conf.
Fluidized Bed Combustion, San Francisco, Calif., April 30-May 3, 1989, p. 887.
75. Bass, J. W., 111, Experience at 20 MW, Shawnee Power Plant, AFBC Development Project Tech.
Papers, TVA/OP/ED and T-87/24, 1987.
76. Smith, I., ManagementofAFBCResidues, I E A CoalRes.Rep.IEACW21,February1990.
77. Berry, E. E., and Holcombe. L. E., FBC waste characterisation, utilization and disposal-recent
experience, 1991 CANMET CFBC Ash Management Seminar (E. J. Anthony and F. Preto, eds.),
Halifax, Nova Scotia, July 2-3, 1991.
78. Kissel, R. K., Ross,G. G., and Anthony, E. J., Experience with the management of CFBC resi-
dues, 1989 Joint Power Generation Conf., Dallas, Tex., Oct. 22-26, 1989.
79. EPS, Interim Recommended Practises for the Management of Solid Residues h m the Circulating
Fluidized Bed Combustion, Environment Canada Rep. EPS 1/PG/4, May 1992.
80. Georgiou, D. N., Kissel, R. K., and Ross, G. G., Geotechnical characteristics and landfilling of
CFBC residues, Eleventh Int. Conf. on FBC, Montreal, Quebec, Apr. 21-24, 1991.
81. Blondin, J., The CERCHAR hydration process, Proceedings of the 1991 CANMET CFBC Ash Man-
agement Seminar (E. J. Anthony and F. Preto, ed~.),1991.
82. Blondin, J., Anthony, E. J., and de Iribarne, A. F?,A new approach to hydration of FBC residues,
Welfth Int. Conf. FBC, San Diego, May 9-13, 1993.
83. Bland, A. E,, Kissel, R. K., and Ross, G. G., Enhanced FBC waste management using pelletiza-
tion, Eleventh Int. Conf. FBC, Montreal, Quebec, Apr. 21-24, 1991.
8 4 . Bulewicz, E. M., Zoldani, E., and Dudek, K., Site Evaluation of the Ash Water Dense Suspension
Process, report to CANMET under contract 23440-1-9061/01-SQ, September 1991.
85. Berry, E. E., Anthony, E. J., and Kalmanovitch, D. F?,The uses and morphology of atmospheric
fluidized bed combustion wastes from Canada's first industrial AFBC boilersJ. Energy Resources
Techno!., 109(3). 148-154 (1987).
86. Bland, A. E., Kissel, R. K., and Ross, G. G., Utilization of CFBC ashes in roller compacted con-
crete applications, Eleventh Int. Conf. FBC, Montreal, Quebec, Apr. 21-24. 1991.
87. Lewnard, J. J., Agricultural applications of CFBC ashes from western coals, Proceedings of the
1991 CANMET CFBC Ash Management Seminar (E. J. Anthony and F. heto, eds.), 1991.
88.Zierold,D.,NISCOcogenerationfacility,ApplicationofFluidized-BedCombustionforPowet
Generation Utility Conf., sponsored by EPRI, Cambridge, Mass., Sept. 23-25, 1992.
89.Gridley, N., andCousins,D.,NovaScotiaPowerCorporationPointAconigeneratingstation:
CFBC residue management, Proceedings of the 1991 CANMET CFBC Ash Management Seminar
(E. J. Anthony and F. Preto, eds.), 1991.
90. Johnson, I., Lenc, J. F., Shearer, J. A., Smith, G. W.,Swift,W.M.,Teats,F. G., "her, C. B.,
and Jonke, A. A, Support Studies in Fluidized-Bed Combustion, Argonne Natl. Lab. Quart. Rep.,
ANL/CEN/FE-79-8, April-June 1979.
91. Johnson, I., Myles, K. M., Fee, D. C., Lenc, J. F.,Moulton, D. S., Shearer, J. A., Smith, G . W.,
'hmer, C. B., and Wilson,W. I., Exploratory and Basic Fluidized-Bed Combustion Studies, Semi-
ann. Rep., ANUCENIFE-81-2, October 1980-March 1981.
Fluidized 485
92. Shearer,J.A.,Smith, G. W., Moulton,D. S., Smyk,E.B.,Myles, K. M., Swift, W.M.,and

Johnson, I., Hydration processfor reactivating spent limestone and dolomite sorbents for reuse in
fluidized-bed coal combustion, Sixth Int. Conf. Fluidized Bed Combustion, Atlanta, Ga., Apr.9-
11,1980.
93. Razbin, V.V.,Anthony,E.J.,Desai,D.L.,andFriedrich. F. D., FluidizedBedCombustionof
High-Sulphur Maritime Coal, ERL Div. Rep. 85-44(0PJ), December 1984.
94. Wolff, E. H. P, Regenerative sulfur capture in fluidized bed combustionof coal: a fixed bed sorp-
tion study, Doctoral Thesis, Delft Univ., 1991.
95. Sedman, C. B., Maxwell, M. A., Jozewicz, W., and Chang, J. C. S., Commercial development of
theADVACATEprocess for flue gas desulfurization, 25th Intersoc. Eng. Conf. Environmental
Control, Reno, Aug. 16, 1990.
%. Marquis, D. L., Couturier, M. F., and Steward, F. R., A Thermogravimetric Study on the Reacti-
vation of Spent CFJ3 Limestone by Hydration, Report to Energy, Mines and Resources, CANMET,
August1991.
Part I11
TREATMENT
WASTEWATER
22
An Overview of Physical,
Biological, and Chemical Processes
for Wastewater Treatment
Kanti L. Shah
Ohio Northern University
Ada, Ohio
1. WATERPOLLUTANTS
Pollutants can originate from either a point source or a dispersed source. A point source is a
channel, pipe, or any other confined source such as a pipe discharging wastewater treatment
plant effluent or untreated wastewater intoa stream. A dispersed sourceis an unconfined area
from which pollutantsenter a body of water. For example, surface runoff from agricultural and
urban areas carrying such pollutantsas silt,fertilizers, animal wastes, pesticides, and oil drips
do not enter at one particular point. These materials can enter a body of water as it flows
through the area. Also, acidic runoff from mining areas is a dispersed pollutant.
Water pollutants from both point and dispersed sources can be classified into groups of
materials, based mainly on their environmental or health effects. The following list indicates
common types of pollutants of concern:
Pathogenic organisms
Oxygen-demanding materials
Plant nutrients
Suspended solids and sediments
Toxic chemicals and metals
Radioactive substances
Oil
Thermal (heat) pollution
Municipal and industrial wastewaters and runoff from farms and other open areas (streets,
parks, lawns, etc.) are sources of the first five types of pollutants.
A. Pathogens
Diseasecausing microorganisms are excreted in the feces of infected humansand animals and
may be carried into the waters receiving the wastewater.
489
490 Shah
B. Oxygen-Demanding Matter
Oxygen is used in the aerobic stabilization of organic waste matter. Anything that can be ox-
idized in water with the consumption of dissolved molecular oxygen is termed an oxygen-
demanding, or aerobic substance. This materialis usually biodegradable organic matter, buta
few inorganic compounds also oxidize in this manner.
Oxygen is needed for bacterial oxidation of pollutants during biodegradation. This con-
sumption of dissolved oxygen may exceed the capacity of surface waters to replenish the dis-
solved oxygen by natural means and pose a threat to higher forms of aquatic life that need
oxygen to live. Thecritical level of dissolved oxygen (DO)' varies among species. Some game
fish may require more than 3.5 mg DOIL.
C. PlantNutrients
Nitrogen and phosphorus are two nutrients that are of concern in water pollution. Both con-
tribute to the growth of algae and the eutrophication of lakes. Nitrogen occurs in many forms,
e.g., organic nitrogen, ammonia, nitrate, and nitrite nitrogen. In wastewater or contaminated
water, the main source of nitrogen and its complex compounds is human and animal feces and
fertilizers. Excessive nitrates in drinking water can pose health problems.
Phosphorus is also an essential nutrient that contributes to the growth of algae and other
plant life in lakes. The sources of phosphorus in water include agricultural runoff containing
fertilizers, animal wastes, and common detergents.
D. SuspendedSolidsandSediments
Organic or inorganic particles that are carried by wastewater intoa receiving waterare termed
suspended solids (SS). Colloidal particles in suspension cause the turbidity observed in many
surface waters. Organic suspended solids also exert an oxygen demand. Inorganic suspended
solids are dischargedby some industries, but their main source is soil erosion due to logging,
stripmining, and construction activities.
E. ToxicChemicalsand Metals
A wide variety of toxic organic and inorganic substancesare found in water in very small or
trace amounts. Some of these substances are from natural sources, but many come from in-
dustrial and agricultural activities. Many of these contaminants can be dangerous to public
health. Some heavy metals that are toxic are cadmium, chromium, lead, silver, and mercury.
Arsenic, barium, and selenium are also poisonous inorganic elements. All these chemicals and
metals must be monitored in drinking water.
E RadioactiveSubstances
Radioactivity is widespread in surface water because of fallout from testing of nuclear weapons
and wastewaters from nuclear power plants, hospitals using radioactive substances for treat-
ments, university labs, and industrial users. Radioactivityin drinking water can be due to nat-
ural or artificial radionuclides. In a few water supplies, radioactivity can reachconcentrations
that pose a risk of cancer.
'See Glossary for definition.

Physical,
Processes
Chemical
Biological, and 491
G. Oil
Oil pollution can enter the surface water and groundwater from various sources such as oil
spills on the groundor surface waterand industrial activity. The majority
of oil and oily wastes
generated are not classified as hazardous. Nonhazardous oils and oily wastes are amenable to
recovery.
H. Thermal Pollution
Heat is considered to be a pollutant because of the adverse effect it canhave on oxygen levels
and aquatic life in rivers and lakes. The cooling water used in industries and power plants
car-
ries away waste heat as it passes through the condensers in the plant. Cooling water temper-
ature may increase up to 15°C after it serves to condense the steam. The discharge of warm
water into surface waters is called thermal pollution.
II. WASTEMANAGEMENT
Waste management is an all-encompassing term. It consists of several processes: the elimi-
nation or reduction of waste, the recycling or reuse of waste material, and the destruction
or treatment of waste to render itharmless through chemical,physical,and/orbiological
processes.
Waste reduction or minimization can be incorporated into all aspects of the production
process, recyclingor reuse occursafter a product hasbeen used anddiscarded, and waste treat-
ment is essentially an addition to end-of-process, i.e., “end-of-pipe,” pollution control. Sec-
tions III-V discuss the state-of-the-art technology of wastewater treatment and disposal.
111. PURPOSES OF WASTEWATER TREATMENT

Wastewater is collected in combined and separate sewers from industries, commercial estab-
lishments, and householdsand transported to the treatment plant. The plant effluentis usually
disposed of by being discharged into rivers, lakes, or estuaries. See Figure 1.
Wastewater typically contains many different substances, both suspended and dissolved,
inorganic and organic. The total amount of organic material is related tothe “strength” of the
wastewater. This is measuredby the biochemical oxygen demand (BOD).Another measurere-
lated to “strength” and “quality” of wastewater is the total amountof suspended solids (TSS).
Another group of impurities of major significancein wastewater are plant nutrients, spe-
cifically compounds of nitrogen (N) and phosphorus (P). Oil and grease are also common pol-
lutants. The amount of pathogens (disease-causing microorganisms) in wastewater is usually
proportional to the concentration of fecal coliform bacteria. BOD,TSS, N, P, and coliform
concentration are important parametersof water quality. Actually, wastewater contains so many
different substances that itis impractical to identify each substanceor microorganism. The ap-
proximate composition of an average domestic wastewater is givenin Table 1.
Wastewater is treatedto meet the minimum level of effluent quality setby the state or the
U.S. Environmental Protection Agency (EPA). The purposes of wastewater treatment are to
remove most of the suspended and dissolved organic and inorganic material and destroy patho-
genic microorganisms. In many cases it is also necessary to remove plant nutrients-nitrogen
and phosphorus.
Some pollutants, both inorganic and organic, are resistant to conventional treatment pro-
cesses. Such contaminants are called “refractory” contaminants. Phosphate, for example, is
present inverylow concentrations in natural waters but is increasedinwastewatersfrom
492 Shah
Industrial
Combined Domestic wastes
wastewater wastewater (usuallypretreated)
t
Disposal
Wastewater
Treatment
Plant
Watersupplies
Figure 1 Location of a municipal wastewater treatment plant.
Table 1 ApproximateComposition of an Average Domestic Wastewater (rng/L)

~
Component
sedimentation
sedimentation
Before
After
Biologically
treated
Total solids 800 I 680 530
Total volatile solids 440 340 220
Suspended solids 30 240 120
Volatile suspended solids 180 100 20
BOD 200 130 30
Ammonia nitrogen as N 15 15 24
30
Total nitrogen as N 35 26
Soluble phosphorusas P 7 7 7
Total phosphorus asP 10 9 8
Source: Adopted with permission from Viessman and Hammer (1993).
Physical,
Processes
Chemical
Biological, and 493
domestic sources due to the use of synthetic detergents and runoff from fertilized fields. Or-
ganic nitrogenous compounds decompose to ammonia and oxidize to nitrates during waste
treatment. Certain high molecular weight materials (e.g., dyes and surfactants) are not bio-
degraded. Also, agricultural land runoff includes pesticides such as chlorinated hydrocarbons.
Excessive concentrations of nutrients often lead to large growths of algae, which in turn
become oxygen-demanding materials when they die and settle to the bottom. Conventional
waste treatment is only 3 0 4 0 % effective in removing these nutrients.Advanced waste treat-
ment methods (tertiary treatment) are required for greater nitrogen reduction and phosphorus
removal.
W. TREATMENTPROCESSES
Conventional wastewater treatment consists of preliminary, primary, and secondary m t m e n t
processes. Primary treatment consists of pumping, screening, and sedimentation, which in-
cludes grit removaland primary settling. Screening, grit removal,and primary settling remove
large and heavy solids and floatable materials. In secondary treatment, biological aeration is
used to metabolize and flocculate colloidal and dissolved organics.
Tertiarytreatment(advanced wastewater treatment), e.g., chemicalcoagulation,isan
additional step applied only after the wastewater has undergone conventional primary and sec-
ondary treatment processes. Tertiary treatment is used to remove contaminants from waste-
water that are usually not taken out by conventional techniques, for example, phosphorusand
nitrogen. Figure 2 is a flow diagram showing the stages of wastewater treatment.
A. PreliminaryTreatment
The first level of wastewater treatment includes the physical processes of screening and sedi-
mentation, which remove large floating objects and settleable solids. These account for about
60% of the total suspended solids (TSS) and approximately 35%of the biological oxygen de-
mand (BOD).
Raw wastewater first undergoes coarse screening. Bar screens made of long narrow metal
bars spaced l in. (25 mm) apart retain floating debris such
as large fish and other bulky objects
that could clog pipesor damage mechanical equipment. In large wastewater treatment plants,
the bar screens are cleaned by an automatic mechanical device. A mechanical cutting device
called a comminutor is installed after the coarse screens in some treatment plants. A commi-
nutor consists of a slotted cylinder with a moving cutter blade that shreds and chops solids that
pass through the bar screen. The shredded material is then removed from the wastewater in the
primary settling tank (Figure 2). In small sewage treatment plants, a manually cleaned bar
screen is generally installed in a channel nextto the comminutor to serve as a bypass during
comminutor repair.
B. Primary Treatment
Wastewater contains suspended matter that has a higher specific gravity than the liquid and is
in a relatively quiescent state, the particles will settle out because of gravity. Grit chambers
remove grit, including gravel, sand, and heavy particulate matter such as corn kernels, bone
chips, coffee grounds, and broken glass. All of this accounts for only a portion of the inert
suspended solids in raw sewage. After grit removal, the wastewater still contains suspended
solids, which are then removed by sedimentation.
494 Shah.
Raw
wastewater
r r
Grit
Chamber
Basin
Tertiary Treatment
Biological
Treatment
Advanced
Waste
Treatment
-
-
*
+
I
Receivine-
Body
Figure 2 Stages of wastewatertreatment.
1. Grit Removal
For design purposes, grit is defined as 0.2-mm particles with a specific gravity of 2.65 and a
settling velocity of 0.075 fps (0.0225 &sec). Grit removal in municipal waste treatment pro-
tects mechanical equipment and pumps from abnormal abrasive wear, prevents pipe clogging,
and reduces accumulationsin the settling tanks. ' b o types of grit removal units that are used
in wastewater treatment plants are the horizontal flow type and the aerated type.
Physical, Biological, and Chemical Processes 495
Figure 3 Grit collector assembly with mechanical scraper.
Horizontal flow type. In sewers, the flow velocity is generally not less than 2.00 fps (0.6
dsec), which is “self-cleaning velocity.” Most of the gritty material settles out of the
flow by gravity if the velocity is reduced to 1 fps (0.3 &sec). Therefore, to prevent scour-
ing of the settled grit and other material, the horizontal velocity of the grit removal unit is
controlled at approximately 1 fps (0.3 dsec). Figure 3 diagrams a chain-and-bucket grit
collector.
Aerated type. Aerated-type grit-removal units may be square or rectangular hopper-bottom
tanks with the inlet and theeffluent weir on opposite sides of the tank.The shearing action
of the air bubbles strips the inert grit of the organic material that adheres to its surface.
These unitsare often designedto keep the organic solids in suspension whilethe grit settles
out. Design of an aerated hopper-bottom grit tank is based on a detention time of approx-
imately 1 min at peak hourly flow. Settled matter is removed from.the hopper bottom by
gravity flow, pumping, screw conveyor,or bucket lift.
The grit removed from thegrit chambers is high in organic content. In most plants, the grit
is washed before disposal in the landfill. Washing can be done by a counterflow grit washer,
which functions like a screw conveyor. The waste organics are returned to the plant influent.
Another methodis to use a centrifugal pump to lift the slurry from the grit pit to a centrifugal
cyclone, which separates the grit from the organic material and discharges it toa classifier for
washing. The wash water with organics is returned to the wastewater.
Primary settling tanks are used to remove the readily settleable solids preceding further
treatment. With chemical treatment and flocculation, the primary settling tank (clarifier) can
remove a significant amount of colloidal particles. Intermediate and final settling tanks are
496
lr
Shah
- Baffle
Effluent Weir
Q- U Outlet
Settling Zone Zone

Inlet
Zone
-- ----------
SludgeZone
(4
Sludge Zone
(b)
Figure 4 (a) Horizontal settling tank. (b) Upflow settling tank.
used to remove the settleable solids following biological treatment prucesses. These settling
tanks can be either circular or rectangular and are designed to operate on a continuous flow-
through basis.
Figure 4 is a sketch showing the four zones-inlet, settling, outlet, and sludge storage.The
inlet zone distributes the flow evenly across the cross section of the settling zone. It consists
of
inlet pipes andbaffles. Wastewater enters at the center behind a stilling baffle and travels down
and outwardtoward the effluentweir. The inletline usually terminates near the surface, butthe
wastewater must travel down behind the baffle before it enters the actual settling zone. The
baffle reduces the velocity and forces downward motionof the solids.
Following the inlet zoneis the settling zone. A good inlet designis important for efficient
removal of suspended solids in the settling zone. The flow velocity decreases in the settling
zone, and suspended solids settle out and accumulate in the sludge zone. Theconfiguration and
depth of the sludge storage zone depends upon the frequency of cleaning, method of cleaning,
and estimates of sludge production. Mechanically cleaned tanks have bottom scrapers. The
sludge is continuously scrapedto the hopper,from which it is pumped out.The tank bottom has
a 1% slope in the direction of the sludge removal point. The sludge hopper is designed with
sides at a vertical-to-horizontal slope of between 1.2: 1 and 2: 1.
The function of the outlet zone is toremove the settled water from the basin without car-
rying particles with the effluent. The outlet zone should prevent short-circuitingand loss and
destruction of floc. A proper outlet design can prevent scouring and thus loss of floc.
Physical,
Processes
Chemical
Biological, and 497
In the design of a sedimentation tank, the settling velocity (V,) of the particles to be re-
moved should be greater thanthe overflow rate (Vo).The determinationof the particle-settling
velocity is different for differenttypes of particles. Settling properties of particles are charac-
terized into the following classes.
Type I sedimentation is characterized by particles that settle in a discrete manner at a constant
velocity, suchas sand andgrit material. Particles do not come into contact with each other.
I settling occurs in grit chambers.
Type IZ sedimentation is characterized by particles that flocculate while settling. Since floc-
culation constantly changes the size of particles, the velocityof the particles is also chang-
ing. These types of particles are present in the settling tanks following tricklingfiltration.
In Qpe IZZ sedimentation, the particles tend to settle as a mass, leading to a separation of a
clear zone anda sludge zone. Zone settling occurs in the tank following an activated sludge
unit and sludge thickeners.
C.SecondaryTreatment(Biological)
Physical treatment of raw municipal wastewater by sedimentation removesmost of those pol-
lutants that will either float or settle out by gravity, which accounts for only approximately 35%
of the BOD. The major purpose of secondary treatment is to remove nonsettleable (colloidal
and dissolved) solids in the wastewater. “Secondary treatment” is generally considered to
mean at least 85% efficiency in reducing BOD and now represents the minimum degree of
treatment required by law in most cases. Some of the plant nutrients are also removed. The
removal of organics and nutrients helpsto protect the receiving watercourse. Secondary treat-
ment processes are almost always biological systems.
Biological treatment systems are living systems that rely on mixed biological cultures to
break down waste organics and remove organic matter from the solution. A biological waste
treatment system provides an artificial and controlled environment suitable for the growth of
microorganisms that can stabilize the organic pollutants in the wastewater before it is dis-
charged intothe surface waters. These living microorganisms, including bacteria and protozoa,
consume the organic pollutantsas food. They metabolize the biodegradable organics, convert-
ing them into carbon dioxide, water, and energy. The primary use of energy is for synthesis.
The maximum rate of synthesis occurs simultaneously with the maximum rate of energy yield
(maximum rate of metabolism). Aerobic metabolism requires oxygen for the processes of me-
tabolism and synthesis. In anaerobic metabolism, the metabolism and synthesis take place in
the absence of oxygen.A low energy yield per unit of organic matter resultsfrom an incomplete
reaction. When the supply of biologically available energyis exhausted, the processes of me-
tabolism and synthesis cease.
To keep the microorganisms productive in their taskof wastewater treatment, they require
an ample supply of oxygen, suitable temperatures and ph, a nontoxic environment, and other
favorable conditions. The design and operation of the secondary treatmentis based upon these
factors.
Several types of biologicaltreatmentsystems are stabilizationpond,oxidation ditch,
biotowers, trickling filter, and activated sludge. The latter two are the most common.
1. TricklingFilters
A trickling filter consists of a bed of coarse material, such as stones, slats, or plastic media,
over which wastewater is applied. A widely used design is a bed of stones approximately5-7
ft (1 S-2.1 m) deep; it is usually circular and may be as large as 200 ft (60 m) in diameter.
Figure 5 shows a trickling filter, and Figure 6 is a flow diagram of a trickling filter plant.
498 Shah
Figure 5 A tricklingfilter.
Trickling filters are usually preceded by primary treatment to remove large and settleable
solids. The wastewater is typically distributed over the surface of the rocks by a rotating arm
that has nozzles along its length and sprays wastewater evenly over the surface of the trickling
filter. The distributor arm is mounted on a center column in the trickling filter. It is driven
around by the reaction force of the wastewater. The underdrain system serves to collect and
carry the wastewater from the bottom of the bed and also permits air to circulate through
the bed.
The primary effluent is sprayed on a bed of crushed rock or other media coated with bi-
ological films. The biological slime layer consists of bacteria, protozoans, and fungi. Sludge
Q + Q.. Q + QR
Wet well
Figure 6 How diagram of a trickling filter plant.

Physical,
Processes
Chemical
Biological, and 499
worms, rotifers, filter-fly larvae, and other higher animals also grow in this environment. As
the wastewater flows over the microbial film, the soluble organics are metabolized and the col-
loidal organicsare absorbed ontothe surface, thus removing organic substances from the waste-
water. Air circulating through the void spaces in the bedof stones provides the oxygen for
stabilization of the organics by the microorganisms.
The rocks in the trickling filter are usually approximately 3 in. (75 mm) in size to provide
a large surface area for the biological growths, and the large voids allow air circulation. Some-
times materials such as modules of corrugated plastic or redwood are used as the medium in-
stead of rocks.
As the microorganismsgrow and multiply, the slime layer thickens. Dueto its weight and
the flushing action of flowing wastewater, the slime is washed off the rock surfaces. The trick-
ling filter effluent is collected in the underdrainsystem, from where itflows to a sedimentation
tank called a secondary or final clarifier.
To maintain a uniform flow rate through the trickling filter and to keep the distributor arm
rotating during periods of low wastewater flow,a portion of the effluent is pumped back to the
trickling filter inlet. Recirculation alsoserves to improve the treatment efficiencyof the trick-
ling filter; it allows a certain portion of the wastewater to make a second pass throughthe film
of microbes on the rocks. Thereare many recirculation patterns and configurations of trickling
filter plants, and these may be direct or indirect.
Recircularion. The amount of recirculation can vary. It is characterized by a recirculation ra-
tio, which is the ratio of recycled flow to raw wastewater flow,
R = QR/Q
where R is the recirculation ratio (dimensionless), QR is the recirculated flow rate (fi3/sec or
m3/sec), and Q is the wastewater flow rate (ft3/sec or m3/sec). The recirculation ratio, R , is
generally in the range of 0-3.0.
Hydraulic Load and BOD Load. The rate at which the wastewater flow isapplied to the trick-
ling filter surface is the hydraulic load. The rate at which organic material is applied to the
trickling filter is called the organic or BOD load.
The hydraulic load depends on the recirculated flow QR;the total flow through the trick-
+
ling filter is equal to Q QR.
Q + QR
Hydraulic load = - AS
where A, is the trickling filter surface areain square meters or square feet. Hydraulic load can
be expressed in cubic feet per square foot per day, cubic meters per square meter per day, or
millions of gallons per acre per day.
The rate at which organic material is applied to the trickling filter is expressed as BOD
load. It doesnot include the BOD of the material in the recirculated flow.The formula for BOD
load can be expressed as
or
Q X BOD
Organic
load = 8340 X v Ib/(lo00 @day)
500 Shah
I
3
Figure 7 An activated sludge unit.
where BOD is the biological oxygen demand of the primary effluent in milligrams per liter or
parts per million and V is the volume of the trickling filterbed in cubic meters or cubic feet.
Eflciency. The BOD reduction efficiency of a trickling filter unit depends on organic load,
recirculation ratio, and temperature. Generally, the efficiency increases with increasing recir-
culation and temperature and decreasing organic load.
2.
ActivatedSludgeTreatment
The activated sludgeprocess is a biological wastewater treatment technique in which a mixture
of wastewater and microorganisms is agitated and aerated. Wastewater is fed continuously int
an aerated tank, where the microorganisms metabolize and biologically flocculate the organics
using oxygen provided in the compressed air. Figure 7 shows an activated sludge unit.
%Fits + oxygen + CO1 + Hz0 + Energy
Aeration and mixingare achieved by continuously injecting compressed air into themix-
ture through porous diffusers located at the bottom of the tank (Figure 8a). Sometimes me-
chanical devices such as propeller-type mixers located at the liquid surface are used (Figure
8b). The propeller blades mix air with the wastewater and keep the contents of the tank in
suspension.
The aerobic microorganisms in the tank grow and multiply, forming an active suspension
of biological solids called activated sludge. The mixture
of the activated sludge and the waste-
Mechanical
Aerator 7
I k/- Air suppl’ Line
Figure 8 An activated sludge unit achieves aeration and mixing (a) with diffused air Or (b) with a
mechanical aerator.
water in the aeration tank is called mixed liquor. In most cases the aeration period is 6-9 hr.
The biological solids are subsequently separated by gravity from the mixed liquor under qui-
escent conditions in the final clarifier. The clarified water near the surface (the supernatant) is
discharged from the final clarifier overweir.a The settled sludge is pumped out from a sludge
hopper at the tank bottom. A portion of the sludge is returned to the aeration so tank
that active
and acclimatized microorganisms can absorband metabolize organics more efficiently. Since
the organisms grow and multiply greatly, it is not possible to pump all the sludge to the aera-
tion tank. Therefore, excess sludge is diverted to the sludge handling unit for treatment and
disposal.
General loading and operational parameters for the activated sludge processes used thein
treatment of municipal wastewater are listed in Table2. The wide rangeof aeration periodsand
BOD loadings used in activated sludge processes differentiate the processes from each other.
Also, the aeration tank‘s size and shape influence the process.
An important indicator used in the design and operation of activated sludge systems is the
food/microorganism ( F M ) ratio. The ‘ 6 f ~ o dor
” the BOD in the influent wastewater (without
regard to return sludge) is expressed in pounds or kilograms per day of liquid volume in the
aeration tank. The concentration of the suspended solids, which mainly consistof active mi-
croorganisms, is called themixed liquor suspended solids(MLSS). FIM can be computed from
the formula
Table 2 Loadings and Efficiencies of Activated Sludge Systems

Loading (Ib BOD/day
Aeration
Efficiency of
Process
per Ib MLSS) period (hr) BOD removal (%)
High rate 1-2 4 80-85
Conventional 0.2-0.5 6 85-90
Extended aeration 0.05-0.2 30 90-95
502 Shah
Waste sludge
Screen & Return sludge
GritChamber
" FF
Sewage
Influent
Final
Effluent
Waste sludge
Return sludge
Screen k
GritChamber
-r I I
Figure 9 Activatedsludgeplant;(a)conventional (b) stepaeration.
BOD X Q
"F = MLSS X V
where BOD is the applied 5-day BOD, in mg/L or ppm; Q is the wastewater flow rate, in
mUday or mg/day; M U S is mixed liquor suspendedsolids, mg/L, and V is the volume of the
aeration tank, mL.
Types of Activated Sludge Processes. Several types of systems have been developed. Many of
these serve to increase plant capacity or reduce the tank volume requirement.
1. In the conventional activated-sludgeprocess, the aeration basin is a long rectangular tank
with air diffusers alongone side of the tank bottom to provide aeration and mixing. Settled
raw wastewater and returning activated sludge enter the headof the tank and flow down in
a spiral flow pattern. The air supply is tapered to provide a greater amount of diffused air
near the head where the rate of biological metabolism and consequently oxygen demand
are the greatest (Figure 9).
Screen &
GritChamber
-
c-
Sewage
Influent
Return sludge A Pump

Screen &
GritChamber
Aeration
Sewage
Influent
Effluent
Waste sludge
Return sludge
1
f
Influent U WEffluent
(c)
Figure 10 Activatedsludgesystems;(a)contactstabilizationplant,(b)completelymixedactivated
sludge plant, and (c) extended aeration plant.
2. The step-aeration activated-sludgeprocess is a modification of the conventional process.

It provides multiple feed pointsof the primary effluent into the aeration tank, unlike
in the
conventional process where flow enters only at the head end. Distributing the influent load
along the tank produces a more uniform oxygen demand (see Figure10).
3. Extended aeration systems are generally small packaged plants used for treatinglow waste-
water flow rates from hotels, schools, suburban residential development, and other iso-
504 Shah
lated sources.In this process the screened wastewater flows directly into theaeration tank
without any primary settling, and the detention time is 24 hr or greater. The system op-
erates on a low fodmicroorganism ratio( F M ) . (See Table2.) The low FIM ratio and the
“extended” period allow for the stabilization of most of the organics. Excess sludge is
generally not wasted continuously, only periodically. Figure 1% is a flow diagram of an
extended aeration system.
4. Table 2 indicates that the high-rate (completely mixed activated sludge)process operates
with a high BOD load per unit volume of aeration tank and a short aeration period. Many
such units use a combination of compressed-air aeration and mechanical mixing. Also, in
large, completely mixed aeration basins a mechanical impeller is placed above an uptake
tube for deep mixing along with surface aeration. (See Figure lob.)
5. The contact stabilization activated-sludgeprocess provides for reaeration of the returned
activated sludge from the final clarifier, allowing the use of a smaller aeration tank and
therefore relatively shorter aeration periods. After a short contact time, the mixed liquor
enters a clarifier and the activated sludgesettles out; the clarified liquid flows over effluent
weirs. The settled sludge is pumped into another aerated tank for reaeration. This type of
process is shown in Figure loa.
6. Air is approximately 2 1% oxygen. The major componentsof a pure oxygen aeration system
are an oxygen generator,a covered aeration tank, a final clarifier, and recirculation pumps.
Primary effluent, return activated sludge, and oxygen are introduced into the first com-
partment of a multistage covered tank. Mechanical agitators mix the oxygen with the
wastewater in the tank. High-purity-oxygen activated sludge has several advantages. High
efficiency is possible at increased BOD loads and reduced aeration periods. Waste sludge
production is also less.
Operation and Control of Activated SludgeProcesses. Operation of an activated-sludge treat-
ment plantis regulated by the quantity of air supplied, the rate of activated sludgerecirculation,
and the amount of excess sludge withdrawn. The settleability of the mixed liquor in the final
clarifier governs the rate of activated sludge recirculation. Poorlyflocculated particles and fil-
amentous growths that do not separate by gravity in the final clarifier contribute to the BOD
and suspended solids in the effluent. Excessive carryover of floc is called sludge bulking. This
condition can be controlled by appropriate adjustments in the mixed liquor suspended solids
concentration andfodmicroorganism ratio. Also, sludge bulkingmay be caused by excessive
agitation or insufficient aeration.
The settleability of mixed liquor is defined by the sludge volume index (SVI), which is
equal to the volume occupied by l g of settled sludge and is expressed in milliliters per gram
(mug). To determine SVI, a sample of mixed liquor fromthe aeration tank is allowed to settle
for 30 min in a l-L graduated glass cylinder.The volume of settled sludgeis read fromthe scale
on the cylinder, and the MLSS is also measured. The SVI is then computed as
SVI = v x lo00
-
MLSS
where V is the volume of settled sludge (mVL), and
M U S is the mixed liquor suspendedsolids
(mg/L).
3. RotatingBiologicalContractors
A rotating biological contractor (RBC) isa secondary treatment devicethat consists of a series
of large plastic disks mounted on a horizontal shaft. The lightweight disks are approximately
10 ft (3 m) in diameter and are spaced approximately 1.5 in. (40mm) apart on the shaft. The
disks are usually made of corrugated plastic sheets bonded together.
Table 3
"bo-stage
High rate
~~
BOD loading
[lb/(lOOO ft3-day)] 25-45 45-70
Hydraulic loading
0.16-0.48
(gPdfi*) 0.16-0.48
1.0 lb/(1000 @.day) = 16 g/(m3.day).
1.0 X Id gal/(acwday) = 0.935 m3/(m2.day).
The disks are approximately 40% submerged in primaryeffluent. As the shaft rotates, the
disks are alternately in contact with air and with the wastewater. The resultis similar to that of
the trickling filter system. When disks are rotated out of the tank, air enters the spaces while
the liquid trickles out over the biological film on the disks. The microbes that form the film
absorb the organic material in the wastewater. These microbial solids grow on the medium.
Excess microbial solids (slime) break away from the medium due to their weight and hydraulic
forces and are carried out in the process effluent for gravity separation in the final clarifier.
4. Stabilization or OxidationPonds
For suburban or rural areas with seasonal industries such as fruit and vegetable canning facil-
ities and where land is relatively cheap, wastewater lagoonsmay be used for secondary treat-
ment. These lagoons are also called stabilizationor oxidation ponds. A stabilization pond is a
flat-bottomed pond enclosed by an earth dike. It canbe round, square, or rectangular of length
approximately three times the width. The operating liquid depths are 2-6 ft (0.6-1.83 m) and
3 ft (0.91 m) dike freeboard. A minimum of 2 ft (0.6 m) liquid depth is needed to prevent the
growth of weeds. Liquiddepths of 6 ft (1.83 m) or greater may give out odors because of anaer-
obic decomposition near the pond bottom. Where the required lagoon area is greater than 6
acres, it is good engineeringto have multiple cells that can be operated individually,in series,
or in parallel. If the soil is pervious, the pond bottom and dikes should be sealed with clay or
other sealantto prevent groundwater pollution. Dikes and surroundingsare seeded with grass,
graded to prevent runoff water from entering the pond, and fenced.
A majority of lagoons are facultative ponds; i.e., both aerobic and anaerobic biochemical
reactions take place. Raw wastewater enters the pond without primary treatment. Organic sol-
ids that settle in the bottom decompose anaerobically, producing organicacids, methane, and
hydrogen sulfide. Near the mid-depth of the pond, most of the organic matter is decomposed
by facultative bacteria, bacteria that can grow in either an aerobic or anaerobic environment.
In the presence of oxygen, aerobic decomposition occurs mostly in the top half of the liq-
uid. A major portion of the oxygen added to the wastewater in the pond is due to the mixing
of air at the pond surface by wind action. A minor portionof the oxygen is from photosynthesis
as algae present in the pond use energy from sunlight. The algae grow and multiply by con-
suming carbon dioxide and other inorganiccompoundsreleased by bacteria. Bacteria and
protozoa in turn use oxygen released by algae and from surfaceaeration to decompose the or-
ganic matter in the wastewater. The overall process in a stabilization pond is the sum of the
reactions of the bacteria, protozoans, and algae.
BOD loadings on a stabilization pond are generally in the range of 20-40 lb of BOD per
acre per day or 0.46-0.92 lb of BOD per lo00 ft2 [2.2-4.4 g/(m2.day)]. Higher loadingsare
possible in areas with warmer climates. Although the algae playa role in the purification pro-
cess in a lagoon, they can causea problem when theyare carried out of the pond in the effluent
flow by increasing the levels of total suspended solids.
506 Shah
Despite many drawbacks, such as difficulty with total suspended solids removal efficiency
and potential groundwater pollution, wastewater lagoons are being used where land is rela-
tively cheap. The low construction costs and ease of operation and maintenance are distinct
advantages.
5. SecondaryEffluentChlorination
The final step in the secondary wastewater treatment process is usually disinfection by chlo-
rination. The main purpose is to destroy pathogens in the effluent before discharging it into a
body of water used for swimming or water supply downstream. The chlorine demand of sec-
ondary effluent is usually high. Chlorine dosage should be adjustedso that a combined chlorine
residual is approximately 0.5 mg/L in the secondary effluent.
D. Tertiary or Advanced Treatment

Secondary treatment followedby disinfection can kill nearly all pathogens and remove8 5 4 0 %
of the BOD and TSS in raw wastewater. However, only very little of some pollutants, suchas
nitrogen, phosphorus, andheavy metals, canbe removed by biological treatment. Nitrogen and
phosphorus are important plant nutrients. If they are discharged into a lake, algal blooms and
eutrophication (accelerated aging) may occur. Also, nitrogen in the secondary wastewater ef-
fluent may be present mostly as compounds of ammonia. These exert an oxygen demand the in
receiving water as theyare converted to nitrates. This process is known as nitrification. Heavy
metals in the effluent may be toxic or carcinogenic, a function of concentration and type
of metal.
In cases where pollutants are not removed to a sufficient extent by secondary treatment,
additional or advanced treatmentsteps must betaken. Thisis also called tertiary treatment. The
cost of construction, operation, and maintenance for this type of treatment is very high.
1. Filtration
By using a filtration process it is possible to remove most of the residual suspended solids,
BOD, and bacteria fromthe secondary effluent. This is accomplished by multimedia filters that
consist of low-density coal for the large grain sizes, medium-density sand for intermediate
sizes, and a high-density medium for the smallest filter grains. Qpically, filtration can reduce
activated sludge effluent suspended solids from 25 mg/L to approximately 10 m@. However,
coagulationandsedimentationfollowed by filtration canremovesuspendedsolidsalmost
entirely.
2. CarbonAdsorption
Many soluble organic materials that are resistant to biological breakdown will persist in the
effluent even after secondary treatment, coagulation, sedimentation, andfiltration. A reliable
and practical method for removing persistent organics is to adsorb them onto activated carbon,
which is usually packed in a cylinder through which the effluent is passed. Organic materials
accumulate at the particle interfaces. Adsorption is a surface phenomenon, and thegreater the
surface area of the carbon, the greater is the capacity to remove organics fromthe liquid. The
large surface areais provided by a large number of pores. After the adsorption capacityof the
carbon has been exhausted, it can be restored by heating the carbon at a high temperature to
burn or drive off the adsorbed organics.
3. Microstraining
A microstraining process can also be used to remove suspended solids. The microstrainers (also
called microscreens) are made of woven steel wire or special cloth fabric mounted on a re-
Physical, Biological, and Chemical
Processes 507
volving drum. The rotating drum is partially submerged in the wastewater after secondary
treatment. The effluent flows into the drum and then throughthe microscreen, where thesolids
are captured.
4. Phosphorus Removal
As previously discussed, phosphorus is one of the key plant nutrients that contribute to eu-
trophication of lakes. Untreated wastewater contains approximately 10 mgL of phosphorus
from household detergentsas well as from sanitary wastes. This phosphorusis primarily in the
form of organic phosphorus and phosphate components. Only 20%of the phosphorus is re-
moved in secondary treatment. (See Table 1.)
The tertiary treatment process used to move phosphorus from the secondary effluent is
typically chemical precipitation of phosphorus with alum, ferric chloride, or lime. The pre-
cipitation reactions are shown below.
Alum: A12(S04), + 2 HP0:- + 2 AIP044 + 2 H+ 3 SO:-
Ferric chloride: FeCl, + PO:- + FeP04i + H+ 3 Cl-
Lime: 5 Ca(OH), + 3 HPOZ- ”* Ca,(P04)30Hi + 3 H20 6 OH- +
The pH is very important for these reactions. The effective range of PH for alum andferric
chloride is 5.5-7.0.
The precipitation of phosphorus requires a reaction basin and a settling tank to remove
the precipitate. However, ferric chloride and alum may be added directly to the aeration tank
in the activated sludge system. In this case, the aeration tank serves as a reaction chamber
and the precipitate is removed in the secondary clarifier. This is not done withthe lime because
the highpHneeded to form a precipitate is not tolerated by microorganisms in thebio-
aeration tank.
5 . NitrogenRemoval
Nitrogen can exist in wastewaterin the form of organic nitrogen, ammonia,or nitrates. Nitro-
gen in any soluble form is a nutrient in the receiving body and can cause algal blooms. In ad-
dition, nitrogen in the form of ammoniaexerts an oxygen demand and canbe toxic to fish. For
these reasons, it is sometimes necessary to remove the nitrogen from the wastewater effluent
before discharge.
Removal of nitrogen can be accomplished either biologically or chemically. The biologi-
calprocess is called nitrificatioddenitrification. Thechemicalprocess is calledammonia
stripping.
NifrificationlDenirrificafion. This process consists of two basic steps.First, the secondary ef-
fluent is further aerated by maintaining a cell detention time of 15 days or more. In this first
step (nitrification), the ammonia nitrogenis converted to nitrate nitrogen, producinga nitrified
effluent. This step is expressed in terms of the chemical reaction
NHQ + 202”*NO; + H20 + 2 H +
A second biological treatmentstep, denitrification, is necessaryto actually remove theni-
trogen from the wastewater. If the nitrogen level is not of concern for the receiving body of
water, the wastewater can be discharged after settling. If nitrogen is of concern, the nitrifica-
tion is followed by denitrification. The denitrifying bacteria use the carbon from the organic
matter and the oxygen from the nitrates in their metabolic processes. This step is expressed in
chemical equation form as
2 NO; + organic matter -+ NZ? + C02 + H20
The organic matter may be a synthetic material such as methanol.
508 Shah
Ammonia Stripping. Ammonia stripping is a physicochemical process. Nitrogen is removed

from wastewater in two steps. First, the pH of the wastewater is raised to convert the ammo-
niumion into ammonia. Second, the ammonia is stripped by passing large volumes of air
through the wastewater. The ammonia stripping reaction is
NH; + OH- + NH3T + H20

The hydroxide is usually supplied by adding lime.
The combination of ammonia stripping with phosphorus removal using lime a coagulant
as
is cost-effective andefficient, since lime canalso serve to raise the pH of the wastewater. Low
temperatures can cause problems suchas reduced stripping.
V. WASTEWATER SLUDGES
In the processof removing pollutants from wastewater during treatment, sludge accumulates in
the settling tanks and mustbe withdrawn, treated, and disposed of. The amount of solids gen-
erated in a wastewater treatment system isa function of the degree of treatment provided and
the amounts of chemicals added. The handling, treatment, and disposal of wastewater sludge
can be a complex and costly operation. The sludge is composedof materials that have settled
out from the raw wastewater and protoplasmof organisms.
Land disposal of sludge or sludge incineration is usually preceded by some type of treat-
ment to render it easier and less offensive to handle and reduce its volume. A discussion of
sludge characteristics and qualities and several common treatment methods follows.
A. Characteristics of Sludges
Sludge initially forms at the bottom of a clarifier orsettling tank. The concentrationof organic
matter in wastewater is approximately 0.02%, while that in a typical raw waste sludge is a p
proximately 4%. This sludge is odorous and putrescible andmust be further processed and re-
duced in volume for final disposal.
The concentration of solids has a significant effect on the total volume occupied by the
liquid sludge.The total sludgevolume is inversely proportionalto the solids concentration. For
example, if the waste is thickened from 2% to 4% solids, the volume is reduced by one-half.
During this concentration processthe water content is reduced from98% to 96%.
Primary sludge typically has a solids concentration of 6-8%. The solids are 70-80% or-
ganic. Primary or raw sludge is highly odoriferous, greasy, and gray.
Secondary sludge consists of microorganisms andinert materials that have been accumu-
lated as wastes from the secondary treatment processes. Trickling filter sludge contains 2-4%
solids, while activated sludge waste is typically 0.5-2.0% solids with an organic fraction
Of 80-90%.
The characteristics of tertiary sludges depend on the nature of the process. For example,
these sludges may contain largequalities of chemical precipitates because chemicalsare added
during phosphorus removal. This chemical sludge is combined with the biological sludge.
B. SludgeTreatment
Sludge is treated prior to ultimate disposal for two reasons: volume reduction andstabilization
of organics. A reduced sludge volume minimizes pumping and storage requirements and lowers
sludge handling costs. Stabilized sludge has a less offensive odor, and health hazard and nui-
sance conditions are minimized.
Physical,
Processes
Chemical
Biological, and 509
Common methods to accomplish the two objectives include thickening, biological diges-
tion, dewatering, and incineration. When incineration is used, there is no need to stabilize the
sludge.
1. Thickening
It isalmost impracticalto treat thin sludges witha very high water content and very little solids
concentration. Thickening serves to increase solids concentration.It is accomplished in oneof
two ways: the solids are floated to the top of the liquid (flotation) or allowed to settle to the
bottom. The later process is called gravity thickening. The objective is to remove as much wa-
ter as possible before final dewatering or digestion of the sludge.
2. Stabilization
The stabilizationof sludge is accomplished by a sludge digestion processin which organic sol-
ids are biochemically decomposed. The organics are converted into simpler and more stable
products. Digestion reducesodors of the sludge, makes less it putrescible andeasier to dewater,
and destroys pathogens. Sludge may be digested under anaerobic or aerobic conditions.
Anaerobic Digestion. The anaerobic digestion of sludge occurs in two stages. The first stage
is commonly referred to as acid fermentation. In this stage organic material is converted to
organic acids, alcohols, andnew bacterial cells.In the second stage the end products the of f i t
stage are converted togases, mainly methane and carbon dioxide. This stageis called methane
fermentation. The two stages are simultaneous. The primary acids produced during acid fer-
mentation are propionic and acetic acids, which are precursors for methane formation. The
methane gas may be burned to provide power for other plant pmesses and equipment as well
as for heating the plant buildings.
In modern anaerobic systems, the digestion process takes place in two covered circular
tanks. These tanks are typically about 80 ft (25 m) in diameter and approximately 50 ft (15 m)
deep. The sludge in the first tank is heated to a temperature of approximately 90°F (35"C), and
the contents are thoroughly mixed. The digestion process is completed inthe first tank within
10-15 days of detention time. The sludge thenflows to the second tank for settling and storage.
The digester supernatant (relatively clean liquid above the digested sludge) is pumped to the
inlet of the treatment plant. Digested sludgeis removed from the bottom ofthe second tank for
further processing (e.g., dewatering) and final disposal.
Aerobic Digestion. In aerobic sludge digestion, the sludge is aerated in an open tank similar
to the activated sludgeaeration tank. The sludgeis aerated fora long period (approximately 30
days or more), during which most organics are stabilized and the amount of sludge is reduced.
The BOD loading on the digestion tank is kept very low. Eventually the microorganisms con-
sume theirown cellular mass. Thisis called endogenous decay. The aerobic digester is followed
by a settling tank unlessthe liquid is to be disposed of by land. The supernatant(effluent) from
the clarifier is recycled back to the head end of the plant.
Not all of the sludge decomposes. Some of it eventually has to be removed from the tank
for disposal. Because the fraction of the volatile matter is reduced, the specific gravity of the
digested sludge solids will be higher than that of the original sludge. Thus, the sludge settles
to a more compact mass,and the clarifier concentration can reachto a maximum of 3%. It is
a thin sludge that is difficult to thicken and dewater.
Conditioning
3.
Conditioning of sludge facilitatesthe separation of the liquid and solids. Chemical conditioning
involves additionof coagulants such as lime, ferric chloride, or organic polymers. Sludge par-
ticles carry a small electrostatic charge that causes'particles to repel each other. The coagu-
510 Shah
lants, however, neutralize the effect of particle charges so that particles can collide and form
larger and heavier particles to facilitate separation from the water. These conditioning chem-
icals (coagulants) are mixed into the sludge just before dewatering.
Heat Treatment. Another methodof conditioning the sludge is to heat it at high temperatures
(175-230°C) and pressures (1000-2000 kPa). Under these conditions, water that is bound up
with organic solids is released. Thus, dewatering of the sludge becomes easier.
Dewatering. The process of removing water from the sludge is called sludge dewatering or
drying even though the dewatered sludge may still be 70-75% water. The dewatered sludgeis
no longer a liquid and can be handled easily. Sludgeis usually dewateredprior to incineration.
There are several methodsby which sludge canbe dewatered. The most popular methodof
dewatering in the past hasbeen the use of sludge dryingbeds. The beds usually consistof 6-9
in. (150-225 mm) of coarse sand supported on a graded gravel bed. The digested sludge is
spread on an open bed of sand, where drying takes place by a combination of evaporation and
drainage. A piping system with open joints placed in the gravel or crushed stone bed collects
the water that drains from the sludge.
Rational designis difficult because several variables affect the dryingrate. These include
climate (temperature,rainfall, humidity, and sludge velocity), sludgecharacteristics (degree of
stabilization, grease content, solids concentration), and frequency of sludge application. Solids
loadings average about 20lb/(ft2-yr)in northern states and about 40 lb/(ft2.yr) in southern cli-
mates. Drying time ranges from a few weeks to several weeks depending on the drainability of
the sludge and weather conditions. Sludge is appliedto the sand bed to a depth of 12 in. (300
mm). A typical dewatered sludge “cake,” as it iscalled, has a solids contentof about 30-40%.
It is removed from the sand with a pitchfork or front-end loader. Sand drying beds are the old-
est, most common type of beds. Since a relatively large amount of land area is required to
construct a bed, this method of sludge drying is most common in rural or suburban areas.
When there is not enough land area available at the plant site or weather is a problem, a
mechanical system may be used to dewater the sludge. A mechanical system needs less space
and offers more operational control than the sand drying beds. ”bo of the most common types
of mechanical systems for sludge dewatering are the vacuum filter and the centrifuge.
A vacuum filter consists of a drum covered witha special filtering fabric, which rotates as
it is partially submerged in a vat of conditioned sludge.A vacuum or suctionis applied inside
the drum to extract water, leaving the solids on the filter medium. A thin layer of dewatered
sludge, called filter cake, sticks to the fabric. As the drum completes its rotational cycle, a
blade scrapesthe filter cake intoa hopper as the drummoves. It is often necessary toadd chem-
icals (ferric chloride, lime, or polymers) to the sludgeto improve the drainability. Thisis called
sludge conditioning.
In the centrifuge dewatering system, the sludge is pumped into a cylinder that rotates at
high speed. Sludge conditioning chemicals are also injected. Thesolids are removed to the wall
of the rotating cylinder by centrifugal force, and the liquid is pumped to the inlet end of the
plant for treatment.
4. Incineration
The dewatered sludge canbe incinerated to convert itinto inert ash. Incineration is used when
suitable land is not available. The exhaust gases from the incinerator must be treated to meet air
quality standards. Thereare two types of incinerators: the multiple-hearth furnace and the flu-
idized bed incinerator.
In the multiple-hearth furnace, dewatered sludge passes through a series of hearths, where
it is dried and heated to the ignition stage. Fuel burners provide the heat for start-up; after-
wards sludge serves as a fuel to keep incineration going. In the fluidized bed incinerator, air
Physical,
Processes
Biological,
Chemical and SI I
flowing upwardis mixed with the sludge andis forced through a bed of hot sand. The passage
of air causes the sand bed to expand (This is the fluidized bed). The sludge is burned as it
passes through the hot sand. The ash, including partially burned particulates, makes up the
exhaust gases and is removed by the air pollution control equipment.
C. Sludge Disposal
The dewatered or incinerated sludge may be applied to plots of land for the purpose of recov-
ering nutrients or reclaiming despoiledland. In contrast to other land disposal techniques, this
type of land spreading is land-use-intensive. Applicationrates are controlled by the soil char-
acteristics and intended crops.
Sludge landfill is the planned burial of wastewater solids, which may include screenings,
grit, processed sludge, and ash, at a suitable site. A trench is excavated, and solids are put in
it and covered with a layer of soil that does not permit water to percolate.
Wastewater sludge may also be used for cornposting or for cofiring with municipal solid
waste.
GLOSSARY
Biochemical oxygen demand (BOD). The amount of oxygen required by microorganisms to
decompose organic wastein water, usually during a 5-day incubation at 20°C (68°F). BOD is
a measure of the amount of organic pollution. It is usually givenin mg/L or ppm. It can also
be expressed in pounds of total oxygen required by wastewater or sludge.
Dissolved oxygen. The amount of oxygenpresentin the water,usuallyexpressedasmg/L
or ppm.
Biodegradable. Readilybrokendown or decomposed into simpler substances by biological
action of microbes.
Eutrophication. The natural aging of a lake due to high concentration of nutrients, exces-
sive plant growth, and accumulation of bottom sediments.
Total solids. The amount of residue on evaporation, including organic matter and dissolved
salts; usually expressed in mg/L or in pounds per unit of liquid.
Suspended solids. Solids carried in water or sewage that would be retained on a glass fiber
filter in a standard laboratory test. The units are mg/L or pounds per unit of liquid.
RECOMMENDED READING
ASCE (1982). Wastewater Treatment PlantDesign, ASCE Manual on Engineering Practice No. 36.
Cheremisinoff, F! N., and Young, R. A. (1976). Pollution Engineering Practice Handbook, Ann Arbor
Science, Ann Arbor, Mich.
Davis, M. L., and Cornwell, D. A. (1989). Introduction to Environmenrul Engineering, PWS Publishers.
Viessman,W., Jr. andHammer, M.J. (1993). Water Supply andPollution Control. 5th d..Harper
Collins.
23
Freeze Concentration: Its Application
in Hazardous Wastewater Treatment
Ray Ruemekorf
NIRO, Inc.
Columbia, Maryland
1. INTRODUCTION
Melt crystallization is a standard chemical industries purification process for chemical products
such as naphthalene, para-xylene, dichlorobenzene,acrylic acid, monochloroacetic acid,
bisphenol A, and others [l]. It is seen as an extremely selective separation process that can
reduce contaminant levelsto the ppm range. This provides an effective means to purify some
products. Freeze concentration (FC) is usually associated with the process when the crystal-
lizing componentis water. In this chapter we focus onthe crystallization of water and limitour
discussion toFC of aqueous solutions. The purpose of isFC to provide a means toseparate pure
water froma solution. This will provide either high quality water and reduced volumes of waste
or, in the case of food liquids, a high quality concentrate with only water removed from the
original feed product.
NIRO (formerly Grenco) process technology has developed anFC system used commer-
cially in the food processing industry (the NFC process). TheNFC process is described, and the
results from pilot plant tests ona caustic wastewater are presented along with economicsfor a
typical treatment case.
Freeze concentration has been applied in the food industry [2,3] for a variety of products
including fruit and citrus juices, coffee and teaextracts, beer and wine, vinegar, anddairy prod-
ucts. It featuresmany product quality advantages over the more conventional concentration pro-
cesses of evaporation and membranefiltration.
Freeze concentration can produceconcentrates up to 45-50% total solids PS),not as high
a concentration as evaporators but significantly higher thanthat achieved with membranes.The
process operates at freezing temperatures. This has obvious benefits for the quality of food
products but also reduces corrosion, which can occurat the elevated temperaturesused in evap-
oration. The crystallization method is extremely selective in that only water is included in the
crystal. Coupled with an efficient separation unit, FC can remove pure water from the product,
eliminating the need for further processing. Evaporation canbe limited by the relative volatility
513
514 Ruemekorf
Table 1 Characteristics of the Niro Freeze Concentration Process

Crystallization of water using ripening process
Pure spherical ice crystals.
No solids incorporated in the crystal itself.
Ice crystal separation using a wash column
Effective separation; losses usuallyin the ppm or ppb range.
No recycle of washwater.
Efficient separation,reliable operation through mechanically forced bed transport.
Low processing temperatures
Always below the freezing point of water.
Operation with heat-sensitive materials.
Reduction of corrosion.
Closed, pressurized, flooded system
No gas-liquid interface; reduces oxidation problems and eliminates loss of volatile materials.
Self-stabilizing process
Simple control system.
Relatively insensitive to changesin feed characteristics.
Low-speed rotating equipment
Low maintenance costs.
Modular design
Flexibility-multistage systems can be split for dual product operation (or online maintenance).
Easily expandable as capacity demands increase.
Clean energy source
Electrically powered, which can provide for a positive environmental impact due to controlled
centralized production.
Local utility companies may provide economic incentives for installation of electric equipment.
of the constituents, some of whichmay be carried over with the water vapor and require an-
other treatmentlrecovery step.
The advantages for hazardous waste disposal lie in the purityof the discharged water.The
NFC process uses separate nucleation and growth zones, which produce pure spherical ice
crystals that can be easily separated and discharged as pure water. This water can be discharged
directly or reused in the process, reducing water requirements. The system operates continu-
ously and does not require shutdown for periodic cleaning of the components. It is a closed
system, which eliminates vapor lossesand oxidation through contact withair. It is a relatively
stable operation with a simple control process. It provides for a 100% turndown ratio from
design capacity, is relatively insensitive to fluctuations in feed rate and composition, and is
modular in design, improving expansion capabilities. These process characteristics are sum-
marized in Table 1.
The FC process is dependent ontwo main characteristics of the concentrated product.The
viscosity of the concentrate at its freezing point determines the maximum concentration ob-
tainable by FC. Figure 1 shows the viscosity curves for caustic wastewater, beer,and milk for
comparison. The maximum concentration is reached when the viscosityof the liquid prevents
the growth of ice crystals. The separation then becomes too difficult to maintain the purity of
the discharged water. Fromthe standpoint of economics, the maximum concentration may be
reached long before the product reaches this viscosity.
The crystal growth rate decreases as viscosity increases, and the system requires longer
residence times (and thus larger equipment) to reach a separable crystal size,The freezing point
curves for the same productsas in Figure 1 are shown in Figure 2. The freezing point depres-
sion due to the solute concentration can be so great that the lower temperature limit for the
Freeze Concentration in WastewaterTreatment 515
90
80 -
Viscosity 70 -
(mm2/s)
60 -
50 -
40 -
30 -
20 -
10-
o o
5 15 10 20 25 30 35 40
Concentration
Figure 1 The relationship of viscosity to concentration for a caustic wastewater solution (% total sol-
ids), skim milk (% total solids), and beer (‘Plato).
refrigerant may be reached. This can be overcome by using specialty refrigerants and multi-
stage refrigeration systems, but these are usually too expensive to be feasible. Qpically the
NFC system can operate with to up40-50% total dissolved solids with a product freezing point
of around - 10 to - 15°C and viscosities of 150-500 cSt.
Evaporation is a well-developed unit operation andbecah used in most instances requiring
concentration. Even though water requires more energy to evaporate than to crystallize(2325
kJkg heat of vaporization compared to334 kJkg heat of fusion for pure water), commercial
evaporators with energy recovery systems use approximately the same amount of energy as FC
systems. The evaporator condensate from a wastewater treatment system is usually not suitable
-
for direct discharge becauseof carryover of volatile organics. The condensate stream thenre-
quires further treatment before discharge or reuse. Many wastewaters contain chemicals that
are quite corrosive at the elevated temperatures in the evaporators and therefore require ex-
pensive materials for equipment construction [4] or limit its lifetime. Precipitates usually build
up on the heat transfer surface, leading to additional cleaning cycles, lost production time, and
production of an additional waste stream thatmust be treated.
0
-2
Milk
-10 -
-12 -
-14-
-16-
-18 - Caustic
-20 - Water
Waste
-22 -
-24 -
-26 ‘
5 10 15 20 25 30 35 40
Concentration
Figure 2 The relationship between equilibrium temperature and concentration
for a caustic wastewater
solution (%TS), skim milk (%TS), and beer (“Plato).
516 Ruemekorf
The treatmentof wastewater streams with membranes depends greatly on the type on con-
taminant found in the wastewater. Membrane systems are effectively used in the treatment of
oily wastewaters[5]. The costs are reasonable, and their operation is routine. As with all mem-
brane systems, pretreatment is necessary to prevent damage and reduce fouling of the mem-
brane. Low molecular weightcompoundsfoundinmanyreactor effluents require tighter
membranes. Membrane use in these situations is generally more expensive due to the larger
surface area necessary and requires additional treatment steps before final dischargeof the wa-
ter. Regular cleaning cycles add to the cost of operation due to lost production time and ad-
ditional treatment systems for the cleaning water supply.
II. DISCUSSION
In its most basic form, FC has been employed since as far back as the Middle Ages. Beer or
wine in wooden barrels would be exposed to the cold winter nights, causing water to freeze
along the barrel walls and leaving a concentrated product in the middle of the ice shell.
In more recent times, a few companies have tried to commercialize FC processes. The
main problem with most of these attempts was the difficulty in separating the ice from the
concentrate. Filter presses, centrifuges, and various types of wash columns have been used
with limited success [3]. Unacceptable losses of product with the ice, low production capaci-
ties, and high equipment cost were normally associated with FC processes during this time.
Professor H. A. C. Thijssen, working at the Technical University of Eindhoven, was the first
to develop a practical solutionfor this problem.His solution consistsof two parts. An efficient
crystallization process provides ice crystals of sufficient size and purity to allow proper sepa-
ration, and an efficient wash column provides for complete separation of the ice and concen-
trate, using the melted ice to wash the incoming crystals without recycling the wash water.
Thijssen’s original work provided the basis for the development of the present NFC pro-
cess. The following sections describe the general NFCprocessandequipmentusedinthe
wastewater project. Commercial applicationsin the food industry use the same basic process.
The NFC can be separated into the twoparts noted in Thijssen’s work, thecrystallization
section and the separation section 161.
A. The Crystallization Section

The crystallization process is built up of three components as shown schematically in Figure 3,
starting with a set of scraped surface heat exchangers (SSHEs) that remove the necessary heat
from the system to provide for icecrystal formation. The SSHEsare connected to the recrys-
tallizer by a recirculation stream through a scraped filter in the recrystallizer. This provides a
continuous crystal free stream over theSSHEs where small ice crystals (nuclei) are formed and
pumped into the recrystallizer. Of these small crystals, some survive and grow while the ma-
jority melt, absorbing energy from the surroundings and causing water to crystallize on the
surviving ice crystals. This growth process is known as ripening and can be described by the
Gibbs-Thomson formula depicted in Figure 4 for an aqueous sugar solution.
Small crystals have a slightly lower equilibrium temperature, the temperature at which they
neither grow nor melt, than larger crystals, When small and large crystals are mixed in an adi-
abatic vessel, the temperature of the bulk solution will reach a value somewhere between the
equilibrium temperaturesof the large and smallcrystals [ 7 ] . This puts the larger crystals in an
environment below their equilibrium temperatureso they will not melt, whereas the smallcrys-
tals are in an environment above their equilibrium temperature so they tend to melt, which
removes energy from thebulk solution that canbe exactly balanced by the recrystallization of
Freeze Concentration in Wastewater Treatment 517
Heat
1
The small ice crystalsform in the S H E
When enoughi c e crystals have formed, a sluny stream

is divertedfrom the recrystallizer to
the washcolumn.
The iceis separated from the concentrate and discharges
after being melted.
The ice crystalstravel in the product flow to

the rec~ystalliier,where the ripeningprocess
begins. Most of the small cryatals melt,but a few
survive and start growing.
Feed
New product from the feed tank replaces the discharged

A aystal-freeliquid stream of product is water so that thesolute concentration in the system
continuously recirculated over the
SSHE increases to the desired production value when we can
prwidinga constant supply of small crystals withdraw part of the recirculation streamas product.
to fuel the ripening process.
Figure 3 Schematic buildup of an externally cooled crystallizer with separation section. (a) The small
ice crystals form in theSSHE. (b) The ice crystals travel in the product flow to the recrystallizer, where
the ripening process begins. Most of the small crystals melt, but a few survive and start growing.A(c)
crystal-free liquid stream of product is continuously recirculated over the SSHE, providing a constant
supply of small crystals to fuel the ripening process. (d) When enough ice crystals have formed, a slurry
stream is diverted from the recrystallizer to the wash column. The ice is separated from the concentrate
and discharges after being melted. (e) New product from the feed tank replaces the discharged water so
that the solute concentration in the system increases to the desired production value when we withdraw
part of the recirculation stream as product.
518 Ruemekorf
Diameter (microns)
100 000
Drivingforce for growth
melt
Driving force for
1 I:
Figure 4 Schematic representation of ripening for ice in a 30% sucrose solution.
water on the larger crystals. Therefore, the small crystals melt and disappear while the larger
crystals grow larger. By providing a continuous supply of small crystals to an existing slurry
of larger crystals we can force the growth of crystals large enough to be cleanly separated
from the concentrate. This recrystallization carried out in a mixed vessel provides for very
pure spherical crystals. The round crystal shape is clearly an advantage in the following s e p
aration section.
B. TheSeparationSection
The separation unit shown in Figure5 can be described as a packed bed pressurized washcol-
umn with mechanically forced bed transport. The piston type consists of a cylinder, a moving
piston with a porous head, and a rotating scraper for ice removal. The slurry from the recrys-
tallizer enters at the bottom of the wash column througha central inletin the porous head. The
liquid concentrate can leave through the head while the ice crystals remain to form a packed
bed of crystals. The round crystals pack, leaving a certain void space that remains filled with
liquid concentrate. The moving piston forcesthe ice bed into the scraper at the top of the cyl-
inder. Iceis scraped off and enters the melting circuit, where itis circulated through and melted
in a small heat exchanger. Controlling the pressurein the melting circuit allows the possibility
to force the melted water back throughthe ice bed, which washesthe incoming crystals. The
area where wash water meets concentrate in the ice bed is called thewash front andis generally
very well defined.This stable displacement also depends on therecrystallizationprocess shown
in Figure 6 .
The water (freezing at OOC) meets crystals coming in with the slurry at the equilibrium
temperature in the recrystallizer, say -8°C. This water willrecrystallize onto the surface of the
existing crystals and force theconcentrate away from the crystal surface and towardthe porous
piston head. The wash water, now frozen, is carried toward the top of the column along with
the washed ice bed to be melted and discharged. Washingcarried out in this manner prevents
Freeze Concentrationin Wastewater Treatment 519
Melter
Water discharge
Fill with slurry Compression and washing
(4 4
Figure 5 Packed bed wash column (piston type). (a) The column is filled with slurry. (b) The piston
compresses the slurry. The upper portionof ice bed is removedby a rotating ice scraper. The crystals are
melted by circulation of ice and water through the melter. Washing the crystal bed is completed by in-
creasing the pressure in the melting circuit.
mixing, or recycling, of the wash water with concentrate, whichprovidesfor an efficient

separation.
C. The Process
When the system is first started, the unit is filled with product without ice. The product is first
cooled to form a slurry of approximately 30% ice. Then the wash column is started, and water
is removed from the system. This discharged water is replaced with fresh feed containing the
solute(s) being concentrated. As water is removed from the system in this manner the solute
concentration of the liquid in the system will increase. When the desired solute concentration,
or the maximum allowed by product characteristics, is reached, concentrate is removed from
the filtrate line of the recrystallizer. The solids removal rate (product output) is controlled to
maintain a constant solute concentration in the final stage.
In practice this is quite simple. A system will be set to produce (and remove) a fixed
amount of ice, and the product flow can be adjusted accordingto the equilibrium temperature
in the recrystallizer. A product has a certain freezing point at each solute concentration. While
operating as a two-phase mixture in the recrystallizer the system has a given equilibrium tem-
perature for that solution. This means that as the solute concentration of the liquid phase in-
creases, its equilibrium temperaturewill decrease. This signal canbe used to control the flow
of product from the system. Therefore, for a given solution, the ice production and product
temperature (concentration) are set so that the system will react automatically to changes in
feed concentration. Higher feed concentrations under the previous conditions will result in
higher production rates and vice versa. This is the basic form for a single-stage FC system.
520 Ruemekorf
Washwater
Washwater moves downward dueto the
pressure differencebetween the top and bottom
of the ice bed.
Water recrystallizesonto the surfaceof

the incoming ice crystals in the form of
dendrites. This increases the flow resistance
of the washed partof the bed.
p, ' p,- Since the washed part now has a greater flow
resistance water will flow along path "A" to maintain
a horizontal washfront.
1
The water that has recrystallized is now carried back
-8 "C P, i to the topof the icebed and discharged. This provides
L
of the
for an efficient washing action without recycle
wash liquid.
Concentrate
Figure 6 Wash water flow in a packed bed wash column. Wash water moves downward due to the
pressure difference between the top and bottom of the ice bed (P,> P*).Water recrystallizes onto the sur-
face of the incomingice crystals in theform of dendrites. This increases theflow resistance of the washed
part of the bed. Since the washed part now has a greaterflow resistance, water will flow along pathA to
maintain a horizontal wash front. The water that has recrystallized is now carried back to the top of the
ice bed and discharged. This provides for an efficient washing action without recycling the wash liquid.
The single-stage systemmust operate at the highest viscosity and lowest equilibrium tem-
perature for a particular product. This implies that the ice crystals must grow and the wash
column must remove these crystals under the least favorable conditions [3]. The high product
viscosity reduces thecrystal growth rate, increases pumping and mixing energy requirements,
reduces heat transfer coefficients, and limitsthe wash column capacity. The refrigeration sys-
tem must remove all the heat at the lowest temperature, increasing its size and reducing effi-
ciency. These have the effect of reducing the overall capacity and total efficiency of the process.
Multistage systems withup to six separate crystallization sections and only oneseparation sec-
tion (which may consist of a number of wash columns) overcome theselimitations by dividing
the ice production over a range of product concentrations. Figure 7 shows an example illus-
trating the increased capacity provided by a multistage system.
In Figure 7 you see a typical single-stage system with a water removal capacity of 250
kg/hr (550 Ib/hr) and in comparisona three-stage system witha water removal capacityof 1500
kg/hr (3300 lbhr). This is twice the sum of the individual units. Each stage is a complete crys-
tallization and recrystallizationsection. The ice crystals formed in one stage are pumped to the
next. This ice is replaced with concentrate from the previous stage, resulting in a counter cur-
rent flow of ice and soluble solids. Multistaging increases the capacityof a freeze concentration
system by separating the ice production section from the separation section. This allows the
wash column(s) tooperate with a liquid much lower in concentration and viscosity. Multistag-
ing reduces energy consumptionby dividing the ice production over the stages so that more ice
is made at higher freezing temperatures and lower viscosities, which improves the energy ef-
ficiency of the scraped surface heat exchangers (SSHEs) and reduces the overall energy needed
for pumping and mixing. The average crystal growth rate is increased by reducing the residence
time needed per stage. The crystals produced in stage 1 are transported to stage 2, where they
ncentration
Freeze 521
522 Ruemekorf
grow larger, andso on. These crystals are also exposed to the more favorable growth conditions
of lowersolute concentrationand lower viscosity. Multistage systemsalso provide for a wider ca-
pacity range since the componentsare modular and can be addedas greater capacity is needed.
111. TEST DESCRIPTION

The purpose of the test run was to demonstrate the operation of the NFC process on a waste-
water and determine the concentration limit forthis particular product. The test was completed
using Niro's FC-W6 Chemie pilot plant. The pilot plant is a complete skid-mounted single-
stage FC system as describedin Figure 3. It has a volume of 150 L, a piston-type wash column,
and 0.5 m*of surface area in two SSHEs. This provides for 10-20 kgihr ice production and
removal for most products.
The test solutionwas prepared to simulate a typical caustic wastewater contaminated with
organics. It contained approximately 1.5%acrylic acid and 3% sodium hydroxide, anda silicon
dioxide suspension was used to simulate suspended solids at -1100 ppm. The freezing point
depression for this mixture was approximately 1°C for each %TS in solute concentration. The
maximum temperature difference for stable wash column operation is normally around IO'C,
so a product concentration of at least 10% TS was expected in a single-stage unit. The wash
column usually will not performsatisfactorily with a slurry supply of much lower than- lO'C,
but this product could probably be concentrated to a much higher degree on a multistage sys-
tem. If the system can operate with some losses, due to the reduced efficiency of the wash
column, then the maximum concentration for the crystallization section can be determined.
Accepting losses and performing a two-step test like this allows us to determine the operating
conditions for a multistage system on a single-stage pilot plant.
A twofold concentration of the caustic solution produced water with only 24 ppm total
dissolved solids with 2 ppm from total organic carbon.The second part of the test showed that
the crystallization section could operate at over a 3.5-fold concentration with expected losses
in the water. Composite samplesof the feed, water, and concentrates taken duringthe run were
analyzed for total dissolved solids (TDS), total organic carbon (TOC), total suspended solids
(TSS), and alkalinity. The results [8] are given in Table 2. This indicates that a commercial
system couldbe designed with twoor more stages to produce a caustic wastewater concentrate
of around 22-23% total dissolvedsolids while maintaining water suitable for reuse inthe process.
Although specific cases must be analyzed individually to determine their economic feasi-
bility, the following example illustrates the cost benefits for FC in one particular system.
Table 2 Results of Analysis of Composite Samples from Pilot Plant Tests using
Niro's Chemie W6 Freeze Concentration Unit
Feed WaterConcentrate
~~~~
Part I (wash column limit)

Total organic carbon 7,860 17,650 2
Total suspended solids 124 24 1 <2
Total dissolved solids 61,400 137 ,000 24
Alkalinity 40.600 91,900 13
Part I1 (crystallizer limit)
Total organic carbon 36,000 6,900
Total suspended solids 389 154
Total dissolved solids 225 ,000 45,300
Alkalinity 174,000 33,000
Freeze Concentration in Wastewater Treatment 523
Table 3 Results of Economic Analysis for Example Wastewater Disposal

Costs (U.S.$/year)
Option' Capital Energy Total
~~ ~
1. Incineration 720,000
420,000 l , 140,000
2. Evaporation 360,000 Ob 360,000
Biotreatment 35,000 70,000 105,000
395,000 ,000
Incineration 95 300,000
860,000
3. Freeze concentration 440,000
70,000
370,000
Incineration 300,000395,000 95 ,000
835,000
"See text.
bzem energy assumes additional heat recovery equipment inuse.
Example Case Study

For this example we assume that a processor has a waste stream contaminated with various
organics havingproperties similar to those of the solution tested onthe pilot plant. The stream
is 2400 kg/hr wastewater with 10% TSS. Three options are determined:
Option 1. Incinerate the complete stream without pretreatment.
Option 2. Concentrate the stream threefold withevaporation, and incinerate the concentrate.
Employ additional biotreatmentof the condensate before reuse.
Option 3. Concentrate the stream threefold with FC and incinerate the concentrate. Reuse
water in process without additional treatment.
Table 3 gives a summary of the economics of the three options [4]. It is clear that straight
incineration (option 1) is the most expensive and also has the highest energy consumption.
Evaporatiodincineration (option 2) offers lower energy costs when a heat recovery system is
incorporated but requires the additional biotreatment process. Freeze concentratiodincinera-
tion (option 3) provides the least expensive processing.
Note that the zero energy costs for evaporation depend the on installation of a heat recov-
ery system for the incinerator,which can double the capital investment for the evaporator. This
additional cost was not included in the calculation.
W. CONCLUSION
Freeze concentration is presently a viable alternative when concentration by evaporation or
membrane filtration is not possible. Present applications for freeze concentration benefit en-
tirely fromthe improved qualityof the final concentrate due to the low processing temperatures
and selective separation of water. Through continuing improvementsin process design and re-
duced equipment costs, the areas of application that can profit from the use of this unit oper-
ation are expanding. Freeze concentration has demonstrated its potential in the treatment of
hazardous wastewater.
ACKNOWLEDGMENTS
The incinerator data for the economic analysis andsupport for the pilot plant test program were
provided by T-Thermal, Inc., Conshohocken, Pennsylvania.
524 Ruemekorf
REFERENCES
1. Wynn, N. P, Separate organics by melt crystallization, Chem. Eng. Prog., 88(3), 52 (1992).
2. Desphande, S. S., Cheryan, M., Sathe, S. K., and Salunke, D.K., Freeze concentration of fruit
juices, CRC Crit. Rev. Food Sci. Nutr., 20(3), 173 (1984).
3. Van Pelt, W. H.J. M., and Swinkels, W. J., Recent developments in freeze concentration, in Food
Engineering and Process Developments (M.LeMaguer and P. Jelens, eds.), Elsevier Applied Sci-
ences, London, 1986.
4. Jansen, H.A., and Klomp, R., Grenco Freeze Concentration Technology, Tech. Rep., Grenco Pro-
cess Technology, 1991.
5. Cheryan, M., Ultrafiltration Handbook, Technomic, Lancaster, Penna., 1986.
6. Niro Process Technology bv, Current Large Scale Commercial Application of Freeze Concentration
in the Food Industry, Tech. Publ., 1992.
7. Huige, N. N. J., Nucleation and growthof ice crystalsfrom water and sugar solutions in continuous
stirred tank crystallizers, Ph.D. Thesis, Eindhoven Univ. Technol., Eindhoven, The Netherlands,
1972.
8. Kom, S., T-Thermal, Inc., personal communication, 1992.
24
Organoclay Sorbents for
Selective Removal of Organics
from Water and Wastewater
Steven K. Dentel, Ahmad I.Jamrah, and Michael G.Stapleton

University of Delaware
Newark, Delaware
1. REGULATORYBACKGROUND
Cost-effective removal, or even reconcentration, of specific organic contaminants from aque-
ous systems is of increasing technological priority in light of increasingly stringent environ-
mental regulations.Thisis the case forwater,wastewater,andcontaminatedgroundwater
treatment. In the United States, EPA regulations developed in implementing the 1986 Amend-
ments to the Safe Drinking Water Act require substantial improvement in water treatment
technologies. Certain organic substances must be removed to extremely low levels. Maximum
contaminant levels (MCLs) havebeen established for eight volatile organic chemicals (VOCs)
[l] and for33 contaminants, including22 synthetic organic chemicals (SOCs) [2]; a wide range
of disinfectant by-products (DBPs) are also be be regulated [l]. The MCL for benzene, for
example, is 5pg/L with an MCL goal (MCLG) of 0 pg/L. Current technologies available for
attaining these low concentrations remain expensive.
In wastewater treatment, the Clean WaterAct of 1977’s list of 129 priority pollutants ne-
cessitated consideration of treatment process efficiency in terms of specific removal of targeted
chemical compounds. These are relevant both for publicly owned treatment works (POTWs)
and for facilities dischargingto POTWs. A desirable removal process in such cases may also be
one capable of specific uptake of one organic contaminant, or group of contaminants, in the
presence of other less critical but more highly concentrated organic components. Industrial
wastewater generatorsmust also be concerned with the presence of hazardous constituents in a
waste, which may determine whether the waste is hazardousby definition. A process capable
of concentrating selected waste components from a complex organic matrix may allow recov-
ery and reuse as well.
Thus a process capable of selective uptake of organic contaminants from watermay have
a variety of uses. A sorbent material that, unlike activated carbon, could exclude innocuous
components from the sorption zone would provide such performance.
525
526 Dentel et al.
II. POTENTIALAPPLICATION OF ORGANOCLAYS

One emerging technologyof possible use in these areas is the useof surfactant-modified smec-
tite clays, also termed organoclays, as a sorbent material. The organoclay is created by in-
sertion of anorganic cationic surfactant into the interlamellar spacings of the clay. The
exchangeable metal cations are replaced, to a varying degree, by the surfactant molecules [3-
51, which act as pillars to hold the aluminosilicate sheetsapart at an increased distance[ 6 ] .The
hydrophobic portions of the surfactant are oriented into. this interlamellar spacing, creating an
organophilic sorption zone. Hydrophobic organic compounds will be sorbed from water into
this organic phase, which actsas a solubilizing medium similar to a bulk solvent phase suchas
octanol or hexane [ 6 ] .
The sorption characteristics of the organoclay that is created are directly related to the
organic cation that has been placed onto the clay surfaces. Essentially, the sorption zone is of
adjustable dimensions, and hydrophobicityis determined by surfactant selection. For example,
if the surfactant possessesat least one aliphatic chain, the chainlength may have the following
effects:
Short chains tend to act as independent agents on the surface and may exclude aqueous com-
ponents from the sorption zone as a function of size and shape.
Longer chains have the ability to overlap onthe surface and form a uniform organic layer. This
layer serves to remove water sorbed on the mineral surface and change the surface to a
more hydrophobic character.
These traits are also a function of the clay properties, since the configurationof the surfactant
is determined by such properties as the cation-exchange capacityof the clay (and thereby the
distance between exchange sites).
Thepotential to produce a selective sorbentthrough the addition of specific organic
cations on the surface is one of the features that makes organoclays attractive. The sorptive
performance of some organoclays, usinga variety of clay and surfactant combinations,is sum-
marized in this chapter.
Some organoclay characteristics were established 20 years ago as such materials were
evaluated for their rheological properties; these materials are used as thickeners in paints, lu-
bricants, and evenlipstick. However, it is more recent research that provides the possibility of
economic applications in environmental engineering areas. According to small-scale studies to
date, properly tailored organoclays may selectively sorb and remove certain organic contami-
nants from water. By contrast, activated carbon, though exhibiting a high overall adsorption
capacity, is relatively nonselective, and substantial adsorptive interference is observed in the
complex chemical matrix of a surface water. By maximizing selectivity toward the uptake of
the organic contaminant in the presence of innocuous, but competing, natural organic matter,
the advantages of organoclays may become significant.
The reported use of organoclay materials in chromatographic applications implies revers-
ibility of this sorption process (at least from a vapor phase). Thus, kinetic aspects of these
applications of organoclays must also be considered. For example, desorptionof the surfactant
pillars must be slow within the time frame of the treatment process if the application is to be
feasible for production of drinking water. At the same time, uptake of organic contaminants
must be relatively rapid. Kinetic data for the sorption process may be necessary for proper
process evaluation and design and should be obtainedin a realistic multicomponent matrix sim-
ilar to the water to be treated.
Organoclay Sorbentsfor Removal of Organics 527
111. AREAS OF APPLICATION

Immobilization or separation of contaminants contained in polluted waters is an objective of
increasing importance in a variety of environmental settings. Recent research has suggested
in clear terms that chemically modified clay minerals represent a new and promising class
of adsorbent materials for accomplishing this. Specific areas of application exist in potable
water treatment [7,8], industrial wastewater treatment [9,10], and treatment or confinement
of contaminated groundwater [11-13]. Specific removal of hydrophobic organic pollutants,
such as benzene-related compounds, certain pesticides, and precursorsof carcinogenic trihalo-
methanes, is of key interest in all such applications.
In the areaof potable watet treatment, removal of such specific micropollutants as these is
often desired inthe presence of much higher concentrations of other innocuous organics. Due
to its high overall adsorption capacity, activated carbon is generally the adsorbent of choice
when adsorption is employed as a treatment process. Unfortunately, activated carbon is quite
nonselective, thus expending muchof its capacity in removal of incidental constituents. Thus,
the presence of natural organic matter (NOM) hasbeen shown to severely impair carbon’s ef-
fectiveness in removing such organics from solution as trichlorophenol, trichlorobenzene, and
trichloroethylene [14-201. The competition and coverage effects of theNOM are exacerbated
with time [20]. Thus, in many water treatment applications, activated carbon adsorption iso-
therms may significantly overestimate its capacity due to background NOM competition. In
this respect, any adsorbent providing more preferential uptake would offer obvious treatment
and economic advantages. Evidence suggests that surfactant-modified clays may provide this
selectivity. Furthermore, production from inexpensive base materials and the possibility of
chemical rather than thermal adsorbent regenerationadd to the potential benefits.
Membrane processes are also being advancedas promising water treatment technologies,
particularly in France and Japan. Although these offer numerous advantages over conventional
water treatment processes, they appear to do poorly in removinglow molecular weight hydro-
phobic organic compounds such as atrazine. Initial research in France indicated [8] that the
addition of a sufficiently selective organoclay sorbent preceding the membrane would cap-
ture such compounds in small enough mass that head loss to the membrane would not suffer,
and the sorbent could be periodically removed from the membrane by backwashing. It should
be added that such an organoclay material could also be added to conventional treatment
schemes in the rapid mix stage and removed in sedimentation and filtrationjust as powdered
activated carbon is sometimes now employed.
The use of organoclays in wastewater treatment has also been suggested. Cadena [9,21]
studied the use of an organoclay in removal of benzene-related hazardous wastes from aque-
ous solution. Srinivasan and Folger [37] investigated application of organoclay sorbents as
“molecular forceps” to remove toxic organics in a waste stream. Elution into an organic sol-
vent would then allow reuse or thermal destruction of the removed organic and reuse of the
organoclay.
Boyd et al. [5] first indicated that claysor soils heated with organic cations mightbe used
to improve attenuationof contaminant migration in groundwaters. Eitherin situ applicationof
the organic cationto a soilor clay or its additionto bentonite slurry wallsor clay landfill liners
were citedas possibilities. Subsequently, Soundararajan et al. [121 suggested the useof organo-
clays in solidificatiodstabilizationof organic wastes. Their approach was to combine the or-
ganoclay, as a minor constituent, with a cement, fly ash, or slag powder binder to enhancethe
binder’s ability to retain the organics. Burris and Antworth [l31 also suggested the use of or-
ganic modifiers for in situ modification of aquifer material to enhance retardationof organic
528 et Dentel al.
chemicals and establish a stationary zone of surfactant-modified aquifer material without sig-
nificant decrease in the hydraulic conductivity.
IV. TECHNOLOGY BACKGROUND

Organoclays are typically smectite slays treated with an alkylamine or quaternarized cationic
surfactant [22]. Adsorptive properties of the clay are modified due to insertion of the surfactant
molecules into interlamella, providing an extensive volumethat apparently serves as a hydro-
phobic “phase” into which hydrophobic contaminants can then be partitioned [3]. Character-
istics of this phase can be altered by appropriate matching of clay and surfactant, enabling in
theorythecustomized design of such sorbents.Variables that may be consideredinclude
charge density of the clay [11,231 and properties of the surfactant such as alkyl chain length
[24], number and basicity of positive charges [10,24], structural aspects (number of alkyl
branches, presence of aromatic moieties), and polarity index of the alkyl groups [12]. Subse-
quent treatment of the organoclay with other inorganic materials can improve uptake as well
(Figure 1).
Wyoming montmorillonite andhectorite are the baseclays that have been usedin research
studies [e.g., 3,25-281 and also used as base materials in some commercially available orga-
noclays (e.g., Bentones B27, B34, B38, produced by NL Industries for use as viscosity mod-
ifiers). These are smectites thatpossessdeficits of positivecharge due to isomorphic
substitution of cations in the octahedral sheets.Substitution in this sheet distancesthe origin of
charge from the interlayer and thus delocalizes the charge imbalance. Because there are no
negatively charged sites per se in the sheets adjoiningthe interlayer, compensatorycations lo-
cated in the interlayer do not serve as firm anchors between adjacent layers. The consequent
disorder may enhance access to adsorption or exchange sites. On the other hand, it is possible
that desorbability of inserted surfactant may also be facilitated. Montmorillonite, with a dioc-
tahedral structure, differs from hectorite (which is trioctahedral) in allowing greater distortions
in the sheet structures due to the unfilled cation sites. This is demonstrated by the substantial
Ce mg/l
Figure 1 Results of adsorption of 2,4,5-trichlorophenol. onto calcium montmorillonite (Ca-M), mont-

morillonite modified withdioctadecyldimethylammonium(dd-M), and montmorillonite modified with di-
octadecyldimethylammonium and then treated with CaCI, (Ca.dd-M). Solid/liquid mass ratio 0.0005;
equilibration time 15 hr. temperature 35°C. analyses by UV absorption. (From Demougeot [25] and Den-
tel et al. [26].)
J
Sorbents
Organoclay for Removal of Organics 529
dimensional differences betweenAi3+ and the substituting Mg2+. Isomorphous substitution in

hectorite instead replacesLi+ for Mg2+ because these have similar dimensions, andlittle dis-
tortion results. The more planar interlayer geometry may provide more uniform adsorption
selectivity.
Charge density or cation-exchange capacity (CEC)of the smectite can have a significant
effect onproperties of the resulting organoclays. If charge densityor the CEC is high, the spac-
ing of intercalated surfactantsis increased and theorientation is more likelyto be parallel to the
silica sheets [23]. However, more recent findings [l11 show superior removals of benzene and
toluene using a smectite with a lower CEC (Wmeqll00 g)than with a higher CEC (120 meq/
100 g). Evidently, the greater amount of free volume provided between pillars is the critical
factor, allowing placement of benzene and toluene parallel to the silica sheets in a more favor-
able configuration.
A range of cationic surfactants have been used in previous studies with organoclays.Early
studies employed primary amines such as propylamine and octadecylamine [e.g., 291. These
were readily intercalatedinto interlayers, but the apparent conformationis with the alkyl chain
parallel to the basal surfaces [30]. The extent and control overd(OO1) spacing is thus limited.
McBride et al. [3] suggested that it is the lowbasal spacing and thus close packing of n-
alkylammonium ions thatrestricts the interlamellar volume availablefor adsorption. A further
limitation is the pH dependency of the cationicity of these surfactants. Wolfe et al. [4,31] re-
ported comparatively poor sorptive removal using 11 different organics with such materials
(dodecylammoniumandpropylammonium). ’
The study also used dodecyldiammonium
[H3N+(CH2),2N+H3]with the assumption that fewer of the divalent ionswould be required to
neutralize the anionic charge on the anionic silicate sheets, leaving morefree interlamellarvol-
ume [22]. Whilethis was apparently thecase in adsorption fromvapor, removals from aqueous
suspensionswerenotimproved.Plausibly,watermoleculesinthe interlayer succeededin
shrinking the cavities regardless of the presence of any of these primary amines. It should be
noted that somedata presented by Wolfe et al. [4,31] are not consistent with more recent find-
ings, possibly due to volatilization difficulties or the use of procedures in which organic sol-
ubility limits were exceeded.
Quaternary ammoniumionshave also beenemployed as claymodifiers. A somewhat
greater basal spacing may provide a looser packing in this case. Furthermore, a significant
change in the properties of the modifiedclay may create a morefavorablesorbent.The
change includes the surface properties, which become organophilic as the mineral’s surface
area covered by the organic exchange cations increases [1l]; this leads to an increase in the
organic carbon content of the clay as well.
The porosity of the clay will also be altered. Since the porosity is related to the distance
between the sheets of the clay andis dependent onthe size and natureof the organic exchange
cations [26], modified clays can be designed to have surface accessibility to adsorbates of
varioussizes.Tetraalkylammoniumanionssuch as tetramethylammonium (TMA+), tetra-
propylammonium, and others with a variety of alkyl and aromatic groups have been used, as
exemplified by Table 1, from Boyd et al. [32]. Boyd et al. found that the larger, more hydro-
phobic pillars led to the best removals of pentachlorophenol (PCP) from solution (Figure 2).
The large? spacing appeared to enable partitioning of the sorbate into an organic “phase.”
(Thus the more general termsorption, rather than adsorption, appears to be more appropriate
‘Low adsorption levels reported by Wolfe have been questioned by Cadena [g] due to the possibility of volatilization
losses, emphasizing the need for zero-headspace procedures.
%e enlarged d(100) spacings after insertionof the larger surfactants are considerable (e.g.. 10-14 A increases with
DODMA+ (281.
530 Dentel et al.
Table 1 Structure of Quaternarized Cationic Surfactants Used in the Research of Boyd et al. [32]
Ion
Dioctadecyldimethylammonium DODMA+ CH3
I
CH3 - H+ - ( C H Z )-
~ ~CH3
I
(cH2) 17 - CH3
Hexadecyltrimethylammonium HDTMA+
Hexadecylpyridinium HDPY +
Trimethylphenylammonium TMPA+
Tetramethylammonium TMA+
CMercaptopyridinium 4"P+ SH
bH
Ammonium m a + H
I
H-N+-H
I
H
~
Source: Boyd et al. [32]. Reprinted with permission.
in describing uptake into organoclays.) Consistent with this hypothesis was the lack of com-
petitive effect in PCP uptake when up to 0.5 mmol of 3,4,5-trichlorophenol was also present.
Boyd et al. [32] suggested that the uptake of hydrophobic organic compounds by smectite mod-
ified with HDTMA was due to solute partitioning into a highly nonpolar organic phase formed
by the hydrophobic HDTMA ions. The partitioning behavior of HDTMA-smectite was sup-
ported by (1) the highly linear isotherms forthe adsorption of the organic compounds,(2) the
dependence of the sorption coefficient on the solubility of the organic compounds,(3) the gen-
eral agreement between the organic matter normalized partition coefficient of the organoclay
and the corresponding octanollwater partition coefficient of the organic compounds, and (4)
the dependenceof the adsorption capacity on the organic carbon content of the modified clay.
Smith and Jaff6 [33] used thermodynamic arguments-low or negative heats of sorption as
Organoclay Sorbentsfor Removal of Organics S31
0.12
t
9 0.10
P
e
E
oy 0.08
W
m
g 0.06
pt
0
U
Q
g 0.04
0.02
PCP EOUIUBAIUM CONCENTRATION (mmole1100 ml)

Figure 2 Results of Boyd et al. [32] for adsorption of pentachlorophenol onto smectite modified with
organics listed in Table1 and onto activated carbon.Temperature 20°C. [From Clays and Clay Minerals,
36 (2), with permission.]
evidenced by isotherms at different temperatures-to support partitioningas the uptake mech-

anism of tetrachloromethane using decyltrimethylammonium bentonite. If a decyltrimethyldi-
ammonium bentonite organoclay was used,however, the predominant mechanism appeared to
be adsorption rather than partitioning. Consistent with the workof Wolfe et al. [4] is a lesser
d spacing due to attachment of the diammonium structure to the same mineral surface. The
diammonium clay exhibited competitive adsorption in the presence of benzene with the tetra-
chloromethane,whilethe decyltrimethyldiammonium bentonitesorbedequalamounts of
tetrachloromethane whether the benzenewas present or not.
Such sorbent materials thus show promise in separation of more hydrophobic classes of
contaminants from wateras a class. One the other hand,Lee et al. [l13 reported that the use of
smaller TMA+ ions allowed quite selective sorption, removing benzene while excluding tol-
uene because of its somewhat larger dimensions. Cadena [9] showed the extent of organic u p
take by a TMA bentonite >> toluene > o-xylene, although each was
to be in the order benzene
removed to a much greater extent thanby an unmodified bentonite. This is consistent with the
findings of McBride et al. [3], who observed high selectivity of “A+-exchanged montmoril-
lonites exposed to single-ring aromatic hydrocarbonsand was greatly favored by small planar
molecules suchas phenol and benzene. Although Cadena surmised a partitioning mechanism,
the consensus of other investigatorsis that adsorption predominates with the smaller cationic
modifiers. Lee et al. [6] suggested “adsorption” as the mechanism of uptake for nonionic or-
ganic compoundsby TMA smectite. Their conclusion was based on the following: (1) A curvi-
linear isotherm was observed for sorptionof benzene by TMA smectite, while a linear isotherm
was observed byHDTMA smectite; (2) more soluble compounds such as benzene showed
532 Dentel et al.
strong affinity for TMA smectite, despite the fact that with a partitioning mechanism the
higher the water solubility,the lower the partitioning coefficient; and(3) the uptake of benzene
from aqueous solution was higher for TMA smectite than for HDTMA smectite, although
TMA smectite has a much lower organic carbon contentthan that of HDTMA smectite. Smith
et al. [34] in comparing the behavior of 10 different organoclays, indicated that those with alkyl
carbon content lessthan 3 functioned by adsorptive uptake; those with 12 carbons or more ex-
hibited removal by partitioning (no carbon contents of 3-11 were characterized).
These studies have made clear the potential for optimizing organoclay configurationfor a
given use or in idealized experimental systems. Results such as those in Figure 2 indicate that
properly synthesized organoclays approach within an order of magnitude the performance of
activated carbon [36] as an adsorbent in a “clean” system. Evidence to date suggests that the
modified clays may perform equally as well as carbon in a complex system where selective
adsorptive properties are advantageous. Cost advantagesmay also be significant in comparing
organoclays to carbons, due to energy costs in production and regeneration of the latter.
Such comparisons may well extend to use in the more complex chemical environment of
water treatment. Recent work[7] suggests the practicability of using these materials in actual
surface waters; however, analytical difficulties may be encounteredin determining removals for
targeted componentsif measures are not taken for proper extraction and separation from a com-
plex water or wastewater matrix.
V. FEASIBILITYSTUDIES
Specific application of tailored organoclay sorbents must accordinglybe evaluated on a site-
specific basis. Organoclay media to be evaluatedmust be chosen with appropriate understand-
ing of clay and modifierproperties and desired interactions with boththe target organic(s)and
the other organic matter to be excluded. Experimental procedures begin with equilibrium iso-
therm data, generated by standard batch-test methods using analytical methods appropriate for
the particular organic and anticipated concentration range.Closed, zero-headspace containers
are to be used, particularly if treatment of volatile organic compounds is considered. Proper
attention must be given to pH and ionic strengtheffects on both adsorption and analytical meth-
ods. A number of past studies have ignored such influences, particularly that of pH in the case
of ionizable chlorophenolics.
Isotherms must also be produced in a system with background components representative
of those to be encountered in full-scale treatment. In water or wastewater applications where
the types and concentrations of background organics, surface-active substances, and/or colloi-
dal material may vary diurnally or seasonally, the effectsof these should be examined by ap-
propriate use of actual or simulatedexperimental matrices, Temperature(s) of anticipated
operation are of particular importance if an adsorptive rather than partitioning uptake is an-
ticipated. In reactor design, the kinetic aspects of sorption and release should be evaluatedby
use of variable equilibration times in batch studies or through use of stirred flow reactor ex-
periments for more rapid reactions.
Standard proceduresfor predicting scaled-up performancefor sorption processes may then
be employed in projecting feasibility and costs. However, recent studies [20,35] have demon-
strated flaws in these procedures when activated carbon is employed as an absorbent. Diffi-
culties lie in proper simulation of competitive effects and apparent catalytic activity at the
carbon surface, neither of which is probable in the use of organoclays. Nonetheless, a com-
parison of activated carbon with organoclay for full-scale use requires attention to accurate
scale-up predictionsfor both alternatives. In addition, the regeneration costs for each should
be
included in any comprehensive economic evaluation.
Sorbents
Organoclay for Removal of Organics 533
Results of such feasibility studies will indicate to engineering practitioners whether orga-
noclays are feasible alternatives to technologies suchas activated carbonand, if so, under what
circumstances larger, field-scale studies of the organoclay sorbents may be warranted. Poten-
tial applications on this basis are likely in water, wastewater, or contaminated groundwater
treatment.
VI. SUMMARY
Current research is characterizing the actual mechanisms responsible for selective adsorption
of water contaminants on modified clays. In an engineering sense, a more fundamental under-
standing of how the modifications determine selectivity will enable the virtual design of ad-
sorbents which are more specific and thus more economical for a given application. Potential
watertreatmentuses of such materials include (1) use as additives to the conventional
coagulation-flocculation-sedimentation sequence;(2) use in a granular form in a column-type
adsorber process; and(3) use in conjunction with advanced membrane processes. Applications
in related areas also exist, such as the creation, possibly in situ, of clay barriers to prevent
transport of organic solvents
fromcontaminatedgroundwatersand the removal of
specific priority pollutants from industrial wastewaters.A selective adsorption process will be
beneficial in all of these applications and would be likely to significantly reduce costsin com-
parison to present, less selective removal technologies such as activated carbon adsorption.
ACKNOWLEDGMENTS
Funding support is gratefully acknowledged from the U.S.Geological Surveyand, for S.K.D.,
from Lyonnaisedes Eaux while on a research sabbaticalat the Institut National Polytechnique
de Lorraine. J. Y. Bottero provided invaluable assistance at INPL.
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3. McBride, M. B., Pinnavaia, T. J., and Mortland, M. M., Adsorption of aromatic molecules by
clays in aqueous suspension, Adv. Environ. Sci. Technol., 8, 145-154, 1977.
4. Wolfe, T. A., Demirel, T., and Baumann, E. R., Interaction of aliphatic amines with montmoril-
lonite to enhance adsorption of organic pollutants, Clay Clay Min., 33, 301 (1985).
5. Boyd, S. A., Lee, J. -F., and Mortland, M. M., Attenuating organic contaminant mobility by soil
modification, Nature, 333, 345-347 (1988).
6. Lee.J. F., Mortland, M. M., Chiou, C. T., and Boyd, S. A., Shape selective adsorption ofaro-
matic molecules form water by tetramethylammonium-smectite,J. Chem. Soc. Faraday Tmns. I ,
85, 2953-2962 (1989).
7. Jamrah,A. I., andDentel, S. K., Selectiveremovaloforganics by surfactant-modified clays,
h o c . Joint CSCE-ASCE Nut. Conf Envtl. Engg., Montreal, 1073-1080, July 12-14 (1990).
sur des zeolithes et des
8. Jucker, C., Isothermes d’adsorption de carbone organique total et d’atrazine
argiles greffees. -Rapport de Stage, Institut National Polytechnique de Lorraine,1990.
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115, 756-767 (1989).
10. Srinivasan, K. R., and Fogler, H.S., Use of inorgano-organoclays in the removal of prioritypol-
lutants from industrial wastewaters, Clay Clay Min., 38, 277-293 (1990).
11. Lee, J. F., Mortland, M. M., Chiou, C. T., Kile. D. E., and Boyd, S. A., Adsorption of benzene,
toluene,andxylenebytwo tetramethylammonium-smectites havingdifferentchargedensities,
Clays Clay Min., 38(2), 113 (1990).
534 Dentel et al.
12. Soundararajan, R., Barth, E. F., and Gibbons, J. J., Using an organophilic clay to chemically sta-
bilize waste containing organic compounds, Hazardous Mar. Control, 3 (l), 42 (1990).
13. Burris. D. R., and Antworth, C. I?,In situ modification of an aquifer material by a cationic sur-
factant to enhance retardation of organic contaminants, J. Contam. Hydrology,10,325-337 (1992).
14. Robeck, G . G . ,Dostal, K. A., Cohen, J. M., and Kreissl, J. F., Effectiveness of water treatment
processes in pesticide removal, J. AWWA, 57 2 (1965).
15. Lalezary, S., Pirbazari, M., andMcGuire, M. J., Evaluating activated carbon for removing low
concentrations of taste and odor producing organics, J. AWWA, 78,11-16 (1986).
16. Milner, R. J., Baker,D.B.,Speth,T.F.,andFronk,C. A., Treatment of seasonal pesticides in
surface waters, J. AWWA, 81(l), 43-52 (1989).
17. Summers, R. S., Haist, B., Koehler. J., Ritz, J., Zimmer,G . , and Sontheimer, H., The influence of
background organic matter on GAC adsorption, J. AWWA. 81(5),66 (1989).
18. Najm, I. N.. Snoeyink, V. L., Suidan, M. T., Lee, C. H., and Richard, Y., Effect of particle size
and background natural organics on the adsorption efficiency of PAC,J. AWWA, 82(1), 65 (1990).
19. Speth, T.F.,EvaluatingcapacitiesofGACpreloadedwithnaturalwater, J. Environ. Eng. Div.-
ASCE, 117(l), 66 (1991).
20. Carter, M. C., Weber, W. J.. and Olmstead. K. I?,Effects of background dissolved organic matter
on TCE adsorption by GAC, J. AWWA. 8,81-91 (1992).
21. Cadena, F., and Jeffers,S. W., Use of tailored clays for selective adsorption of hazardous pollutants,
Proc. 42nd Indust. Waste Conf., Purdue Univ., West Lafayette, Ind., 113-119.
22. Barrer, R. M., Zeolites and Clay Minerals as Sorbents and Molecular Sieves, Academic, London,
1978.
23. Weiss, A., Mica-type layer silicates with alkylarnmonium ions, Clays Clay Min., 10, 191 (1961).
24. Barrer, R. M., andMillington, A. D.,Sorptionandintercrystallineporosity in organo-clays, J.
Colloid Interface Sci., 25, 359 (1967).
25. Demougeot,H.,Adsorptiondemoleculespolluantesdel’eau:phenol,2,4,5-trichlorophenol et
acide tannique sur des argiles modifiees, DEA Rep. Institut National Polytechnique de Lorraine,
1990.
26. Dentel, S. K., Bottero, J. Y., Demougeot, H., Duguet, J. E,and Anselme. C., Adsorption of tannic
acid, phenol, and 2,4,5-trichlorophenol on organoclays, Water Res., (1993), submitted.
27. Wolfe, T. A., Addition of aliphatic amines to montmorillonite to improve its adsorption capacity for
organic pollutants in aqueous solution, Ph.D. dissertation, Iowa State Univ., Ames, Ia (1981).
28. Hommeril, F., Utilisation d’argiles greffks en vue de 1’6limination de micropolluants organiques,
Rapport de Stage, Institut National Polytechnique de Lorraine, 1986.
29. Jordan, J. W., Organophilic bentonites. I. Swelling in organic liquids, J. Phys. Colloid Chem., 53,
294-306 (1949).
30. Theng, B. K. G . , The Chemistry of Cluy-Organic Reactions, Wiley, New York, 1974.
31. Wo1fe.T. A., Demirel, T., and Baumann, E. R., Adsorption of organic pollutants on montmorillo-
nite treated with amines, J. Water Pollution Control Fed., 58,68 (1986).
32. Boyd, S. A.,Shaobai, S., Lee,J.-F.,andMortland, M. M., Pentachlorophenolsorptionby
organo-clays, Clays Clay Min., 36(2) 125 (1988).
33. Smith, J. A. and Jaffk,I? R., Comparison of tetrachloromethane sorption to an alkylammonium-clay
and alkyldiammonium-clay, Environ. Sci. Technol.,25, 2054-2058 (1991).
34. Smith, J. A., Jaff6, I? R., and Chiou, C. T., Effect of ten quaternary ammonium cations on tetra-
chloromethane sorption to clay from water, Environ. Sci. Technol.,24, 1167-1 172, 1990.
35. Vidic, R. D., Sorial, G . A., Papadimas, S. I?,Suidan, M. T., and Speth, T. F., Effect of molecular
oxygen on the scaleup of GAC adsorbers, J. AWWA, 8,98-105 (1992).
36. Dobbs, R. A., and Cohen, J. M., Carbon Adsorption Isotherms for Toxic Organics, EPA 609/8-
80-023, MERL, Office of Research and Development, U.S. Environmental Protection Agency, Cin-
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342,1989.
25
Removal of Chromate, Cyanide, and
Heavy Metals from Wastewater
Klaus Schwitzgebel and David M. Manis

EET
Austin, Texas
1. INTRODUCTION
The Clean Water Act of 1983 imposed national limitations on the concentrationof metals al-
lowed to be discharged into the waters of the United States.States and municipalities have the
authority to impose even more stringent pretreatment standards. In order to comply with the
regulations, technologies were developed and continue to be developed that reduce the con-
centrations of metals in wastewater effluentsto acceptable levels. The technologies currently
available to reach the treatment goals have been reviewedin several EPA documents [l-61.
In September 1988, the State of California Department of Health Services published a
study of the technologies availableto treat aqueous waste. The California study made recom-
mendations regarding the adoption of wastewater pretreatment standards prior to discharge.
Performance data of treatment plants are included in this report [7]. The treatments include
oxidation of cyanide complexes, reduction of chromates, precipitation of metals as hydroxides
and sulfides, coprecipitation with iron, and ion exchange. The basic chemistries for cyanide
oxidation, chromate reduction, and the precipitation of metals as metal hydroxides and metal
sulfides are discussed in Section 11.
Wastewater treatment gets complex if cyanide, chromate, and a mixture of heavy metals
are generated in a plant. A novel process [8] to treat such a complex matrix from a custom
plating shop is described in Section VI. Cyanide-containing streams are separated from the
general rinse and destroyed by hypochlorite in the cyanide reactor. The effluent from the cy-
anide reactoris fed together with the general rinse into the main reactor. Here chromate(Cr"')
is reduced by ferrous sulfate, with Cr"' and Fe"' being the reaction products. Heavy metals
present are coprecipitated with Fe(OH),. Chromate reduction and heavy metal precipitation
can be performed in one vessel at pH 9.5-10. This approach greatly reduces the number of
clarifiers and reactors needed for treatment. Performance data for this treatment scheme are
provided.
535
536 Schwitzgebel and Manis
II. CHEMISTRY OF AQUEOUS TREATMENT FOR CONTROL O f

CYANIDE, CHROMATE,AND HEAVY METALS
The removal of heavy metals as hydroxides or sulfides from aqueoussolutions requires the ox-
idation of cyanide and the reduction of chromate before the precipitation step. Cyanides are
oxidized above pH 11 using elemental chlorine (Cl,) or hypochlorite (C10-) solutions. Rapid
decomposition of the intermediate, cyanogen chloride (CNCl), occursat this high pH with cy-
anate (CNO-) as the end product. This compound can be further oxidized to N2 and CO2 ina
second chlorination step at pH 7.5. Very concentrated cyanide solutions, such as cyanide-
based heat treatment melts used in the metal industry or spent cyanide-based electroplating
baths, are best destroyed electrolytically.
Chromates are normally removed in a two-step process: reduction of chromate at pH 2-3
using sulfite and precipitation of chromium hydroxide at pH 8.5. The reduction and precipi-
tation can be reduced to one step in the alkaline region using a ferrous compound.
Precipitation of metals as hydroxides encountersdifficulties in a multielement matrix, es-
pecially if amphoteric elements are present. Coprecipitation with iron widens the pH region
suitable for metal precipitation. Sulfides show lower solubilities than hydroxides, but dosage
and odor problems are the main obstacles to the wide use of this precipitation reagent.
A.CyanideOxidation
Cyanide (CN-)-based plating baths exhibit the unique property of producing fine crystalline,
shiny metal coatings. They are therefore widely in use despite the high toxicity of cyanide and
the greater control effort necessary in pretreatment.
Cyanide destruction is commonly achieved through oxidation inthe alkaline region using
chlorine gas or sodium hypochlorite. Peroxide oxidation and treatment with ozoneare reported
to be feasible. Electrolytic oxidation has advantages in treating highly concentrated cyanide
solutions stemming from heat treatment melts and spent cyanide baths [9].
1. AlkalineChlorination
Oxidation of cyanide (CN-) to cyanate (CNO-) in the alkaline region is achieved either
through chlorination with chlorine gas or through treatment with hypochlorite. The highly toxic
cyanogen chloride (CNCl) is formed as an intermediate. The overall chemical reactionsare
2 Cl2 + 2 NaCN 4 2 CNCl+(1)
2 NaCl
2 CNCl + 4 NaOH 4 2NaCNO + 2 NaCl + 2 H20 (2)
The cyanogen chloride in reaction (1) is formed instantly, andthe formation rate is independent
of pH. The hydrolysisreaction, reaction (2), however, is pH- and temperature-dependent. Ent-
wistle [9] reports that at 15°C and pH 11the cyanogen chloride hydrolyzes to about 0.1% of its
original value within10 min. The CNCl decompositionrate slows appreciablyat lower pH val-
ues. The cyanide oxidation is therefore performed at pH values of 11or greater to avoid buildup
of cyanogen chloride and the escape of toxic CNCl gas.
The useof gaseous chlorine (Cl,) necessitates the installation of a chlorinator. This is
avoided by adding thechlorine in the form of sodium hypochlorite (NaC10). Sodium hypochlo-
rite is commercially available as an aqueous solution with15% available chlorine. The overall
reactions using hypochlorite are
2 NaOCl + 2 NaCN + 2 H20 + 2 CNCl + 4 NaOH
(3)
2 CNCl + 4 NaOH + 2 NaCNO + 2 NaCl + 2 H20 (4)
Removal of Chromate, Cyanide, and Heavy Metals 537
Table 1 DissociationConstants of MetalCyanideComplexes

at 25°C
Complex Equilibrium expression
Cd(CN):- 1 x 10-6 Cd(CN):- G Cd" + 4 CN-
Zn(CN):- I X 10-17 Zn(CN)z-Zn2+ + 4 CN-.
Ag(CN); 1 x 10-2' Ag(CN); e Ag+ + 2 CN-
Fe(CN):- 1 X Fe(CN);- S Fe2+ + 6 CN-
Cu(CN)Z- I X 10-25 Cu(CN)z- e Cu2+ + 4 CN-
Ni(CN)z- 1 X 10-30 Ni(CN):- S Ni2+ + 4 CN-
Fe(CN)Z- 1 X 10-31 Fe(CN)Z- S Fe3+ + 6 CN-
Source: From Refs. 10 and 11.
The cyanate (CNO-) formedin reactions (2) and (4) is much less toxic than cyanideitself.
HCNO + 2 H20 -
It decomposes slowly in water to form ammonia and carbonic acid:
NH3 + H2CO3
Local regulations may allow direct dischargeof cyanate (CNO-). If cyanate (CNO-) dis-
(5)
charge is prohibited, its decomposition into CO, and N, can be accomplished ina second chlo-
rination step using chlorine [reaction (6)] or hypochlorite [reaction (7)l.
3 Cl2+ 6 NaOH + 2NaCNO + 6 NaCl + N2 + 2 NaHCO3 + 2 H20 (6)
3 NaOCl + H20 + 2 NaCNO 3 NaCl + NZ + 2 NaHC03
(7)
These reactions take place at a pH 7.2-7.7. At higher pH values, other oxidation products such
as nitrates are also formed. This causes additional chlorine consumption.
In the presence of heavy metals, e.g., zinc, cadmium,or copper, cyanideis complexed and
the initial cyanide-chlorine reaction rate is slowed down. This necessitates reaction times of
30-40 min in the cyanide reactor. Nickel cyanide complexes require 24 h for destruction, while
Fe cyanides are only oxidized to the ferricyanide complex (Fe(CN)d3-. For this reason it is
essential tostrictly separate cyanide-containingstreams from nickel-andiron-containing
rinses. Further destruction of ferricyanide is reported to be feasible with hydrogen peroxide and
ultraviolet light irradiation' [ 5 ] .
The dissociation constantsof the heavy metal cyanide complexes givean indication of the
difficulty of cyanide destruction throughchlorination. Table 1 lists these constants for themet-
als commonly encountered in the plating industry [10,1l].
2. Electrolytic Oxidation
Special problemsarise during treatmentof highly concentrated cyanidesolutions such as spent
electroplating and heat treatment baths. Heat treatment baths typically contain BaCI, (26%),
NaCN (m%),Na2C03 (13%), NaCl (21%), and graphite.
Cyanide destruction can be achievedin a process described by Entwistle [9]. The process
equipment consists of five elements: spray dissolution chamber, settling chamber,electmlytic
cell, crystallizer, and scrubber.
The destruction of heat treatmentsalts is possible in a closed-loop operation. The salts are
dissolved in a spray dissolution chamber, and insolubles are removed through settling. The
electrolytic cell is constructed of a mild steel tank, graphite anodes, and mild steel cathodes.
A dc voltageof 2.8-3. l V is applied. The current reaches several thousand amperes depending
on the cell size. Chloride must be presentin sufficient quantityto generate hypochlorite within
the cell.
Products generated in the electrolytic cell are sodium carbonate and bicarbonate, sodium
formate, sodium oxalate, and ammoniumcarbonate. Sodium cyanateis present as a minor com-
ponent (0.5%). Some ammonia escapes with the off-gas and is controlled by wet scrubbing.
The waterin the feed stream canbe balanced through evaporation losses and water of crys-
tallization, which is mainly removed with the sodium carbonate decahydrate. Barium forms
insoluble BaCO,. Heavy metals like Cd, Cu, and Zn can be recovered a metal deposits on the
cathodes. The process efficiency depends on the NaCN concentration. Direct current power
consumption ranges from 0.004 to 0.019 k W g CN- for cyanide concentrations of 100 g/L
and 5 g/L, respectively. At lower cyanide concentrations the efficiency drops sharply (Figure
1). Iron and nickel cyanides are reported to be destroyed in the process [9].
B. ChromateReduction
Hexavalent chromium is toxic, and most chromates are water-soluble. OnlyBa2', Pb2+, Hg ,+
and Ag+ form insoluble chromates. Pollution with chromatesis especially troublesome, since
chromates are not adsorbed by soil and thus reach the groundwater table rapidly.
Most chemical control strategies are based on the reduction of hexavalent chromium (Cr")
to trivalent chromium(Cr"'). Trivalent chromium is much less toxic than chromates and forms
a hydroxide with a solubility minimum inthe pH range 8.0-9.0. Common reducing agents used
are sulfur dioxide (SO,) and its salts, ferrous salts, and iron sulfide.
1. ChromateReductionwithMetabisulfite
The most widely used reducing agent in SO2-based processes is metabisulfite (Na2S205).It
crystallizes from solutions containing NaOH and SOz in a mole ratio of 1 :1. In aqueous so-
lutions it forms an equilibrium with the disulfite ion:
S2052- + H20 e 2HS03

disulfite metabisulfite
Aqueous solutions of sodium metabisulfite react acidicly. The solubility in water is 54 @l00
mL at 20°C [ 121.
Metabisulfite reduces chromates in acidic solutions:
4 H2CT04 + 3 Na2S205 + 6 H2SO4Cr2(SO4)3 + 6 NaHS04 + 7 H20 (9)
The sulfite (S4+) is oxidized to sulfate (S6'). The reaction consumes acid and is strongly
temperature- and pH-dependent. The reaction rate increases with decreasing pH. The sulfur
dioxide equilibrium pressure also increases with decreasing pH, causingSOz gases to escape
that are toxic and cause corrosion. Thereforea pH range of 2-3 is generally maintained in the
reduction reactor as a compromise between SO2 backpressure and reaction rate.
2. Chromate Reduction with Fe" in Acidic Medium
Chromate reductionis feasible with ferrous salts in acidic solutions.The redox potentialof the
Fe"'/Fe" chain is pH-independent in the acidic region, while the oxidation potential of chro-
mate is strongly dependent on the hydrogen ion concentration. Chromate reduction using fer-
rous ions in the acid region is performed at pH values 1 3 [13]. The overall reaction,
2 H2CT04 + 6 FeS04 + 6 HzS04 + Cr2(SO4)3 + Fe2(SO4)3+ 8 H20 ( 10)
consumes 3 mol of Fe" per mol of Crv' reduced to Cr"'. Fe" is oxidized to Fe"' in the reac-
1.5 mol
tion. This stoichiometry is less favorable than using SO2-based reducing agents where
100
80
60
40
2c
c
0.00 0.01 0.02 0.03
[kWh/g CN]
Figure 1 Electrolytic decompositionof cyanide. Effect of cyanide concentration (glL NaCN) on pro-
cess efficiency (kwhlg CN- destroyed). (Data from Ref. 9.)
of SOz is oxidized for every molof Crv' being reduced. An additional disadvantage is the
introduction of iron into the solution, which increases the sludge production in the chromium
precipitation step.
These disadvantages must be weighed against the advantages offeredby the iron process.
Chromate reduction by iron is odorless. No toxic and corrosive gases escape from the reactor
as in SO2-based processes. In addition, heavy metals are precipitated to concentrations one to
two orders of magnitude lower than is achievable by hydroxide precipitation of these metals in
the absence of iron. These advantagesare compounded if the chromate reductionis performed
in the alkaline region. Chromate reduction and metal precipitation can be achieved in one re-
actor at one pH under alkaline conditions.
3. ChromateReductionwithFe"inAlkalineMedium
Iron (11) andiron (111) precipitate in the neutralandalkalineregion as hydroxides.The
Fe"'
hydroxide is by 24 orders of magnitude less soluble than the Fe" hydroxide
[Ks,,(Fe(OH)3) = 10-37.4; KSp(Fe(OH)J = 10"3.8]. The Nernst equation describes the redox
potential of the Fe"'/Fe" cham:
E = 281 - 59 X pH (m V) ( 12)
The Fe"' and Fe" activities are expressed as functionsof pH using the solubility productsof the
hydroxides, the ion product of water (K,,,), and the definition of pH.
2
Ksp(Fe(OH)2)= URII U OH- ( 13)
K,(Fe(OH)3) = 20"-
U ~ I U (14)
pH = -IOg aHt (17)
The potential described by Equation (12) is more negative in the entire alkaline rangethan the
oxidation potentialof the Crvl/Cr"' chain. This makes the reductionof chromate feasible in the
pH range of 7-1 1. Fe" can be added in the formof ferrous sulfate, which is a by-product from
acid pickling in steel mills. The Fe" can also be produced electrochemically by anodic disso-
lution of steel anodes [7].
4. ChromateReductionwith Iron Sulfide

Chromate can be reduced by the addition of FeS at pH 7. Fe" is oxidized to Fe'", and the
sulfide ion is oxidized to elemental sulfur [4].
H2CI04 + FeS + 2 H20 + Cr(OH13 +(OH)3

Fe +S (18)
The reaction time needed for the completion of reaction (18) is several hours [14].
Table 2 Theoretical pH for Metal Precipitation to 0.1 ppm
4.9
3.4
1.6
'Kspvalues from Ref. 15.
C. Metal Hydroxide Precipitation

After the oxidation of cyanide and reduction of chromate, the metals can be precipitated as
hydroxides. A prerequisite isthe absence of strong complexing agents suchas ethylenediamine
tetraacetic acid (EDTA). The degreeof metal precipitation is dependent onpH. At a given pH,
different metals exhibitdifferent solubilities. The amount of metal in solution as a function of
pH can be calculated theoretically from the solubility product (Ks,,)of the hydroxide. For di-
valent metals this takes the following form:
Kw
COH- = G
This correlation relates the equilibrium metal concentration CM:+ with the hydrogen ion con-
centration C, +.Ion pairing is neglected, and the activity coefficients are assumed to be unity
in this derivation.
Table 2 lists the solubility products for the most common metal hydroxides W]. The the-
oretical pH values necessary to reach an equilibrium metal concentration in solutions of 0.1
ppm are calculated from Equation (23).
In practice, the equilibrium concentration of 0.1 ppm is not reached at the pH values in-
dicated in Table 2. This is due to ion pairing and the tendency
of freshly precipitated hydroxide
solutions to stay supersaturated. The metal solubility can
be reduced by a pH increase above the
values given in Table 2. This increases the driving forcefor hydroxide precipitation. However,
this approach has limits, especially when dealing with hydroxides that resolubilize in excess
base. Such amphoteric behavior is typical for beryllium, lead, zinc, tin, chromium, aluminum,
and antimony. The hydroxides of these metals redissolve in excess base and form [Be(OH),]'-,
[Pb(OH),I'-, [Zn(OH),]-, [Sn(OH),]-, [Cr(0H),l3-, [AI(OH),I-, and [Sb(OH),I- complexes.
Ammonium salts, if present, also can hinder hydroxide precipitation due to the formation of
soluble ammonium complexes: [Ag(NH,),] +,[Fe'1(NH,)6]2+,[Ni(NH3)6I2+, [cd(NH,),]'+,
[Mn(NH3)612',[Zn(NH3)412't [CU(NH~)~I*+.
The previously mentioned tendency of freshly precipitated hydroxide solutions to stay
supersaturated becomes obvious if the results of Table 2 are compared with the experimental
data shown in Figure 2. The metal concentration in solutions for single-metal precipitation ex-
periments are one to two orders of magnitude higher than would be expected from theoretical
calculations.
Also shown in Figure2 are the residual metal concentrations in a mixture of 20 ppm each
of CrV1,Pb, Cu, Cd, Zn, and Ni. CrV1was reduced with Fe", and the hydroxides precipitated
at different pH values. Due to coprecipitation with Fe(OH), there is considerable decrease in
residual metal concentrations compared to that measured for individually precipitated metals.
This coprecipitation is the reason for the good performance of iron-based processes observed in
the industry, especiallyfor the removal of a number of elements in the presence of chromate.
D. Metal SulfidePrecipitation
The solubility productsof metal sulfides are several orders of magnitude lower than thoseof the
corresponding hydroxides. This should make it feasible to precipitate the heavy metals from
solutions containing complexing agents that prevent metal removal by hydroxide precipitation.
Also, the pH range for the precipitation of metals as sulfides is much broader.
Table 3 lists the solubility products for metal sulfides of the type MeS, Me$, and Me2S3
[15]. Metal sulfide precipitation occurs if the solubility product is smaller than the product of
metal concentration times sulfide ion concentration:
Table 3 Solubility Products (Ksp)for Metal Sulfides of Type MeS, Me& and Me$,
MeS KSP Me$ 6, KSP
MnS 10- 15.2 TI$ 10- 19.9 10-28.4
10-21.6 FeS Hg2S 10-47.0 Sb2S3 10-58.5
10-21.7 ZnS Bi2S3 10-71.8
a-Cos 10-21.3 10-85.0
Ag2S 10-52.2
p-cos 10-26.7 c02s3 10- 124.0
a-NiS 10-20.5
p-NiS 10-26.0
10-27.0 SnS
10-27.9 CdS
PbS 10-28.6
cus 10-40.2
10-51.2
HgS
PtS 10-72. I
Source: Data from Ref. 15.
100
P
5 .l
.Ol
Imp
l
0 0
S
-
e
S ’
Figure 2 Metal removal efficiency by hydroxide precipitation and Fe”’ coprecipitation. (---) Solu-
bilities of metals precipitated with NaOH from single-metal solutions
as a functionof pH. (0)
Solubilities
of metals precipitated with ferrous sulfate-NaOH from a solution containing 20 ppm each of Cr”’, Pb,
Cu, Cd, Zn, and Ni as a function of pH.
544 Manis Schwitzgebel and
Ksp S CS2-
Sulfide (S2-) is the dissociation product of H2S. The solubility of H2S in water is 0.1 moYL.
H2S dissociates in two stages:
H2S +
P HS- + H" K1 = 10-6.9m01/l (25)
HS- "* S2- + H+ KZ = 10"2.9 mol/! (26)
We find for the overall reaction:
H2S + 2H+ + S*- K 3 -- 10"9.8 (mo1/1)2 (27)
From Equation (27). we calculate that at pH 7 a hydrogen sulfide solution of 0.1 mol/L con-
tains only 10" mollL of free S2- ions. The most solublesulfide (MnS) listed in Table 3 would
shownanequilibrium concentration of [Mn] = K,,,/lO" = moYL = 5.5 mg/Lunder
these precipitation conditions.
In practice, processes are designed to operate with lower sulfide concentrations in order to
minimize the H2S odor in the working environment. Theodor detection level of hydrogen sul-
fide is 0.1-1 ppm. Because H2S is toxic, the workplace H,S limit is set by the Occupational
Safety and Health Administration (OSHA) at IO ppm.
Sulfide can be added in soluble form as Na2S or NaHS. The problem with this approach
is the correct sulfide dosage. Encouraging results using a sulfide-specific electrode were re-
ported [4]. The Sulfex process [4] uses freshly precipitated FeS as the source for sulfide and
operates in the neutral pH range. FeS dissolves to its equilibrium concentration. The sulfide
ions liberated in this fashion precipitate all sulfides with a solubility product smaller than that
of FeS. From Table 3 it is seen that only manganese would not be precipitated as MnS. The
dissolved iron precipitates as Fe(OH),.
The FeS dosage necessary in this approach is several times the theoretical amount. The
amount of sludge produced is therefore large in comparison to the amount of heavy metals re-
moved. Chromate, if present, is reduced and precipitates as Cr(OH),.
111. ORP and pH MEASUREMENT

To apply the chemistry discussedin Section I1 to an automated process, it iscritical to control
the pH and the oxidation reduction potential(ORP). The adjustment of the pH and the ORP is
achieved with electrodes in combination with millivolt controllers and chemical feed pumps.
The electrode system for pH determination consists of a glass electrode and a reference
electrode. The mostcommonreference electrode is the saturated calomel electrode [Hgl
Hg,Cl,/KCl(sat)] with a constant potential of 241.2 mV at mom temperature. Similarly, the
ORP is determined with a platinudcalomel electrode chain. The electrodes are interfaced with
a pH/ORP meter.
The pH electrode system is calibrated using buffersof known pH. A pH 7 solution is used
to set the intercept at the pH meter, while buffers at pH 10 or 4 are used to set the slope. If no
commercially available solutionsare at hand, the buffers can be prepared from base standards
W].
Buffer systems for other pH values are given in the Handbook of Chemistry and Physics
W].
The ORP measuring system canbe calibrated using a buffer solution saturated with quin-
hydrone. Quinhydrone decomposes in aqueous solution intoan equimolecular mixtureof hyd-
roquinone and quinone, which in turn impose a fixed potential on the platinum electrode. The
Removal of Chromate, Metals
Cyanide,
Heavyand 545
potential of the quinhydrone is pH-dependent. If a calomel electrode is used as a reference elec-

trode, the following potential difference results:
AE (Wcalomel in saturated quinhydrone) = 699.7 (mV) - 241.2 (mV)
- 59.2 (mV) X pH (28)
For a buffer of pH 4.00 saturated with quinhydrone, a potential difference of 222 mV results.
The potential of a saturated silver electrode is 45.5 mV less than the potential of a satu-
ratedcalomel electrode. Thepotential of a WAglAgClchainin saturated quinhydroneis
therefore
AE(WAglAgC1 in saturated quinhydrone) = 699.7 (mV) - 195.7(mV)
- 59.2 (mV) X pH (29)
For quinhydrone dissolved in a buffer of pH 4.00, a potential difference of 267 mV results.
The ORP measuring devices (ORP controllers) normally requirean intercept and a slope
for calibration. The intercept is set by shorting the electrode input terminals (AE = 0). The
slope is set usingthe known potentialof the Pt/Ag/AgCl or Pt/Hg/Hg,CI2 chain in pH 4 buffer
saturated with quinhydrone. Quinhydrone is very insoluble in water; only 50-100 mg need be
added to 250-500 mL of the buffer solution.
The pH and ORP curves necessary for process control are determined during bench-scale
testing in the laboratory. Figure 3 gives the ORP curve for a sodium cyanide-based solution
titrated with sodium hypochlorite solution. In the example shown, the equivalence point is
reached at 100-200 mV. For the purposes of process control, the amount of NaCIO) added for
cyanide oxidation is therefore sufficient if the potential in the reactor is in the 250-350 mV
range.
Figure 4 shows the ORP curve for a 100 ppm Cr"' solution titrated with FeSO, reagent at
pH 9.5. The equivalence point is reached at -200 mV. The amount of iron (11) added is suf-
ficient for chromate reduction if the potential is slightly more negative than -200 mV.
Chemical addition control usingelectrodes is feasible for both batch and continuous sys-
tems once the ORP curve is established. The oxidation reduction potential is often dependent
on pH. In this case, simultaneous control of the pH is necessary. ORP curves for chromate
reduction with sulfite are established in this manner. These curves are strongly pH-dependent;
therefore close pH control is necessary. The pH range of 2-3 is normally chosen, becausethe
SO2 backpressure gets too high below pH 2 and the reaction rate is not fast enough above
pH 3.
IV. DOSAGE OF CHEMICALS USING PROPORTIONAL FEED PUMPS

The slopes of the ORP curves shown in Figures 3 and 4 are steepest at the equivalence point.
This creates the potential of overdosing the amount of reactant, which is alleviated by the use
of a proportional addition system.For this purpose a millivolt-to-frequency converter is added
to the ORP controller.This converter is interfaced with the chemical feed pump and controls the
pump stroke frequency linearly betweenlow and high setpoints as indicated in Figure 5. In this
fashion, the chemical feed rate increases linearly with an increase in the ORP deviation from
the ORP set point. The feed rate (pump stroke frequency) slows downas the ORP approaches
the desired ORP set point. The dosage of the chemicals with proportional feed pumps is es-
pecially useful ifthe pollutant concentrations vary in the feed streams.The pH adjustments are
achieved in the same way. In addition, ORP and pH controllers can activate relays at low and
high alarm set points. In this fashion, visual or acoustical alarms can be activated and feed
pumps can be shut off.
Electrode
Potential
[mVI joO1 EquivalencePoint
t
4001
""""""""""""""""""""""""-.
I 1 - 1
0 2 4 146 8
12 10
HypochloriteSolution [ml]
Figure 3 Oxidation-reduction potential (ORP) of a KCN solution. 100 ppm of CN- titrated with hy-
pochlorite reagent. Electrodes: Pt/saturated calomel.
V. PROCESS PERFORMANCE IN INDUSTRY

The State of California Departmentof Health Services collected performancedata on treatment
of aqueous wastes. The findings were published in 1988 [7].Table 4 summarizes a portion of
the performance data established in this study for Cd, Cr, Cu, Pb, Ni, and Zn. Unfortunately,
the pH operating ranges are not well defined in the report.
VI. AUTOMATED PROCESS FOR REMOVAL OF CYANIDE, CHROMATE,

AND METAL MIXTURES
In this section, the chemistry andcontrol principles described inthe previous sections will be
used for effluent pretreatmentin a custom plating shop.Very complex situations were encoun-
Potential
[mVI
'"1 EquivalencePoint
Iron SulfateTitrant
[m11
Figure 4 Oxidation-reductionpotential (OW) of a K,CrO, solutiontitrated with FeSO,reagent.

Electrodes: Wsaturated calomel.
tered here, since these shops perform a multitude

of plating, cleaning, and stripping operations.
A control system had to be installed to meet effluent guidelines that were site-specific.
A. Problem Definition
Table 5 shows the bath types and chemicals used in the custom plating shop. The effluent
concentrations vary because some baths are used intermittently. The following ranges were es-
tablished through effluent monitoring: Cr"', 1-4 ppm; Ni, 7.5-107 ppm; Cu, 1.5-9 ppm; Zn,
1.4-19 ppm; CN-, 1.9-18 ppm. In addition, small amounts of Cd, Pb, Mn, and Se were found
to be present. The amounts of Au dragged out from the gold bath as well as the Ag and Sb from
the silver bath were small since the precious metal baths
are used sparingly. The streams listed
in Table 5 can be grouped into four categories:
Pump
Stroke
Freqjsnq
100% '
1 1
Low Alarm High Alarm
Electrode
0 I I Potential
t t
-100 0 100
[mvl
*0° 300 400

Low Set High Set
Figure 5 Chemicaldosage by proportionaladditionusing an O W controller and amillivolt-

to-frequency converter in combination with a proportional feed pump. The set points for hypochlorite
addition to KCN solution are shown.
Cyanide streams containing Cu, Zn, Ni

Chromate streams containingCr"'
Metal streams containing Zn, Ni, Se
Other: containing Pb, Sn, Fe, Cu, Zn, Ni
After elimination of the cyanide-based Ni-stripping operation, CuandZn are the primary
heavy metals in the cyanide stream. Cyanide can be destroyed at pH 2 11. Cu(OH)*and
Zn(OH), require a precipitation pH range of 10-1 1.
The conventional procedure for Cr"' removal using sulfite operates at pH 2-3 in the re-
duction tank and at pH 8.5 in the C I ~ O Hprecipitation
)~ reactor.
The last two streams containPb, Zn, Sn, Cu, and Ni, with optimum hydroxide precipita-
tion pH ranging from 8.5 (Pb) to 11 (Ni).
An additionalcomplication arises when chlorine is used to treatcyanide-containing
streams. Excess chlorine used in the cyanide oxidationstep must be destroyed before discharge.
The pH of the discharge stream must lie within a pH range of 6-10.
Conventional pretreatment technology for treating copper cyanide, chromium (VI), and
nickel wastewater streams requires the system arrangement shown in Figure 6. In the situation
at hand, a fourth treatment line mayhavetobe installed to treat the lead-, zinc-, and tin-
containing streams,which require a lower pH environment than nickel forquantitative precip-
itation of metal hydroxides. The expense of a continuous systemwould be excessive dueto the
multiple reactors, clarifiers, and controls. Batch treatment would be complex and very labor-
intensive.
A great simplification can be achieved if the treatment scheme shownin Figure 7 is im-
plemented. The cyanides are destroyed in reactor 1. The effluent of the cyanide reactor isfed
together with the chromate and generalrinse into reactor 2, which operates at pH 9-10. Here
chromate and excess chlorine from reactor 1 are reduced with Fe", and all metals are copre-
cipitated with Fe"' generated in the reduction of Cr"' and hypochlorite.The effluent from re-
actor 2 can then be further processed in the conventional way.
Removal of Chromate,Metals
Cyanide,
Heavyand S49
Table 4 Process Performance Data for the Control of Cd, Cr, Cu, Pb, Ni, and Zn
Average
Metal Process treatment (mg/L)
Hydroxide precipitation
NaOH
mfg.
battery
Cadmium
Lead 0.055
battery
NaOH
Lead
mfg. 0.08
Zinc
battery
mfg.
Lime
precip. 0.067
Lime
finishing
Metal 0.02
gMetal Copper 2.63
Commercial
precip.
Lime
TSD 0.58
eryLead Lead 0.11
components
Electr.
NaOH 0.14
H
ponents
Electr.Nickel 0.52
Lime
Commercial
TSD 1.8
Lime mfg. Battery 0.5
D
ommercial
Zinc 1.05
Hydroxide precipitationin the presence ofof FelAlum
Cadmium
finishing
Metal FeCI, + base 0.07
Metal finishing FeSO, + base 0.579
Lead battery mfg. Ferrite coprecip. 0.008
components
Electr.
Copper NaOH + FeSO, 0.17
Electr. components NaOH + FeSO, 0.59
Metal finishing FeSO, + hydroxide 0.505
Commercial TSD NaOH + FeCI, 1.2
Commercial
TSD Lead NaOH + FeCI, 0.07
Lead battery mfg. Ferrite coprecip. 0.01
components
Electr.
Nickel NaOH + FeSO, 0.165
Electr. components NaOH + FeSO, 0.63
Commercial TSD NaOH + FeCI, 1.1
Battery mfg. Ferrite coprecip. 0.2
ng
Metal Zinc FeSO, + hydroxide 0.005
Commercial TSD NaOH + AI coprec. 4.1
Surfide precipitation
Cadmium
Copper
smelter N%S + lime 0.01
Commercial TSD Lime + sulfide 0.5
Army report Na,S + FeSO, coprec. 0.06
Commercial
Copper
TSD Lime + sulfide 0.15
EPA test run Sulfide + ion exchange 2.3
Commercial
TSD Lead Lime + sulfide 0.01
Copper smelter Na,S + lime 0.05;0.2
EPA test run FeS + ion exchange 0.5
Commercial
TSD
Nickel Lime + sulfide 0.34
EPA test run Sulfide precip. + ion exchange 13.4
ng
Metal Zinc FeS + ion exchange 0.5
Foundry Sulfide precip. 0.88
550
Manis and Schwitzgebel
Table 4 Continued
Chromium treatment
Average treatment (mg/L)
Process Plant
Metal finishing Reduct. precip. 2.14
Metal finishing Reduct. precip. 2.36
Commercial TSD NaHSO, reduct.
0.12 0.1
Commercial TSD NaHSO, reduct. 0.63
Lead battery FeS precip. 0.014 0.04
Lead battery Na,S precip. 0.005 0.005
Source: Data from Ref. 7.
Table 5 Bath Types in Custom Plating Shop, Estimated Dragout and Bath Composition
azardous
edients
(gallday)
Dragouttype Bath
Aluminum
cleaner 114 Sodium tetraborate
pentahydrate,
zinc
sulfate,
sodium
nitrate,
tetrasodium pyrophosphate
Steel cleaner 1l2 Sodiumcarbonate,tetrasodiumpyrophosphate,sodium hy-
droxide, ethtoxylated amphoteric sodium salt, sodium meta-
silicate
Mild acid 112 Sodium bisulfate, sodium fluoride, sodium chloride
Die cast boil 118 Not given
Nickel strike 118 Nickel sulfate solution
Copper solution 114 Copper cyanide, potassium hydroxide, sodium cyanide, zinc
cyanide, sodium hydroxide, thallium carbonate
Chrome solution 1 Chromic acid, magnesium silica fluoride, sulfuric acid.
Nitric acid 114 Nitric acid
Zincate 114 Sodium hydroxide, zinc oxide
Nickel solution 3.0 Nickel carbonate, nickel chloride, nickel sulfate, sulfuric acid,
boric acid, saccharin (Besniflec 812)
Gold
solution 1110 Potassium
cyanoaurate,
cobalt
complex,
nickel
complex, po-
tassium citrate
Brass solution 114 Copper cyanide,
zinc
oxide,sodiumcyanide
Silver strike 1/10 Sodium cyanide,
potassium cyanide,
silver
cyanide
Silver solution 114 Potassiumcyanide,sodiumcyanide,silvercyanide,potassium
antimonyl tartrate
Antiquing 114 Selenous
cupric
acid,
sulfate,
phosphoric
sulfate,
zinc
acid,
ammonium molybdate
Antiquing 114 Cupric
sulfate,
selenous
acid
nitric
acid,
Cleaner 114 Sodium
hydroxide,
sodium
metasilicate
pentahydrate,
sodium
carbonate, tetrasodium pyrophosphate
stripping
Paint 112 Sodium
hydroxide,
phenyl
diethanolamine,
sodium
meta-
silicate
stripping
Silver 114 cyanide
Sodium
stripping
Nickel 112 acid
Sulfuric
Nickel
stripping 112 Sodium
cyanide,
sodium
hydroxide
Hydrochloric
acid 112 Hydrochloric
acid 50%
corrm OXlDAllON
CYANIDE e And EXCESS
PREclPrrAnoN
p11 11.5
SWWE
HOLDINQ
CHROMAT6
NICE e PRECIPITATION
pH 11.2
Figure 6 Conventionalpretreatmentsystemarrangement for treatingwastewatercontainingcopper

cyanide, chromate, and nickel.
CHROMATE
AND
GENERAL
RINSE
7
CHROMATE
CYANIDE REDUCTION
CYANIDE- DESTRUCTION AND -+ ClARlFlER "I-IARGE
METAL
pH 11.5 PRECIPITATION
pH 9.5 to 10
Figure 7 'bo-step system arrangement for treatment of cyanide, chromate, and heavy metals. chro-
mate is reduced by Fe". and all metals are coprecipitated with Fe"' at pH 9.5-10 in one reactor.
Table 6 SyntheticStreamComposition (mg/L)

Noncyanide Cyanide
Inorganic
(pH 11.7). stream 1 (pH 2.7). stream 2
~~ ~~~ ~~~~
Copper 90 1.4
Nickel 8.6 99
Zinc 14 5.9
Silver 22 -
Chromium - 67
Cyanide 250 -
Selenium 0.02 0.22
Cadmium - 0.087
Lead - 0.18
Manganese - 0.05
-
Gold 0.87
B. Process Implementation
The cyanide streams contained nickel stemming from the nickel stripping operation. Since
Ni(CN)42- cannot be destroyed throughchlorination, this bath was substituted by a bath con-
taining noncyanide chemicals. The feasibility of the process arrangement shown in Figure 7 had
to be tested in the laboratory. Flow rates and stream compositionswere needed. Theflow rates
were estimated from the individual rinse water streams to be approximately 5 gal/min for the
cyanide-containing streams and 15-20 galhin for the remaining streams (general rinse). The
cyanide-based baths were operated intermittently whereas the chromium and nickel lines were
in continuous use.
The concentrations expected in the cyanide and general rinse streams after stream segre-
gation were estimated from the bath dragout rates. A dilution of 1:250 to 1 :loo0 is expected
in the rinse tanks.With these data, a synthetic cyanideand synthetic general rinse effluent was
composited from bathconcentrates, which were mixed in the sameratios as the estimated bath
dragout rates. The resulting composite was finally diluted 1:250 to obtain simulated cyanide
and general rinse effluent streams. These synthetic effluents contained all the chemicals, ad-
ditives, and brighteners used in the process in their approximate ratios and concentrations and
were used in bench-scale testing to prove system feasibility. Analysesof these composites are
shown in Table 6 .
The cyanide was treated for cyanide destruction using hypochlorite at pH values greater
than 11. The hypochlorite addition was monitored through measurement of the redox potential.
The cyanide concentration decreased from 250 ppm to <0.02 ppm in this step.
Following cyanide destruction, the treated cyanide streamwas combined with the general
rinse streamsin a ratio of 1:4 to simulate the reactor 2 influent. This solution was treated with
FeS04 reagent at pH 10. The metal concentrations before and after the bench-scale treatment
are summarized in Table 7. The discharge limitsare also shown for comparison. The treatment
strategy results in an effluent quality well below the discharge standards.
The data obtained in the bench-scale study were used to build a fully automated systemas
shown in Figure 8. It incorporates the following features.
1. The cyanide stream is collected in a holding tank and is uniformly fed to the cyanide de-
struction reactor.
Table 7 TreatmentEfficiency and DischargeStandards (mglL)

Tteated effluent Discharge
standards
Inorganics
Reactor influent (pH 10) (pH5.5-10.5)
Copper 18 0.20 2.02
Nickel 82 0.12 2.33
Zinc 7.4 0.02 l .45
Silver 4.1 0.03 0.24
Chromium 55 C0.05 1.67
Selenium 0.18 <0.008 0.02
Cyanide <0.02 <0.02 0.64
Arsenic - - 0.70
Cadmium 0.07 <0.009 0.07
Lead 0.15 <O.W 0.42
Manganese 0.04 <0.016 1. 0 0
Gold 0.16 0.17 NA
~~
NA = not available.
2. This reactor is well stirred. The pH and the ORP are continuously monitoredby electrodes.
NaOH and hypochlorite are automatically fed into the reactor to maintain preset pH and
ORP values determined duringthe bench-scale phase of the program.
3. The effluent of the cyanide reactor is fed by gravity feed into the main reactor.
4. The daily rinse is collected in a holding tank and is uniformly fed into the main reactor.
This vessel is well stirred. The pH and the redox potentials are monitored by electrodes.
FeSO, reagent and sodium hydroxide are automatically metered into the reactorto main-
tain preset ORP and pH values. This allows for chromium reduction andheavy metal pre-
cipitation in one reactor and at one pH:
Chromium reduction:
Cr6' + 3 Fe2' + C?+ + 3 Fe3+
Metals precipitation:
C?' + 3 OH- + Cr(OH)3
Fe3+ + 3 OH- + Fe(OH)3
CU" + 2 OH- + CU(OH)~
Ni2+ + 2 OH- + Ni(OH)2
Cd2+ + 2 OH- "* Cd(OH)2
Pb2+ + 2 OH- + Pb(OH)2
Zn2+ + 2 OH- -+ Zn(OH),
5 . Precipitated metal hydroxides usually form fine particles, which settle slowly. Addition of
a polymer achieves agglomeration of the precipitate, greatly improving the solid-liquid
separation in a gravity clarifier.
6. The main reactor effluent solution is transferred to a lamella clarifier with built-in floc-
culator. The flocculator provides gentle, shear-free mixing for about 3 min of retention
E1echodes
&
Feed Tank
Level
Sulfate
Conmllers Control Panel
Filter Press
9r;( I II I I
I Cyanide
Collection
1I Rinse
collectioo
,II I Hydroxide Sludge
-.
7 Sludge Tank Overflow Return

1
Figure 8 Flow schematic of a two-step system for cyanide oxidation, chromate reduction, and metals precipitation.
Removal of Chromate, Cyanide, and
Metals
Heavy 555
Table 8 SystemPerformance,Values in mglL

osite 24-hr samples Grab
startup period monitoring
compliance
Parameter
8/26/90 8/27/90
8/30/90
8/31/90
9/1/90
10/9/90
12/3/90
2/25/91
4/2/91
As co.01
co.01
co.01 - - C0.005 c0.005 C0.005 C0.005
C0.7-C0.7 C0.7
Ba - - 0.02 <0.02 c0.02 c0.02
Cd co.01
co.01
co.01 - - co.01
co.01 co.01 co.01
Cr C0.06
C0.06
C0.06 - - c0.02 c0.02 c0.02 c0.02
cu 0.40
0.03 0.03 - - 0.17 0.12 0.07 0.05
Pb C0.06
C0.06 -50.06 - - co.10
co.10
co.10 0.190
Mn co.04 CO.04 co.04 - - co.02 c0.02 c0.02 c0.02
Hg c0.02
c0.02
c0.02 - - co.001
co.001 <0.001 co.001
Ni co.04 co.04 co.04 - - 0.200.14 0.13 CO.10
Se <0.008 CO.008 CO.008 - - 0.005 C0.005 CO.005 C0.005
Ag c0.02 c0.02 c0.02 - - c0.02 0.02 c0.02 c0.02
Zn 0.06 CO.01 cO.01 0.12
- -
0.10 0.14 0.11
Fe 0.4 0.2 0.3 - - - - - -
CN 0.30 0.04 C0.02 0.04 0.06 - - 0.08 c0.02
COD - - - - - 43 19 28 16
time, allowing the particlesto grow. The clarifier overflow is discharged to a holding tank.
A final filtration step can be added if needed.
7. The sludge collected in the clarifier is discharged from the bottom via a diaphragm pump
for which the frequency and duration of operation can be adjusted by a timer located on the
central control panel. Sludge from the clarifier is collected in the sludge holding tank,
from which it is pumped to the filter press. A level indicator will alert operators if the
sludge exceeds a preset level.
8 . Sludge that has been separated and prethickened by the clarifier is further thickened to
25-35% solids using a filter press equipped with gasketed, recessed polypropylene filter
plates and a high pressure feed pump. Thickened sludge is collected in a self-dumping
sludge hopper or in 55-gal drums.
9. A final pH adjustment is not necessary, since the system is operatedpHat 9.5-10, a which
is well within the discharge limits of 5.5-10.5.
C. System Performance
The system described was started up during Julyand August of 1990. Table 8 summarizes the
system performance during thestartup period as well as the monitoring results established us-
ing 24-hr composites.
SYMBOLS
akw Fe3+
ion
Activity
theof
a,+" Activity ofFe2+
ion
the
CH + Concentration of the hydrogen
ion H+
Concentration
hydroxyl
the
of ion OH-
CM:+
cOH-
Concentration
theof Me2+ ion
Schwitzgebel and Manis
Concentration of the sulfide ion S''

Normal potential
Potential
Faraday constant
Dissociation constant
Solubility product
Solubility product of Me(OH),
Ion product of water
Metal
Oxidation reduction potential
Gas constant
Absolute temperature, "K
REFERENCES
1. EPA, Environmental Regulations and Technology, The Electroplating Industry, EPA 625/10-80-001
(1980).
2. EPA, Control and Treatment Technology for the Metal Finishing Industry, In-Plant Changes, EPA
62518-82-008 (1982).
3. EPA, Environmental Pollution Control Alternatives: Economics of Wastewater Treatment, Alter-
natives for the Electroplating Industry, EPA 625/5-79-016 (1979).
4. EPA, Control and Treatment Technology for the Metal Finishing Industry, Sulfide Precipitation,
EPA 625/8-80-003 (1980).
5. EPA, Control and Treatment for the Metal Finishing Industry, Ion Exchange, EPA 625/8-81-007.
6. EPA, Environmental Pollution Control Alternatives: Centralized Waste Treatment Alternatives for
the Electroplating Industry, EPA 6235-81-017 (1981).
7. Lee. B., Staff Report on Proposed Treatment Standards for Metal-Containing Aqueous Wastes, Fi-
nal Draft, State of California, Department of Health Services, Sacramento, Sept. 8, 1988.
8. Schwitzgebel, K., Integrated process for cyanide and heavy metal removal from plating process
waste streams, U.S. Patent 5,106,508 (1992).
9. Entwistle, J. E., The electrolytic processingof cyanide wastes,Efluent Water TreatmentJ . , March
1976.
10. Brown,T. L., andLeMay, H. E., Chemistry: TheCentralScience, Prentice-Hall,Englewood
Cliffs, N.J., 1977, p. 51 1.
11. Blackmer, G. L.,Analytical Chemical Methods, Texas Tech Univ. Press, 1980, p. 245.
12. Handbook ofchemistry and Physics, Weast. R. C., (ed.). 59th e d . , CRC Press, 1978-79.
13. U.S. EPA, Treatability Manual,Vol. 2, Technologiesfor ControllRemovalof Pollutants, EPA-600-,
2-82-001c, U.S. Environmental Protection Agency, Washington, D.C., 1981.
14. Grosse. D., A review of alternative treatment processes for metal-bearing hazardous waste streams,
JAPCA, 36(5), 603-614 (1986).
15. Jander, G., and Blasius, E., Lehrbuch der analytischen and prc7parativen anorganischen Chemie,
S. Hirzel Verlag. Stuttgart, 1988.
26
Neutralization Tactics for Acidic
Industrial Wastewater
Christopher A. Hazen and James I. Myers

Miles Inc.
New Martinsville, West Virginia
1. INTRODUCTION
This chapter was written to provide insight into the background and tactics surrounding the
neutralization of acidic industrial wastewater. Several major topicsare covered, including pH
measurement, lime and caustic use,and design considerations when using either of these two
chemicals alone or in a two-stage neutralization technique. This chapter is meant only as a
guide to neutralization tactics; more detailed technical information can be obtained in the ref-
erences listed at the end of the chapter.
II. pH MEASUREMENT
pH is a unit of measure that describes the degree oforacidity
alkalinity of a solution.The origin
of the terminology comes from the letterp , meaning power, and the letter H symbolizing hy-
drogen [l].
Formally defined, pH is the negative logarithm of the hydrogen ion activity:
pH = -loglo[H+]
Since pH is a logarithmic function, a change of one pH unit represents a tenfold change in

hydrogen ion concentration. Figure 1 includes a table correlating pH to the hydrogen ion and
hydroxyl ion concentrations, [H+] and [OH-].
The control and measurement of pH are necessary in a variety of chemical processes. In
acidic industrial wastewaters it is necessaryto maintain pH within the range6-8 to effectively
meet state and/or federal permit conditions.
A rough indication of pH can be obtained using pH papers or indicators, which change
color as the pH level varies. These indicators have limited accuracy and can be difficult to
interpret correctly in colored or murky samples.
557
Hazen and Myers
Acid Neutral Base

pH Range 0 “- ”_ ””_ -> 7 ”””””“
> 14
pH = -Log of Concentration of H+
pH of 1 = -Log(. 1)
pH H+Conc. OH- Conc.

1.0000E-14
1 0.1
2 0.01 1.0000E-13
3 0.001 1.0000E-12
4 o.Ooo1 1.0000E-l1
5 o.oooo1 1.0000E-10
6 0.000001 0.00000000
7 0.0000001 0.00000001
8 0.00000001 0.0000001
9 0.00000000 0.000001
10 1.0000E-10 o.oooo1
11 1.0000E-11 o.Ooo1
12 1.MxHIE-12 0.001
13 1.oooOE-13 0.01
14 1.oooOE- 14 0.1
Figure 1 Understanding pH.
More accurate pH measurements are obtained with a pH measuring system. The basic pH
measuring system consists of three parts: a glass electrode, a reference electrode, and a high
input impedance pH meter.
The glass electrode is a hydrogen-ion-sensitive glass bolb with a millivolt output thatvaries
with the changes in the relative hydrogen ionconcentrationinside and outsidethe bulb. The milli-
volt output is developed as a result of differences betweenthe hydrogen ion activity in the sam-
ple and that in the standard solution contained within the electrode. This potential, measured
relative to the potential of the reference electrode, gives a voltage that is expressed as pH [2].
As stated before, the glasselectrode alone is not sufficient to measure the potentialof the
liquid system. A reference electrode is needed to complete the measuring circuit. The reference
electrode provides a stable potential by surrounding an internal elementwith a known solution.
The reference electrode has three principal parts:an internal element, a filling solution, and a
permeable junction through which the filling solution escapes from the electrode. The liquid
junction can take several forms, but its principal function is to allow small quantities of the
reference electrode’s filling solution to slowly leak or migrate intothe sample being measured.
Reference electrodes are available in a variety of types to accommodate many different types
of samples.
The third componentof the pH measuring systemis the pH meter. The glasselectrode bulb
has a high resistance acrossit of about 100 megohms. This fact prevents the use ofan ordinary
voltmeter for reading out the electrode potentials. A meter that has a high input impedance or
low bias current is required [l].
It is important, when trying to maintain proper functionof the pH measuring system, that
the electrode and the samplebe in intimate contact and thatthere be no surface contamination
to provide a barrier between the ions in solution and the surface of the glass [2].
Tactics
Neutralization Wastewater
for Acidic 559
Devices usedto measure pH are generally rugged and built to withstand very adverse con-
ditions. Several electrode systems and highly reliable electronic circuits havebeen developed
for pH measurement and control. Among these devices and techniques are specific-ion elec-
trodes, coulometric analysis, and polargraphic analysis [3].
The accuracy of a pH measurement depends to a large extent on bias, span, and nonlin-
earity errors from a varietyof sources. Even under the best industrial conditions, pH electrode
potential measurements are only accurate to within k0.017 pH. At pH 13 this is an error of
approximately 20.13%. Common sourcesof error in a pHmeasuring systemare broken bulbs,
fill contamination, bulb abrasion, bulb dehydration, and coating of the bulb [4].
Periodic maintenance of glass electrodes is normally requiredto keep the glass membrane
free of pluggage and prevent coating with the alkali. To obtain accurate pH measurements, a
regular schedule must be establishedto clean the pH probes and calibrate the devices.
111. LIME: TYPES, USES, COMPOSITION, AND TREATMENT

Acidicindustrialwastewatercan be neutralizedwithslakedlime[Ca(OH),],causticsoda
(NaOH), or soda ash (Na2C03). Since slaked lime is less expensive than other bases, it is the
most commonly used chemical for acidic neutralization [5].
W Otypes of commercial lime with their associated hydrates are high calcium quicklime,
otherwise known as calcium oxide (CaO), and dolomitic quicklime (CaO MgO). and The com-
position of these will depend on the source of the parent limestone and the method of lime
production, particularly the type of fuel used to convert the limestone to quicklime [6].
A high calcium quicklime will produce a high calcium hydrated lime containing 72-74%
calcium oxide and 23-24% water in chemical combination with calcium oxide. A dolomitic
quicklime will produce a dolomitic hydrate. Under normal hydrating conditions the calcium
oxide fraction of the dolomitic quicklime completely hydrates, but generally only a small por-
tion of the magnesium oxide hydrates. The compositionof a normal dolomitic hydrate will be
46-48% calcium oxide, 33-34% magnesium oxide, and 15-17% water in chemical combina-
tion with the calcium oxide.
npical compositions of commercially available lime are given in Tables 1 and 2. Note the
differences between the compositionsof high calcium hydrated lime and pebble quicklime.
Slaked lime, commonly known as hydrated lime, is obtained by adding enough water to
quicklime to satisfy its affinity for water. Wettingor dissolving tanks are usually designed for
5 min of detention time with 0.5 lb/gal (0.06 kg/L) of water or 6% slurry at the highest feed
rate. Hydrated lime is often used where the maximum feed rates are less than 250 lb/hr (113.3
kg/hr) [7].
A general reaction of hydrated lime with acidic wastewater is
Ca (OH)2 + acid S salt + H20
A common system for the storage, transfer, and reaction of hydrated lime is diagramed in
Figure 2. Hydrated lime is loaded into a storage silo and metered out using a lime screw/auger,
rotary valve, or other metering device. The lime is then transferred by either a lime auger or
pneumatic line to themix tank. The mix tank or other device should provide the retention time
necessary for complete reaction of the lime. Neutralization is not instantaneous, and contact
time mustbe provided, usually not to exceed 5 min, depending on the wastewater composition.
It should also be noted that it is very difficult to hold pH values between 6 and 8, since
slight changes in lime feed causes wide swings in pH as neutrality is approached [8].
In one industrial wastewater treatment center the lime storage was silo used for limestone,
and a pneumatic transfer system was used to transfer the lime from the silo
to a mix tank. When
560 Hazen and Myers
Table 1 High-CalciumHydratedLimeAnalysis
results testanalysis
Chemical
Total calcium oxide, CaO 72.5
Available calcium oxide, CaO 70.6
Calcium hydroxide, Ca(OH), 95.8
Magnesium oxide, MgO l .02
Silicon dioxide, SiO, 1.5
Total sulfur, S 0.01
Iron oxide, Fe,O, 0.33
Aluminum oxide, AI,O, 0.37
Free moisture 0.97
Physical analysis test results
% Passing 100 mesh screen 99.5
Bulk density
Loose 27 PFC
Settled 40 PFC
Table 2 PebbleQuicklimeChemicalAnalysis-
Test Results (%)
CaO Total, 98.8
Available
calcium
oxide,
CaO 93.7
MgOMagnesium
oxide, 1.9
Si Silicon, 1.36
AI,O,oxide,
Aluminum 0.64
oxide, Iron Fe,O, 0.34
sulfur, Total S 0.035
Zinc, 0.013
r
l Ume Sllo
U
Figure 2 Schematic diagram of lime transfer and use.
Tactics
for Acidic 561
the change was made to hydrated limeit quickly became apparent that the “dusty” nature of
the hydrated lime made it very difficultto handle with the off-gas collection system. At the exit
from mix tank was awet scrubber, meantto scrub out any chlorine that may have been released
during the neutralization process andto knock out any dust particles entrained in the air. This
scrubber was overwhelmed by the magnitudeof dust particles and could not effectively remove
them from the air. The change was then made to a lime auger, which eliminated the majority
of the “dusting” problems while still providing effective transfer.
Also particular to this system is themix tank. This mix tank is operated as a slurry tank
for the hydrated lime. Lime introduced to this tankis combined with water exiting the scrubber,
and the mixture is gravity fed to a process trench. The process trench and subsequent basins
provide adequate retention time for complete reaction of the lime. Itbeshould noted thatat this
time the neutralization requirements are not completely satisfiedby hydrated lime. A two-stage
neutralization system is used. This type of system uses limeto raise the pH initially and finish
the neutralization process using caustic soda (NaOH). This process is detailedin Section V.
W. CAUSTIC SODA: TYPES, USES, COMPOSITION, AND TREATMENT

Causticsoda,otherwise known as sodiumhydroxide(NaOH),isanothercommonwaste-
50% sodium hydroxide
water neutralizing agent. Its most popular form is a solution containing
by weight.
A.ManufacturingMethods
Several well-known processes by which caustic soda is produced are those employing a dia-
phragm cell, bipolar diaphragm electrolyzers, mercury cell, or membrane cell.
In the diaphragm cell process, water is added to sodium chloride with direct current to
produce chlorine, hydrogen, and sodium hydroxide. The overall reaction is
2 NaCl + 2 H20 + direct current + Cl2 + H2 + 2 NaOH

An asbestos diaphragm is used to separate the anodeand cathode; this serves to keep the
caustic soda and hydrogen separated from the analyte as well as to control the flow of elec-
trolyte to the cathode. This situation allows for the most efficient formation of caustic soda
and chlorine.
Bipolar diaphragm electrolysis is similar to the diaphragm cell process but employs a
number of bipolar diaphragm cells in a series circuit of electrolyzers. This design permits cur-
rent to flow internally within an electrolyzer from one cell to another. Major benefits from this
type of design are a higher current efficiency, lower power consumption, and decreasedfloor
space requirements.
The mercury cell process involves two stages or two cells. In the first stage, sodium and
chlorine are releasedby the electrolysisof brine. The sodium dissolves in the mercury cathode,
forming an amalgam, while the chlorine is drawn off. In the second stage this amalgam reacts
with water to form sodium hydroxide and release hydrogen. The main reactions are
1ststage: 2 NaCl + H& + directcurrent 2 Na + H& + Cl2

2nd stage: Na (Hg), + 2H20 + direct current + 2 NaOH + H2 + 2 (Hg),
This type of reaction can occur in several different types of designs, most often in a hor-
izontal or vertical arrangement.
562 Hazen and Myers
Table 3 PhysicalDatafor100%SodiumHydroxide(NaOH)
Property
Molecular weight 40.01 Holtzclaw [101
Boiling point at 760 mm Hg 1390°C ~ e r r y[31
Melting point 318.4"C P ~ W[31
Specific gravity at 20°C 2.13 Perry 131
Solubility in Water at 0°C 42 g/100 mL Perry P I
Solubility in water at 100°C 347 @l00 mL perry [31
Heat of formation at 25°C 101.96 kg callmol Perry [3]
Latent heat of fusion at 320°C 42.5 callg h g e [l11
And finally, the membrane cell process is verysimilar to the diaphragm cell process except
that it involves the use of an ion-exchange membrane in place of the asbestos diaphragmused
in a diaphragm cell, and nickel instead of steel for the construction of the cathode compart-
ment. This system is used with both monopolar and dipolar arrangements and can produce a
higher strength, higher purity caustic [9].
B. Selection
Factors thatenter into the selection of the most economical grade and formof caustic soda for
a particular application, in addition to purchase price, are the cost of transportation, unloading,
handling within the plant, preparing caustic soda for use, and the investment in equipment for
unloading, storage, handling, and preparation of the solution [9].
Tables 3 and 4 list the general properties of 100% sodium hydroxide and a 50% solution
of sodium hydroxide.
Other factorsare the safety and handlingaspects of caustic soda. Caustic sodais poisonous
and can be dangerous if handled improperly. To avoid accidental spills, all pumps, valves, and
lines shouldbe checked regularly for leaks. Operators should be properly instructedin the pre-
cautions needed for the safe handling .of this chemical. Emergency eyewashes and showers
should be provided close to the caustic soda storage and feed area to protect personnel fromthe
harmful effects of accidental spills [7].
Table 4 Physical Data for 50% Sodium Hydroxide, 50% Water

Property
Molecular weight
NaOH 40 [IO] Holtzclaw
18 H*O [IO]
Boiling point at 760 mm Hg 288°F PmPI
Melting point 12-15°C MSDS [l31
Specific gravity at 20°C 1S253 P11
Solubility in water at 0°C 42 g1100 mL err^ [31
Solubility in water at 100°C 347 gll00 mL Perry [3]
Heat of formation at 25°C 101.96 kg caVmol Perry [3]
Average molecular wt. 29 Calculated
Viscosity at 40°C 22.1 CP P m 191
Viscosity at 70°C 7.1 CP pm [91
Specific heat of 120°F Solution 0.775 Btu (Ib-"F) Calculated
Tactics
for Acidic 563
Caution must also be exercisedin selecting materials of construction for the caustic soda
storage and handling equipment. Iron and steel are the usual choice for equipment handling
50% solutions of caustic sodabelow 140°F. The most popular choice for storage tank construc-
tion is mild steel because of its lower cost and adequate performance under most conditions.
Certain metals, e.g., aluminum, magnesium, zinc, and tin, are attacked by caustic soda. In
addition, silica-containing materials suchas glass, brick, and tiles are broken down by caustic
liquor. The action is slow and willat first only contaminate the caustic with silica, but failure
of the material will eventually follow [9].
V. DUAL NEUTRALIZATION: A TWO-STEP APPROACH TO

NEUTRALIZING WASTEWATER
A. Background
Because of the downturn of the economy during 1991, the Environmental Control Department
(ECD) at Miles Inc. began looking for ways to reduce variable costs within its department [12].
Utilizing a breakdown of departmental costs, the .variable expenses attributed to the neutral-
ization of wastewater were identified as an area of major concern (Figure 3).
This wastewater, which has an average pH less than 2, must be treated to meet discharge
standards as set by the West VirginiaDepartmentofNaturalResources(WVDNR). The
WVDNR issues permits that regulate wastewater discharges and require constant monitoring of
the plant effluent pH. Adjusting the wastewater to pH 7 would be similar to raising the pH of
vinegar (acidic) to that of tap water (neutral).
Consider the historyof wastewater neutralizationat this site. In the 1970s and early 1980s,
lime was used as the primary neutralizing agent for wastewater. However, lime loses its effi-
ciency as a neutralizing agentas the pH approaches 7 , and any excessor unreacted lime settles
out during clarification. (See Figure 4). Dueto the organic compounds in the wastewater, the
resultant sludge is classifiedas a hazardous wasteand must be disposed of accordingto RCRA
hazardous waste regulations.
In 1986 the switch was made to caustic sodaas the principal neutralizing agent
in an effort
to reduce sludge generation rates. This system was very effective in limiting the amount of
1
Ash blspoeal l Caustlc
FigUte 3 General cost breakdown. Caustic soda used to neu-

tralizethewastewater is seen to represent the greatest cost
factor.
564 Hazen and Myers
Lime EfficiencylSludge Generation

50%
10096 I I I I I I 1
0 1 2 3 4 5 6 7 8
PH
Figure 4 Lime efficiency/sludge generationversus pH.
wastewater sludge produced, but in 1990 caustic soda experienced a 52% increase in price,
which dramatically increased the variable cost of neutralization.
B. Approach
The solution selected to lower neutralization costs while minimizing sludge generation rates
was to employ a dual neutralization process. This process uses less expensive materials to ad-
just the wastewaterpH from less than 2 to approximately 3.5 and then finishes the neutraliza-
tion to pH 7 by using the higher priced caustic. This means that approximately95% of ECD’s
neutralization requirements can be met usingthe lower priced lime. (Figure 5 presents a general
pH diagram that displays the change in pH achieved with hydroxideaddition, and Figure 6 plots
the cost of neutralizing agent versus pH achieved.)
The process was tested initially in the laboratory, using several neutralizing materials. It
was found that lime couldbe used successfully to achieve lowerpH values with highefficiency.
In implementing this process, limewas metered viaa rotary valve to a screw conveyor that
conveys the lime into a mixing tank. In the mixingtank, water is addedto create a lime slurry,
which is then directed to the process trench and combined with wastewater. This operation oc-
curs just upstream of our neutralization basin, wherecaustic is then used to finish the neutral-
ization process. (See Figure 7.)
Implementation of this process is being conducted on a staged basis to evaluate its effect
on the rest of our treatment system. To date, no adverse effects have been noted.
C. Results
The dual neutralization process has been active since September 24, 1991. During this time
caustic use has decreasedby 37% and the variable cost associated with neutralizing wastewater
has decreased significantly. There have been nodeleterious effects to the incineration system,
and the percentage of acid neutralized with lime is being increased.
Neutralization Tacticsfor Acidic Wastewater 565
PH
10
~ ~~~
Hydroxide Addition
Figure 5 Hydroxideaddition versus pH.
cost
0 ...............................................
-................................................................................................................................................................................................ ..""""~.."""'~""~~""
- - &"...........
""""a." ...........................
_. .................. .........................................................................................
-
-"--".y" &,..W
......................................... " YYUU"UUl.r.fl.'.......
................. -.".... L ..........
8 ""-L's's':'5. ...............*.
---.:&.L
""""": ................
:&.
8 --""".
I I I I I I I
1.4
1.6 1.55
1.45 1.5 1.65 1.7 1.75 1.8
PH
Caustic Ume
......Both
0......
Figure 6 Cost of neutralizing Agent vs. pH. (0)Caustic soda; (A) lime; (0)both.
566 Hazen and Myers
Wastewater Flow -W
Neutralization
Basin -0 caustic
M
W
Mixing Tank
Figure 7 Limeneutralizationprocessdiagram.
REFERENCES
1 . Wescott, C. C., pH Measurements, Academic. New York, 1978. pp. 1-12.
2. OMEGA. The pH and Conductivity Handbook, OMEGA Engineering, Inc., Stamford, Cl', 1992,
pp. A-3, A-4,A-8.
3. Perry, R. H., Perry's ChemicalEngineers' Handbook, 6th ed., McGraw-Hill, New York, 1984,
pp. 3-20, 3-153, 22-50.
4. McMillen. G . K.,pH Control, Instrument Society of America, Charlotte, N.C., 1985, pp. 54-68.
5. Wentz, C. A., Hazardous Waste Management, McGraw-Hill, New York, 1989, p. 146.
6. Gutschick. K. A., Lime for Environmental Uses, ASTM Spec. Tech. Publ. 931, ASTM, Philadel-
phia, 1987, pp. 54-68.
7. Culp, G . L., and Williams, R. B., Handbook of Public Water Systems. Van Nostrand Reinhold,
NewYork, 1986, pp. 263-273.
8. ASTM Committee D-19, Manual on Industrial Water and Industrial Waste Water, 2nd ed., Spec.
Tech. Publ. 148-E, American Society for Testing and Materials, Philadelphia, 1960. p. 72.
9. PPG, NaOH: Caustic Soda. Tech. brochure. PPG Industries, Inc., Pittsburgh, Penna, 1986, pp.
6-68.
10. Holtzclaw, H. F., Jr., Robinson, W. R., and Nebergall, W. H., General Chemistry, 7th ed., D.C.
Heath,Lexington,Mass., 1984, p. 105.
1 1 . Lange, N. A., Lunge's Handbook of Chemistry, Tenth Edition, McGraw-Hill, New York, 1967,
p. 1150.
12. Hazen, C. A., Dual Neutralization: a two step approach to neutralizing wastewater, Hazardous and
Industrial Wastes: Proceedingsof the Twenty-Fourth Mid-Atlantic Industrial Conference, edited by
Brian E. Reed and William A. Sack. Technomic, Lancaster, Penna., 1992, pp. 431-434.
ADDITIONAL READING
Boynton, R. S. (1980). Chemistry and Technology of Lime and Limestone, 2nd ed., Wiley, New York.
Mattock, G . (1961). pH Measurement and Titration, Macmillan, New York.
Part IV
FOR POLLUTION
MODELING CONTROL
27
Introducing Uncertainty of
Aquifer Parameters into an
Optimization Model
Robert L. Ward
Ohio Northern Universiv
Ada, Ohio
1. INTRODUCTION
'Qpically, some of the parameters of conceptual hydrologic models are calibrated using limited
hydrologic information. The purposeof this chapter is to describe how uncertain knowledgeof
aquifer parameters can be incorporated into an optimization program. The optimization pro-
gram used as the basis for this paper has been described in detail elsewhere [l].
The mathematical description of groundwater flow requires specific assumptions in order
to fit the physical events into a set of equations for which a solution exists. The expression of
the physical events by mathematical equations, the estimation of the aquifer parameters, and
the approximation of complex analytical expressions by their discrete analogs are important
sources of error. Because theseerrors introduce uncertainty into groundwater modeling, future
projections cannot be made with absolute certainty. The validity of these mathematical equa-
tions and the errors introduced by numerical methods have been discussed elsewhere. This
work is only concerned with errors introduced by inaccuracies in aquifer Parameters. In the
practical simulation of real dynamic systems we are immediately faced with uncertainty as to
exact physical parameters. The investigator must establish tolerances within whichthe param-
eters of the physical system may vary without appreciably affecting the model results.
In light ofthe inherent randomnessof subsurface flowand the existenceof uncertainties in
aquifer parameters, the groundwater flow system should be treated as a stochastic process, and
aquifer parameters should be considered random variables. To carry this argument further,
groundwater management modelsshould, if possible, be able to consider the random nature of
the subsurface flow system andderive management decisions accordingly.
Inthischapter,thedevelopment of a multiperiod stochastic groundwater contaminant
management model is illustrated using the Theis equation. The model considers explicitly the
random characteristics of transmissivity and effective porosity in a confined aquifer. The sto-
chastic management model is formulated by transforming theobjective function and constraint
569
570 Ward
equations containing random aquiferproperties into a chance-constrained expression that spec-

ifies the reliability requirements of the system performance (i.e., the user’s confidence in the
system results).
II. PREVIOUS WORK

There have been very few studies that have used stochastic concepts at the macroscopic scale
in subsurface flow models. The work that has been done can be placed into one of the three
possible categories of uncertainty that have been investigated in model solutions: (1) uncer-
tainties caused by measurement errors in the input parameters, (2) those caused by spatial
averaging of the input parameters, and (3) those associated with the inherent stochastic de-
scription of nonhomogeneous or heterogeneous porous media.
The error propagation study of Sagar and Kisiel [2] falls into the first category. They in-
vestigated the influence of errors in initial head, transmissivity,and effectivity porosity on the
drawdown patterns predicted by the Theis equation for pumpage from a homogeneous isotropic
confined aquifer. They used uniform frequency distributions for the input parameters, noting
that this is the usual Bayesian “know nothing” prior distribution. They produced plots that
show the growth throughtime of the percent error in hydraulic head at various radial distances
from a pumping well with various input errors. They also concludedthat a far more general and
better (yet mathematically complicated) method of investigating error would be to consider the
parameters as stochastic processes.
McElwee and Yukler [3] looked at the sensitivity of groundwater models with respectto
variations in transmissivity and effective porosity. They obtained sensitivity coefficients by
finding the partial derivatives of the Theis equation with respectto each of these parameters.
In general, they discovered that a 20% deviation in transmissivity or effective porosity can be
handled adequately (error of less than 5% of drawdown) by the first-order formulation that is
used in this chapter.
The work of Bibby and Sunada[4] combines aspectsof categories 1 and 2. In their analysis
they used a numerical simulation model of transient flow toa well in a confined aquifer. They
used Monte Carlo simulation to investigate the effect on the solutions of normally distributed
measurement errors in initial head, boundary heads, pumping rate, aquifer thickness, hydraulic
conductivity, and storage coefficient. In addition they analyzed the uncertainties introduced
into the solutions by choosing spatially averaged parameter values at each grid point in the
nodal mesh used in the numerical method. They assumed that within each nodal block, each
input parameter (hydraulic conductivity, for example) can be represented by a general linear
function that fully describes the spatial trends within the block. Theuncertainties in the values
of the coefficients of this general linear function (whichare related to the number of available
measurements) leadto uncertainty in the spatially averaged value usedat each node in the sim-
ulation. This type of analysis leads to the normal distribution for the hydraulic conductivity
values. This normal distribution identifies the approach as having more in common with the
analysis of measurement errors (category 1) than with stochastically defined media (category
3) where hydraulic conductivity is usually recognized as being log-normally distributed.
A paper by Freeze [5] falls into category 3. He concluded that the most realistic repre-
sentation of a nonuniform homogeneous porous mediumis a stochastic set of macroscopic el-
ements in which the two basic hydrogeologic parameters (hydraulic conductivity and porosity)
within these elements are assumed to come from frequency distributions.
lbng [6] developed a multiperiod stochastic groundwater management model using the
Cooper-Jacob equation and the concept of unit response functions. His general conclusions
were that effort should be given to better evaluate transmissivityand its variability. The effec-
Parameters
Uncertainty of Aquifer 571
tive porosity in a modeling process canbe treated as deterministic, and its accuracy is not crit-
ical. However, when the uncertainty of transmissivity is large, the normality assumption for
random drawdown may not be appropriate. Furthermore, the assessment of statistical proper-
ties of drawdown using first-order analysis may not be appropriate. There have been some in-
vestigations regarding the appropriateness of first-order analysis applied to situations where
variation of system components is large.
Loaiciga and Marino [7] develop a method for estimating the elementsof parameter ma-
trices in the governing equation of flow
in a confined aquifer.The estimation techniques for the
distributedparametersinverseproblemincludelinearleastsquaresandgeneralizedleast
squares methods. Second, a nonlinear maximum likelihood estimation approach to the inverse
problem is presented.The statistical properties of maximum likelihood estimators are derived,
and a procedure to construct confidence intervals and do hypothesis testing is presented.
111. MODELDEVELOPMENT
A. Deterministic Model
Unit response functions describe relationships between state variables of an aquifer system
such as drawdown and management decision variables suchas pumping. The continuous form
of convolution relations between aquifer drawdown and discharge for a linear flow system can
be expressed as
M
i= 1
where si,,is drawdown at observation point j at time t; 6ij,T"1+1 is drawdown at observation

point j resulting from a unit impulse of pumping at point i during time t; qi,,is unit pumpingat
well i during time t; and M is the total number of pumping wells under consideration. The
time-dependent drawdown response function, aiJVt,represents incremental drawdownof each
observation point at j at time t resulting from a unit impulse of pumping at each discharging
well applied at time t = 0. When the time scale is discretized, Equation (1) can be expressed
in an equivalent form as
M n
i=l k=l
where si," is drawdown at the jth observation point at the end of the nth period; aijakis the
response function for the kth period relating drawdown at the $h observation point to unit
pumping at the ith discharging well; and qi.n"k+I is pumping at the ith discharging well during
the kth period, k < n.
In groundwater management practices, the entire planning horizon is generally divided
into operational intervals. An operation policy or management decision may vary from one
operational interval to another, but it generally remains the same within each operational in-
terval. As a result, a discrete formulation of the convolution relation, Equation (2), is more
practical than the continuous formulation in groundwater management.
The unit response function 6 can be obtained from a distributed parameter groundwater
simulation model.However, when hydrogeologic information of an aquifer systemis lacking or
unavailable, some closed form of analytical solution to an idealized condition can be used to
572 Ward
derive the unit response function. Inthis paper, a stochastic groundwater management model is
developed for a confined, homogeneous, and nonuniform aquifer with the following assump-
tions: (1) The aquifer is nonleaky and infinite in horizontal extent; (2) there is a radial flow
pattern; (3) wells fully penetrate the entire thickness of aquifer; and (4) the piezometric head
prior to pumping is uniform throughout the entire aquifer. Under these assumptions, the unit
response function can be obtained from the well functions:
where qiJ,k= ( I / ~ ) ~ T W [ ~ U ~ ~ , ~W.]

in which ] , is the well function, UiJ,k = ( ? ~ ) / ( 4 ~ r , )r; is
the distance betweenthe pump well and the observation point; S is the storage coefficient; T is
the aquifer transmissivity; andtk is the time at the end of the kth period.
The well function for the Theis equation can be written as
In this paper,the Theis equation is used to demonstrate the development of a stochastic ground-
water management model.A groundwater contaminant plume management model will be used
to demonstrate our developmentof a stochastic management model. A detailed description. of
the model is presented in a previous paper by Peralta and Ward [l].
The problem is to determine the optimal pumpage and pumping pattern over a specified
planning horizon such that there are no undesirable consequences.In general, undesirable con-
sequences such as depletion of aquifer and land subsidence can be avoided by properly con-
trolling aquifer drawdown.
Since the response function characterizes an aquifer pumping-drawdown relationship, a
groundwater managementmodel can be very easily formulated once the response functions are
defined. Without considering the random natureof aquifer properties, the deterministic man-
agement model can be stated as follows.
Objective: Minimize the cost of pumping to produce as nearly as possible a horizontal
hydraulic gradient within a specified time frame, subject to
1. Upper and lower limits ondrawdown
2. Upperandlowerlimitsonpumping
The details of the objective function and constraints are also described in detail in Ref. 1.
Values for transmissivity T and storage coefficient S are normally derived from a pump
well test, and as such a test provides in situ values of aquifer parameters averaged overa large
and representative aquifer volume, T and S should be treated as random variables. Conse-
quently, the response function 6 and the drawdown constraint are random in nature because
they contain random variables T and S.
The objective function equation and the drawdown constraint equations are affected by
drawdown. This implies that theobjective function and constraints cannotbe known with cer-
tainty. Thus, it is more appropriate and realistic to examine both probabllistically. In a sto-
chastic environment, we want to specify limitations on allowable risk or required reliability of
constraint performance.The reliability we specifyfor our constraintsis actually the confidence
limits we are setting for our optimal pumpingvalues. This reliability can be determined based
on the confidence of the model user in his measurement of the aquifer parameters. Our ex-
pert system (the preprocessor for user input before optimization) uses the confidence in the
input and, onthe basis of Bayesian theory, producesa confidence factor (reliability pj,Jfor its
Uncertain0 of Aquifer Parameters 573
input into the optimization program. Then, if we impose a restriction on drawdown at any point
j at the end of the nth period resulting from the pumping over the entire well field that can-
not exceed a specified value sjmnwith a reliability pj,n, the drawdown constraints can be ex-
pressed as
Pr { 9
ki == ll
6 i jq. ik. t - k + I
A probability statement of drawdown constraint(or anywhere drawdown is used suchas in the

objective function in our case) like Equation ( 5 ) is not mathematically operational, andfurther
modification is needed. To make Equation ( 5 ) operational, it is necessary to assess statistical
properties of random terms in chance-constrained equations.
There havebeen a number of field investigations and laboratory experiments assessing the
probability distributionof aquifer transmissivityand hydraulic conductivity. Most findings in-
dicate that the hydraulic conductivity has a log-normal distribution. Because the response func-
tion 6 is a nonlinear function of transmissivityand effective porosity, the probability function
of 6 as well as drawdown at any observation point cannot be easily be assessed. Therefore,
first-order analysis is applied to estimate statistical properties of the response function and
drawdown at each observation point.
First-order analysis is a useful method to estimate statistical characteristics such as the
mean and variance of a function involving random functions.In first-order analysis, the func-
tion containing random variables is expandedin a Taylor series about the mean values ofran-
dom variables, that is,
2! n!
fly) = A V ) + f’(v) [x-x(v)] +p(v,[x-x(v)]* +- - (6)
in which&) is a function involving a random variable x,flv) is themean value of&), and x(v)
is the value of the random variableat the mean.
Derivations of statistical properties of drawdownat each observation point, assuming in-
dependence of tranmissivityand effective porosity, are given in the Appendix, and the results
are as follows.
I t
i=l k=l
in which E[sjJ and var[sj.,] are the mean and variance, respectively of drawdown at observa-
tion wellj at the endof the t period; sdt and sdsare the standard deviations of the transmissivity
and effective porosity, respectively, e
and B_,A_, are coefficients that are functions of the mean
transmissivity and effective porosity.As can be seen, the mean of drawdownis a linear function
of pumping, but the variance is a quadratic function of the pumping. Derivation of Equations
(7) and (8) enables the development of a deterministic equivalent for Equation ( 3 , as shown in
the nextsection, that is mathematically operational, and the random characteristics of the aqui-
fer properties are explicitly incorporated in the management model.
574 Ward
B. Stochastic Model
The total drawdown at any control point is the sum of the drawdowns created by many indi-
vidual pumps. Since drawdown is a random variable, the central limit theorem applies. That
theorem states that if n is large, a set of random variables has approximatelya standard nor-
mal distribution. Therefore, the total drawdown at each observation point can be assumed to
have a normal distribution with a mean and variance given by Equations (7) and ( 8 ) , respec-
tively. Under the normality assumption, the original chance-constrained Equation (5) can be
expressed as
where Z is a standard normal randomvariate with mean zero andunit variance. By substituting
Equation (7) into Equation (9), an equivalent expression can be written as
in which F" [ p ] is a standard normal deviate correspondingto the normal cumulative distri-
bution functionof p. A plus sign producesthe equation stating that thereis a p probability that
the actual drawdowns at pumping wells are less than the calculated values ~ , whereas
~, a minus
sign produces the equation stating that there is a 1 - p probability that the actual drawdowns
at observations wells are less than the calculated value.
Note that the second termin Equation (10) involvesa square root of the varianceof draw-
down at each observation point, which, in turn, is a quadratic function of unknown decision
variables q. The determidistic equivalent of a chance-constrained equation is nonlinear. Stan-
dard linear programming codes cannot solve problems with nonlinear constraint equations.
However, as suggested by lhng [ 6 ] ,quasi-linearization can be employed to linearize the non-
linear term in Equation (10).
The quasi-linearizationresults in a linear approximation for the stochastic equivalent
to the
original deterministic constraint on drawdown:
I t
i=l k=l
where Eij,k = 5 j . k i-F"[p]gij,k for the drawdown Constraint, Eij,k = 5 j . k - F"[P]gij,k

for the objective function, and O_ is a stochastic term derived during this process.
Checking the signs for the B_ and O_ coefficients reveals that the stochastic unit influence
coefficient E responds the same whether showing the influence of an injection well or that of
an extraction well. At injection wells, bothB_ and Q are negative values. Therefore, E is larger
in absolute magnitude than the deterministic unit influence coefficient for the drawdown con-
straint. E is smaller than the deterministic coefficient for theobjective function. At extraction
wells, both B_ and O_ are positive, producing a larger absolute value for E in the drawdown
constraint and a smaller value for the objective function.
To convert the original deterministic model into a stochastic model, replace the drawdown
constraint with Equation (10) and use for 8iJ.k in the objective function. Clearly EijVkcan
Uncertainty of Aquifer Parameters 575
..., -. .. ..- - -
DOES NOT EXCEED
GROUND SURFACE
FINAL ELEVATION
95% CERTAINTY THAT FINAL

ELEV. AT OBSERVATION WELL
MODEL 2 ELEVATION
BYISCALCULATED
BY MODEL
-””
X S s X CERTAINPI THAT FINAL

ELEV. AT PUMP WELL DOES
A CRITICAL
NOT DROP BELOY
LOWER ELEV.
._ INITIAL
DIRECTION
OF FLOW
Figure 1 Cross section demonstrating sample stochastic constraints on final water levels.
be considered a stochastic unit response function derived from the Theis equation. And it
should be noted that the deterministic model actually represents a reliability of 0.50 (when
F”[0.50] = 0).
1. ReliabilityDetermination
There are drawdown terms (for observation wells) in the objective function as well as in the
drawdown constraint (for pumping wells). Reliability is treated differently in the two cases.
Refer to Figure 1 during the following discussion.
Let’s assume a reliability level of 0.95. In a drawdown constraint one wishes to be 95%
sure that the change in water level does not exceed the prespecified maximum change (i.e.,
does not violate predetermined bounds on the head). One uses the standard normal deviate
(F”[p]) corresponding to a reliability of 0.95 for the drawdown constraint (i.e., F-It.951 =
1.M) . procedure described previously computesa stochastic unit response coefficient for
The
the 95% confidence level. The coefficient is larger than a deterministic coefficient (which cor-
responds to a 50% confidence level). Since unit pumping causesa greater change in head using
the 95%probability influencecoefficient, less pumpingis feasible before drawdown constraints
become tight.
When considering the objective of raising water levelsto prevent contaminant movement,
one wishesto be 95%confident that head changes equalor exceed calculated values. Therefore,
with the objective function one uses the standard normal deviate correspondinga to reliability
of 0.05. This produces stochastic influence coefficients thatare numerically smallerthan 95%
of all deterministic influence coefficients. For identical pumping values, the 95% probability
change in water levelsneeded to achieve a horizontal gradientis much greater than that needed
using deterministic coefficients. This guarantees that pumping values calculatedby the model
are equal to or greater than those required by the deterministic model to produce a horizontal
gradient.
However, this guarantee also causes the constraintthat final heads at downgradient obser-
vation wells are greater than the final head at the source to force the objective function value
576 Ward
to be larger than an objective function value resulting from only trying to minimize the head
differences between the contaminant sourceand all observation wells. Greater pumping values
may actually cause the heads at the downgradient observation wells to “overshoot” the head
at the source and produce a reverse gradient. This is demonstrated in Section IV, where the
objective function and reverse gradient increaseas aquifer parameter uncertainty increases. The
“tight” downgradient observationwell is the one whose final head is equal to the final headat
the source. All other downgradient observation well headsare higher than the source head and
therefore produce a larger objective function value.
2. Determination ofAquifer Parameters
Estimation of transmissivity and effective porosity has received much attention in the literature
in recent years and was discussed in Section 11. From Equations (7) and (8), it is seen that the
mean and variance of transmissivity and effective porosityare needed in the stochastic version
of the optimization model. Many methods for determining these statistics are described in the
literature. Here a Bayesian approach is usedto derive the mean and variance for transmissivity
and effective porosity.
The Bayesian approach uses a prior (also called unconditional) probability distribution
function (pdf) and a likelihood pdf to determine the mean and variance forthe aquifer param-
eters. This mean and variance describe the posterior or conditional pdf used within the sto-
chastic model. The prior pdfisbasedonknowledgeoftheaquiferobtainedfrompast
experience. This study suggests using aquifer material(soil type) as the basis for the prior pdf.
The likelihood pdf is developed from current information (field or lab data) about the aquifer
in question.
In this chapter the standard deviationof transmissivity and effective porosity are varied to
determine how these changes affect the objective function value. However, in a real situation,
one would estimate a mean and variance for these aquifer parameters from a prior pdf and a
“likelihood” pdf. The user would select a description of the soil type from a given list. Based
on a range of values of transmissivity and effective porosity associated with each soil (de- type
rived from numerous references), a prior pdf mean (Xo) and variance (V,) are determined. This
determination is made by assuming that the range of values spans three standard deviations
each side of the mean (99% confidence interval). With this assumption and assuming a log-
normal pdf for transmissivity and a normal pdf for effective porosity, one can compute the
mean and standard deviation. If there are no field data values for the problem, the prior pdf
becomes the posterior pdf.
If one has field data values, the mean (X) and variance ( V ) are determined using standard
equations for mean and variance of a data population. This mean and variance for the field data
values define the likelihood pdf. Themean and variance for transmissivityare calculated using
the natural log of all transmissivity values because these log values are known to be normally
distributed. The relationship between posterior pdf,the prior pdf, andthe likelihood pdf can be
expressed as
Posterior distribution a prior distribution X likelihood distribution
The mathematicsof multiplying a normally distributed likelihood pdf by a normally distributed
prior pdf has been previously derived [ S ] . Assuming that the natural logdata values for trans-
missivity and the data values for effective porosity are normally distributed, the posterior
mean, E ( . ) , and posterior variance, var (.),for either parameter are calculated from
and
var (.) = ( v ~+-V~- * ) - ’ ( 13)
The expected value, E(.), and the variance, var(.), for effective porosity are used as the pos-
terior mean and variance. However, because natural log values are used to determine the ex-
pected value and variance for transmissivity, these values must be converted back to represent
the mean and variance of the actual transmissivity values.Standard equations for the mean and
variance of a population that has a log-normal pdf (when the expected value and variance of its
natural log values are known) are
- -
Mean = exp [ E +
and
Variance = [exp (var + 2E)] [exp (var) - 11 (15)
These two equations are used on the assumption that the entire population of values is avail-
able. Since the prior pdf uses the knowledge of a large amount of data for each soil type, this
assumption is sound.
IV. APPLICATION,RESULTS, AND DISCUSSION

The stochastic optimization model was applied to the same hypothetical groundwater contam-
ination problem that was usedto analyze the deterministic version. Aquifer parameters (trans-
missivity and effective porosity), coefficient of variation (CV, ratio of standard deviation to
mean), and required solution reliability were varied in consecutive runs.
The simulation component and optimization component were run on anIBMATwith
640K bytes of RAM, a 30 MB internal hard disk a with a floppy disk drive, and math co-
processor.
Physical parameters for model run Id include a transmissivity of 1255 m2/day (13,500ft?/
day) and an effective porosity of 0.3. The original hydraulic gradient was 0.54%. Maximum
and minimum acceptable pumping rates, based on available equipment, are 135 and 0 Usec.
This was based on the performance curve fora pump that can discharge 150Usec against 6 m
of head at 80% efficiency. The upper limit on head at all injection wells wasthe ground surface
(5.8 m, above the initial water table). This should prevent pressurized injection[9]. The lower
limit on head at extraction wells prevented such changes in tranmissivity that would invalidate
the use of superposition. In general, if the changein transmissivity is less than lo%, the aquifer
can be treated as a confined aquifer system.
The stochastic model was applied to the same hypothetical system described for the de-
terministic model in Ref. l . Results are shown in Tables l and 2 for comparison with the de-
terministic model (run Id). The coefficients used for this analysis were Wf = l .O and c‘ and
c’’ equal to their original values. Therefore,the results shown for this analysisare for a strongly
hydraulic objective function.
The initial pumping (Q,) used in the iterative solution procedure of the stochastic model
was the optimal pumping from the deterministic model run. It was found that two iterations
brought acceptable agreement (convergence within 5%) between the “estimated” pumping val-
ues and the final optimal pumping. The weight factor in the objective function was adjusted for
identical runs as described in the previous paper [l], but, as was found then, all weight factors
of 1.O and greater produced the same results. Subsequent tests used a weight factor of 1.O.
578 Ward
Table 1 Effect of AquiferParameterUncertaintyon 95% ReliableOpti-

mal Unsteady Pumping Strategy for Hypothetical Problem'
Run
5s 4s 3s 2sId 1s
Pumping (Vsec)
Day 1 96.1 85.8 70.2 51.4 85.3 83.3
2 90.1 76.4 63.4 47.1 74.8 70.9
3 84.9 70.4 59.3 44.7 68.3 63.7
4 80.2 66.3 56.4 43 .O 64.0 59.2
5 76.9 63.2 54.2 41.7 60.9 56.2
6 36.9 57.3 52.5 40.7 58.7 54.2
7 0.0 0.0 28.7 40.0 0.0 52.8
8 0.0 0.0 0.0 25.6 23.3 0.0
Avg. pumping 58.1 52.4 48.1 41.8 54.4 55.0
Avg. gradient (%) 0.08 0.079 0.085 0.095 0.098 0.14
Gradient SD 0.058 0.043 0.057 0.062 0.061 0.084
Sum of squared 1.24 1.08 1.30 1.72 1.79 4.99
head diff. (m')
Obj. function 15.63 13.54 15.66 19.82 21.18 55.53
0 & M costsb 2.31 1.93 1.65 1.32 1.93 1.84
($10~)
Transmissivity
CV Run CVporosity
Effective
~~
1s
2s
3s
4s
5s 0.2 0.8
'Run Id is deterministic model.
bo C% M = operations and maintenance.
In all, 10 stochastic optimizations were performed. These used a range of values for the
coefficient of variation (CV) for both transmissivity and effective porosity and used two reli-
run). Figures 2 and 3 graphically
abilities (a constant for all wells and all time periods for each
depict the pumping strategies developed for the five stochastic model runs made at the 95%
reliability level. Figure 2 shows the pumping trends as the uncertainty of transmissivity in-
creases from run 1s to 3s as compared to the deterministic run (Id). Figure 3 shows the pump-
ing trends as the uncertainty of effective porosity increases from run1s to runs 4 s and 5s. The
same general pumping trendsare evident for the runs made at the 80% reliability level.
To analyze the predictabilityof these results we look first at the equation forthe stochastic
influence coefficientE [Equation (1l)] and refer to Figure1. From a table of standard normal
deviates it is known that as reliability [p = F(z)] increases, z (which equalsF"[p]) increases.
Therefore, lookingat Equation (1 1) we see thatas reliability increases,E for the objective func-
tion decreases and E for the drawdown constraint increases. In summary, an increase in the
uncertainty of aquiferparametersproduces the sameresult as an increase inreliability-
smaller E for the objective function and larger E for the drawdown constraint.
As stated, for the drawdown constraints, increasing reliabilityor uncertainty of parameters
produces a larger influence coefficient. This causes a greater reaction of the potentiometric
Table 2 Effect of Aquifer Parameter Uncertainty on 80% Reliable

Optimal Unsteady Pumping Strategy for Hypothetical Problem
5s 4s 3s 2s
Id 1s
Pumping (Usec)
~
Day 1 %.1 94.6 85.7 69.8 93.2 90.6

2 90.1 86.0 76.7 63.2 85.1 82.0
3 84.9 78.8 71.1 59.2 77.6 74.7
4 80.2 73.9 67.1 56.4 72.4 69.3
5 76.9 70.2 64.1 54.3 68.7 65.6
6 36.9 21.5 44.9 52.7 36.2 63.O
7 0.0 0.0 0.0 20.1 0.0 0.0
8 0.0 0.0 0.0 0.0 0.0 4.9
Avg. pumping 58.1 53.1 51.2 47.O 54.1 56.3
Avg. gradient (%) 0.08 0.067 0.070 0.076 0.076 0.097
Gradient SD 0.058 0.047 0.048 0.050 0.049 0.060
Sum of squared 1.24 .77 .85 1.04 1.01 1.70
head diff. (m2)
Obj . function 15.63 10.37 11.03 12.80 12.89 20.36
0 & M costs 2.31 2.04 1.89 1.62 2.04 2.06
($10~)
Figure 2 Daily pumping strategies for increasing uncertainty of transmissivity as compared to the de-
terministic strategy (95% reliability level).
580 Ward
Figure 3 Daily pumping strategies for increasing uncertaintyof effective porosity as compared to the
deterministic strategy (95% reliability level).
surface to a unit of pumping. Therefore, this increase allowsfor less pumping during a unit of
time because the upper bound on drawdownis reached more quickly. In thecase of a reliability
of 0.95 we know that the F” [0.95] value (1 .a) is equal to or larger than 95% of all F”[p]
values; thusthe E value for a reliability of 0.95 is equal to or greater than 95% ofE values for
the same aquifer parameters. This confirms the stochastic constraint that in the field the upper
bound on drawdown will not be exceeded 95% of the time. Tables 1 and 2 reflect the trend of
increasing reliability or increasing uncertainty of parameters and the resulting decrease in al-
lowable pumping.
Why, then, does the pumping increasefor the last time period, or why are there more time
periods of pumping as reliabilityor CV increases? Whilethe large coefficients are causing large
head increases at the injection wells (thus restricting the amount of pumping), the small sto-
chastic influence coefficients for the objective function cause a much smaller reaction of the
potentiometric surfaceat the observation wells. Thus, lower pumping values caused by increas-
ing the reliability or uncertainty have even a smaller effect on drawdown at the observation
wells. Yet the goal is still to minimize the objective function. To do this, additional pumping
periods are needed or more pumping is required during the last time period as reliability or
uncertainty increases. This trend is shown in Tables 1 and 2. The objective function uses the
large drawdowns at the pumping wells to calculate pumping costs, thus producing the highest
costs. The objective function uses the small drawdowns at the observation wells to determine
the difference in head, thus producing a large sumof head differences.Thus we are assured that
the objective function valueis the largest expected for the given input andthat the results in the
field will probably not exceed the calculated value.
However, the constraint that downstream heads must be higher than the head at the con-
taminant source, because it uses the smaller E values for the observation well head calcula-
tions, actually causes the hydraulic gradient to “overshoot” horizontal. The smaller E values
produced at the 0.05 reliability level forobservation well head calculations give usa 95% con-
fidence that the heads are those calculated (using these E values) or greater, thus causing the
Parameters
Uncertainty of Aquifer 581
Table 3 Summary of TrendsProducedbyStochasticAnalysis(HydraulicObjectiveFunction)

Effect on uncertainty
Value affected Effect on reliability IntransmissivityIneffectiveporosity
1. Influence coefficient used with:
Objective function Decrease Large decr. Small decr.
DD constraint Increase Large incr. Small incr.
2. Dailypumping Decrease Large decr. Small decr.
3. Totalpumping Decrease Large decr. Small incr.
4. Gradient (reverse) Steeper and Steeper and less smooth
less smooth
5 . Objective function value Increase incr.
Large
incr.
Small
reverse gradient. Remembering that the final gradients are always reverse gradients, Tables 1
and 2 show that as reliability or uncertainty increases, the final gradient is larger in the reverse
direction. The confidence in the final gradient is further complicated by the fact that the target
elevation (normally the head at the contaminant source) is itself stochastic. Therefore, the ac-
tual reliability of the final gradient will be something less than the specified value, but that
reliability cannot be determined with precision.
Table 3 summarizes the trends that developed as uncertainty of aquifer parameters and
reliability were systematically varied. Figures 4 and 5 graphically show the trends in total
pumping and the resulting final gradient. Figure 4 shows the five stochastic runs using a re-
liability of 95% normalized to the deterministic run (Id). Figure 5 shows the five runs nor-
malizedusingareliabilityof 80%. As the coefficient of variation (CV) for tranmissivity
increases (runs Is, 2s, and 3s), the influence coefficients for the drawdown constraint increase
and those of the objective function decrease. The expected result is a decrease in pumping for
each time period (but larger total pumping) and an increase in the final average gradient and
objective function value.
Runs Is, 4s, and 5s show the results of increasing the CV for the effective porosity while
holding the transmissivity CV constant. The general trend for these runs is the sameas those
for runs Is, 2s, and 3s. The resulting gradient and objective function for runs4s and 5s show
0f i n a l gradient
160
l20
100
80
60
Stochastic Runs
Figure 4 Comparisons of final gradient and total pumping for the stochastic runs at the 95% reliabil-
ity level.
582 Ward
-
ae
Y
c
.4
180- 0f in81 gradient -total pumping - 180
io0
eo
60
Stochastic Runs
figure 5 Comparisons of final gradient and total pumping for the stochastic runs at the80% reliabil-
ity level.
a sharp increase from run 1s. The increased CV produces larger influence Coefficients for the
drawdown constraint and smaller coefficients for the objective function just as the increased
CV for transmissivity does. However, the changes in these coefficients are small compared to
those produced by comparable increasesin transmissivity CV and cause only small differences
in pumping between runs Is, 4s, and 5s. In comparison, the resulting gradient and objective
function are much worse than those resulting Erom comparable tranmissivity changes runs in 2s
and 3s.
To explain this difference we look at the difference in sign between the A_ coefficients,
Equation (19), which are affected by changes in transmissivity CV, and the P_ coefficients,
Equation (21), which are affected by changes in effectivity porosityCV. The negative sign with
the P_ coefficient indicatesit will affect the optimalstrategy in a manner oppositeto that of the
A_ coefficient. As the CV of transmissivity is increased, there is a large changein pumping and
a small change in gradient and objective function. For the same CV increase in effective po-
rosity, thereis a small changein pumping anda large changein gradient and objective function.
The two parameters (transmissivity andeffective porosity) cause an opposite relationship be-
tween pumping and its effect on the objective function and the constraints.
Table 2 displays results of the same variation in the CV of the two parameters, computed
using a reliability level of 0.80. As expected, the reduction in reliability increases the optimal
pumping values and improvesthe final gradient and objective function. The smaller reliability
produces smallerstochastic unit response coefficients. Resultingstrategies and water levelsare
more similar to those from the deterministic madel (reliability = 0.50) than are those devel-
oped using a 0.95 reliability.
Strategies for runs 4 s at the 95% reliability level and5s at 80% reliability have no pumping
on day7 and yet require pumping on day 8. This is a definite change in the overall pattern of the
stochastically optimal pumping strategies. However, a look at the sensitivity values for the
pumping during days 7 and 8 gives an indication that it is not a major change. The sensitivity
value (amountthe objective function would change witha unit increasein pumping during that
day) associatedwith each pumping value for days7 and 8 for those tworuns is very small. For
example, these sensitivities are in the range of 10-4-10"5 as comparedto a sensitivity of 0.7-
1.3 for the tight pumping value in most other runs. This indicates that the pumping for day 8
could also be 0 without any significant change in the objective function. Therefore, the zero
Parameters
Uncertainry of Aquifer 583
pumping for day 7 and a pumping valuefor day 8 of these runs could be zero pumping for both
days 7 and 8 without a dramatic change in the overall pattern of the results.
Comparisons to Tung’s [6] analysis are difficult to make because his objective function
was to maximize pumping, which is not affected by the stochastic influence coefficient. The
only constraint was on drawdown. In addition, the Cooper-Jacob equation (which is only ap-
propriate for small values of the Boltzmann variable, U 5 0.02) used to derive the stochastic
unit influence coefficient shows P_ to be equal to 0 except for the first time period. However,the
general trends "brig speaks of concerning transmissivity applyto is analysis: (1) Pumping in-
creases as reliability or CV decreases and (2) uncertainty of tranmissivity causes a larger
change in pumping than does a comparable change in effective porosity. This study indicates
that effective porosity has an effect on the drawdownat the observation wells (something Tung
considers negligible) and hence has an effect on the objective function value. In addition, the
daily pumping increases with decreasing effective porosity CV, but at the same time the total
pumping decreases. In summary, the trends shown in this analysis are found in Table 3.
V. CONCLUSIONS
A procedure developed by Tung [6] was used to incorporate uncertainty of aquifer parameters
into our model. A stochastic unit response function ( E , based on the Theis well function) was
developed and usedin the same manneras the unit response functionin a deterministic model.
This E value is dependent upon the uncertainty of aquifer parameters as measuredby the CO-
efficient of variation and a specified reliability of the solution.
Drawdown at observation wells (which affect the objective function and gradient con-
straints) must be treated differently than drawdown at the pumping wells (which affect the
drawdown constraint). For example, if a reliability of 95% is specified for our solution, an E
value correspondingto a reliability of 0.95 is used for the drawdown constraint because the user
wants to be 95% confident that the resulting drawdown produced bq’the optimal pumpingat the
pumping wells is the value calculated or less, whereas the E value corresponding toa reliability
of 0.05 is used to determine drawdown at the observation wells because the user wants to be
95% confident that the actual drawdown (produced by the optimal pumping)at the observation
wells equals or exceeds the calculated value. This meansthat E values corresponding to a re-
liability of 0.95 are used for the drawdown constraint, and those corresponding toa reliability
of 0.05 are used with the objective function, Equation (10).
This theory guarantees the user a 95% confidence levelfor the drawdown constraint. How-
ever, because the objective function minimizes the head differences between the observation
wells (whose valuesare stochastic) and the source (whose valueis also stochastic), a joint 95%
confidence level cannot be guaranteed. It would be some value slightly less than 95% and can-
not readily be determined.
The major differences between Tung’s analysis and this study are that (1) Tung used the
Cooper-Jacob equation to derive the stochastic coefficients and (2) Tung’s objective function
was to maximize pumping, and therefore the objective function did not incorporate stochastic
coefficients.
The study results shown in Tables 1 and 2 agree in general with the conclusions of Tung.
As the reliability leveldecreases or as aquifer parameter uncertainty decreases, the pumpingfor
each time period increases. As a consequence, the objective function improves.
The results of changes in uncertainty of effective porosity differ from those of Tung. Tung’s
derivation of the P_ coefficient (the partial derivative of drawdown with respect to effective
porosity) usingthe Cooper-Jacob equationshowed it to have a value of zero for alltime periods
except the first. Therefore, changesin uncertainty of effective porosity had almost no effect on
584 Ward
the optimal pumping values. This may be due to the fact that the Cooper-Jacob equation
is only
valid for small values of the Boltzmann variable (U 5 0.02). Our study shows that the P_ co-
efficient has values for all time periods. For equal changesin CV, effective porosity produces
smaller changes in pumping than does transmissivity. However, the resulting final gradients
produced by these small changesin pumping are much poorer than the final gradient produced
by a comparable changein CV of transmissivity. These results indicate that uncertainty in ef-
fective porosityhas little effecton allowable pumpingas Tung concluded, but the final gradient
is affected in an adverseway.
Four general statements canbe made from the stochastic analysis of this mode:
1. Introducing stochasticity into the optimization model increases the value of the objective
function.
2. Lowering the reliability level produces a model that allows more pumping (increased op-
erations and maintenance cost) and produces an improved final gradient.
3. Changes in uncertainty of transmissivity and effective porosity both produce the same gen-
eral changes in optimal daily pumping and final gradient.
4. Changes in uncertainty of transmissivity and effective porosity produce opposite effects on
the total optimal pumping required.
List of Symbols'
A_ stochastic coefficient producedby taking the partial derivative of drawdown with respect
to transmissivity, [T/L2]
&J,k the unit response function for a stimulus at well i on an observation point j at time
period k; calculated using the mean values of transmissivity and effective porosity, [T/L2]
8iJ.t-k + I the incremental drawdown at a well j in time period t caused by unit volume of
pumping at well i in time k , [l/L2]
CV coefficient of variation
g stochastictermusedtofindstochasticunitresponsefunction
E(Sj,,) mean of drawdown at observation well j at endof time period t , [L]
EiJ,k stochastic unit response function for stimulus at well i and response point j for time
period k, [T/L2]
E(T) mean
of transmissivity, [L*/"]
E($) meanof effectiveporosity
$ effective
porosity
AQ) standarddeviationofdrawdown,[L]
F"[p] standard normal deviation corresponding to a normal cumulative distribution func-
tion
4.g groundelevation at pump i, [L]
hi,o head at pumpwell i at time 0, [L]
hit head at pumpwell i at time t , [L]
hzi lowerlimitonhead at pump i, [L]
hui upperlimitonheadatpump i , [L]
(hj,=)d head at observation well j , which is downgradient of the contamination source at
the end of the modeling period TT, [L]
head at ,contaminant source at end of modeling period T T , [L]
I totalnumber of pumpingwells
'Dimensions given in terms of unit length [L] and time [TI.

,i hydraulicgradientinthe x direction, [UL]

i, hydraulicgradientinthe y direction, [UL]
J totalnumber of observationwells
n porosity
P_ stochastic coefficient producedby taking the partial derivative of drawdown with respect
to effective porosity
q Darcy'svelocity, [UT]
lower limit on pumping at all wells, [L~/T]
4" upperlimitonpumping at allwells, [L~/T]
qf pumping at allwells at time t , [L~/T]
Q, initialestimateofoptimalpumpingforstochasticmodel, [L3/Tl
r distancefromstimulus i to observationpoint j , [L]
re effectiveradius of thepumpwell,[L]
r,, radiusofthepumpwell,[L]
p specified
reliability
S storage
coefficient
sdtstandarddeviationoftransmissivity
sdsstandarddeviation of effectiveporosity
calculated drawdown at pump i at time I , [L]
TT totaltimeforoptimalpumpingstrategy,[TI
T transmissivity,
[L2/T]
Tavg averagetransmissivitybetweenpumpwell p andobservationwell 0 , [L2/T]
t timeperiodwithintime T T , [TI
U Boltzmannvariable
v seepagevelocity, [UT]
var(sj,,) variance of drawdown at observation well j at the end of time period t
var(T)varianceof
transmissivity,
var(+)varianceofeffectiveporosity
V varianceoffield data
V, varianceofpriorprobabilitydensityfunction
W, weight factor to convert the square of hydraulic head differences to dollars, [$/L2]
X mean of field data
X, meanof priorprobabilitydensityfunction
Z standardnormalrandomvariatewithmeanzeroandunitvariance
APPENDIX-ANALYSIS OF UNCERTAINTY IN DRAWDOWN

Discrete formulation of drawdown at observation point j at theend of the nth period is
given by
i=l &=l
where Gij,,"k+I is the unit response function, which can be derived from the Theis equa-
tion as
586 Ward
where
Since T (transmissivity) and0 (effective porosity)are random variables, the unit response func-
tion and drawdown are both random variables because theyare functions of random variables.
To estimate statistical properties of random variables, the first-order analysis of uncer-
tainty is employed, Taylor’s expansionof drawdown about the mean values of T and @ can be
expressed as
i=l k=I
where 5 . J . k iscomputedusingmeanvaluesand m,
and HOT represents the higher order
terms. The time increments of k and t - k + 1 are reversed from those in (Al),but they pro-
duce the same result.
First, we compute the middle term onthe right-hand side. The first-orderpartial derivative
of S,., with respect to T can be obtained by the Leibnitz rule for differentiating an integral [lo,
p. 181:
Performing the mathematics of the differentiation in three parts, we define
L i=l k=l
J
For the first time on the right-hand side of (A3),
For the second term,

db
f l b ( c ) , c ] a= 0 because b = constant (m)
For the third term,
where
du
”” - ”=” U
dT- dT 4T2k T
Therefore,
1
c b= -
f l a ( c ) ,da 4 i T k-iu - -
y ]-= 4nT2
e"'
Adding the three terms, we have
i=l k=l
in which
Similarly, the first-order partial derivative of drawdown with respect to the effective porosity
can be obtained in three parts from the Leibnitz rule.
For the first term on the right-hand side of (A3),
For the second term,

db
A b ( c ) , c h= 0 because b = constant (m)
For the third term,
where
Therefore,
Only the third has a value, and
I t
i=l &=l
where
588 Ward
1
"
4zT+ e"'t atk = 1

5j.k = 1
" 4nT+(e"'' - e"'"') at k > 1
The partial derivatives of drawdown with respectto transmissivity and effective porosity agree
with those shown by McElwee and Yukler [3].
Ignoring the higher order terms in (A5),
the expectation of drawdown canbe approximated
by the equation
i=l &=l
Which is Equation (7) of the text. Furthermore, assuming independency of T and +, the vari-
ance of drawdown can be approximated as
'sdt']+ [asj.t
[z
var(sj,,) = 8Sj.t -1 sds'
which is expressed in the text as [Equation (8)l
where sdt and sds are the standard deviations of the transmissivity and effective porosity,re-
spectively.
REFERENCES
1. Peralta, R. C., and Ward, R. L., Optimal piezometric surface management for groundwater con-
taminant control, Paper no. 86-2513, Presented at ASAE Winter meeting, Chicago, 1986. Copies
may be obtained by writing ASAE.
2. Sagar, B., and Kisiel. C. C., Limits of deterministic predictability of saturated flow equations,
Pro-
ceedings of the Second Symposium on Fundamentals of Transport Phenomenain Porous Media, Vol.
1, International Association of Hydraulic Research, Guelph, Ont., Canada, 1972, pp. 194-205.
3. McElwee, C. D.,and Yukler, M. A., Sensitivity of groundwater models with respectto variations
in transmissivity and storage, Water Resources Res., 14(3), 451-459 (1978).
4. Bibby, R., and Sunada, D. K., Statistical error analysis of a numerical model of confined ground-
water flow, Stochastic Hydraulics: Proceedings First IntemutionalSymposium on Stochastic Hy-
draulics (C. L. Chiu, e d . ) , 1971, pp. 591-612.
5. Freeze, R. A., A stochastic-conceptual analysis of one dimensional groundwater flow in nonuni-
form homogeneous media, Water Resources Res., 11(5) 725-740 (1975).
6. mng, Y. K., Groundwater management chance-constrained model, J. Water Resources Planning
Manage., 112(l), 1-19 (1986).
7. Loaicigia, H. A., and Marino, M. A., The inverse problem for confined aquifer flow: identification
and estimation with extensions,Water ResourcesRes., 23( l), 92-104 (1987).
8. Lindley, D. V., Bayesian Statistics: A Review, Society for Industrial and Applied Mathematics,
Philadelphia,1970.
9. Lefkoff and Gorelick, 1986. Design and cost analysis of rapid aquifer restoration systems using flow
simulations and quadratic programming. Groundwater,24. No. 6, pp. 777-790.
Uncertain@ of Aquifer Parameters 589
IO. Greenberg,M.D., Foundations of Applied Mathematics, Prentice-Hall, Englewood Cliffs, N.J.,

1978.
ADDITIONAL READING
Bear, J. (1979). Hydraulics of Groundwater. McGraw-Hill, New York.
Dagan, G. (1985). Stochastic modelingof groundwater flowby unconditional and conditional probabil-
ities: the inverse problem,Water Resources Res., 21(1). 65-72.
Freeze, R. A., and Cherry, J. A. (1979). Groundwater, Prentice-Hall, Englewood Cliffs, N.J.
McWhorter, D., and Sunada, D. K. (1977). Groundwater Hydrology and Hydraulics, Water Resources
Publications, Colorado.
Murtagh, B. A., and Saunders, M. A. (1983). MINOS 5.0 Users Guide, Tech. Rep. SOL 83-20. Stan-
ford Univ., Stanford, Calif.
Todd, D. K. (1980). Groundwater Hydrology, 2nd ed.. Wiley, New York.
28
Application of Total Quality
Management (TQM) Principles to
Pollution Prevention Programs
Prasad S. Kodukula
Woodward-Clyde Consultants
Overland Park, Kansas
1. INTRODUCTION
Total qualitymanagement ("QM) and pollution prevention are relatively new conceptsin
American industry. Although TQM may be a new concept to many American companies, Jap-
anese manufacturers have been implementing TQM principles in their manufacturing processes
for several years. On the other hand, environmental regulatory emphasis the United
in States is
shifting from end-of-pipe controlsto pollution prevention and waste minimization. The latter
approaches are not new to some American manufacturers, however. For example,3M Company
has been a pioneer in minimizing waste generation in manufacturing, and saved over half a
billion dollars during the last decade.
Both TQM and pollution prevention represent major shifts in the philosophy underlying
production and environmental management, respectively. These new concepts are beginningto
replace traditional methods. They have many conceptual similarities. These similarities are
briefly discussed in Section11, and Section 111 presents a case study wherein TQM principles
are being applied to achieve pollution prevention and waste minimization.
II. TQM AND POLLUTIONPREVENTION

According to W. Edwards Deming, an American management visionary, some of the core
TQM principles are
Top management commitment to quality

Zero defects
Quality through process improvement, not product inspection
Continuous process improvement
Measurement of success through statistical methods
Team effort
591
592 Kodukula
Empowerment of workers
Training
Interestingly enough, successful pollution prevention programs also involve the same core
principles. Unless there is strong commitment at the top management level (e.g., corporate
CEO or president), neither TQM nor pollution prevention programs can be successful. The
main reason is that the goals of these programs are extremely ambitious and require strong
commitment. TQM has an absolute goal of zero defects, and pollution prevention strives for
zero pollution.
The traditional American manufacturing practice has been to inspect the product for de-
fects, and defective productsare either thrown outor reworked. But according to TQM, quality
comes through process improvement. This improvement should take place starting at the re-
search and development stage and continuing through design and manufacturing. Similarly,
pollution prevention cannotbe achieved by simply monitoring wastestream discharges for en-
vironmental compliance. Manufacturing processes and waste management practices need to be
improved or even completely altered starting at the drawing board to minimize, preferably to
eliminate, the creation of waste in the first place. The ambitious goalsof zero defectsand zero
pollution can be achieved through continuous process improvement. Further, statistical meth-
ods can be used effectively to measure the success of achieving both of these goals.
The “team” concept is important in the TQM philosophy, and pollution prevention can be
effectively achieved only by team effort. This is especially true because environmental issues
typically are multidisciplinary andrelate to several different aspects of manufacturing. By em-
powerment of the team members as well as other individuals involved, innovation canbe pro-
moted thatcanpositively affect the bottomlinefor the company.Training is extremely
important in the environmental area, especially considering the rapid evolvement of new reg-
ulations and new technologies and practices developed to keep up with the regulations.
111. CASE STUDY

The case study presented herein involvesa large chemical manufacturing plant with more than
25 individual production units.As with many other chemical manufacturers, this plantand the
parent corporation as a whole, are finding itdifficult to meet the applicable environmental reg-
ulations in a cost-effective manner. Furthermore, due to the ,nature of the types of chemicals
handled, this particular facility has been under rigorous scrutiny by the regulators. In this cli-
mate, the company has no other choice but to seek pollution prevention and waste minimization
not only to comply with the regulations but also to minimize overall environmental costs.
The corporate CEO of the subject facility has recently made a commitment to reduce waste
generation at each of the company’s manufacturing plantsby 20% each year over the next 5
years. As a first step, a task forcewas formed to undertake the waste reduction programat this
facility.
A. Phase I
As part of Phase I of the program, one of the first objectives the task force accomplished was
to develop a waste generation database for the plant. The major categories of wastes included
in this inventory were
Hazardous wastes shipped to a hazardous waste landfill
Solid wastes shipped to an industrial landfill
Other hazardous and solid wastes sent off-sitefor treatment and/or disposal
Application of TQM to Pollution Prevention 593
Hazardous and solid waste residues sentto the on-site industrial boiler
Liquid waste streams treated in the on-site wastewater treatment facility 0
Fly ash from the power generation facility at the plant
Air emissions at the plant
Among these waste categories, liquid waste streams producedby the manufacturing units
were identified as top priority for further study for the following reasons.
1. From the waste generation data collected, liquid waste streams were determined to be a
major source of pollutants. Furthermore, the costs associated with treatment of these
streams is a major portion of the overall environmental management costs at the plant.
2. The effluent of the WWTF, where the liquid wastes are treated, exhibited aquatic toxicity
and recently resulted in discharge permit violations. Further violations would trigger a for-
mal investigation under a regulatory-controlled consent order, that could potentially cost
the plant several hundreds of thousands of dollars.
3. The surface impoundments that serve as the aeration basins of the WWTF’s biological
treatment system need to be replaced with above-ground tanks in the near future. This is
based on a corporate decision to eliminate the use of surface impoundments in order to
minimize any potential future liability. Since the capital cost associated with the tank-
based system is basically a function of the organic loading in the waste streams to be
treated, there is a great incentive to minimize the loading.
A team was formed to address the more pressing aforementioned effluent toxicity problem.
This team was headedby the director of the environmental department of the plant. Other team
members consisted of aWWTF operator, two chemists, two technicians, and a technical con-
sultant. The primary goalof the team wasto reduce the effluent toxicity.
The team used a TQM
approach to accomplish this objective. Since the corporation had already been involved in
TQM and the team members had been exposed to the quality principles, it was easyto integrate
TQM into this project.
The team met twice a week over a period 2ofmonths. The initial meetings involved goal
setting and program organization followedby investigation of sources of toxicity. Based on a
review of the existing WWTF data and results from previous investigations, itwas suspected
that there were three sourcesof toxicity:
1. A cationic polymer used in the waste treatment processto enhance separation of biologi-
cal solids.
2. Unused ammonia nitrogen (ammonia fromthe WWTF influent, ammonia formedby min-
eralization of organic nitrogen in the influent, and ammonia addedto the WWTF influent
to supplement the biological requirement of the microorganisms in the treatment system)
in the biological treatment system
3. Untreated organics of the WWTF influent and possible intermediates formed during the
biological treatment
After the identification of “suspect” causes, laboratory tests were conducted for confir-
mation. Then pilot-scale testing was conducted to verify if removal of the suspect sources
would result in toxicity reduction. At the end of these studies, the following remedies were
suggested:
1. Replacement of the cationic polymer with another, less toxic polymer

594 Kodukula
2. Better process control of the polymer system (including regular “jar tests” to estimate
proper polymer doses, proper maintenance of polymer feeding system, etc.)
3. Monitoring of ammonia levels within the waste streams (including regular monitoring of
influent and effluent nitrogen parameters, supplemental addition of nitrogen to the bio-
logical treatment system onlywhen required, proper aeration basin pH control, etc.)
4.Operatorandtechniciantraining
Furthermore, it was recommended that the WWTF influent and the individual process
streams constituting the influent should be better characterizedto evaluate the presenceof po-
tentially toxic and nonbiodegradable substances. The project team was given authority to in-
vestigate and implement selected remedies in an expeditious manner, especially consideringthe
enormous costs associated witha potential consent order-driven investigation.
The recommended remedies were implemented immediately.As a result, no effluent tox-
icity permit violationshave been experienced for the last 3 years. Furthermore, the replacement
of the polymer has so far resulted in an operational cost savingof $750,000. Thiswas possible
because thenew polymer demand was much lower than the previous one. Also, since a consent
order from the regulatory agencieswas avoided, additional savings of several hundreds of thou-
sands of dollars were realized. As part of Phase I1 of the waste reduction program, studiesare
currently under way to reduce the amount of toxic organics released intothe WWTF influent.
B. Phase II
The ultimate goal of this phase of the program is to reduce the amount of toxic as well as
nontoxic organics in the liquid waste streams producedby different manufacturing unitsat the
plant. The specific objectives of this program are
1. To review the existing waste stream flow and TOC loading data of all the manufacturing
units
2. To prioritize the individual process streams based on their TOC loading
3. To characterize the flow and chemical composition of the top five waste streams
4. To evaluate waste minimizatiodpollution prevention options at each waste stream source
5. To implement those options that are deemed most cost effective
The first three tasks have already been completed. Out of 15 significant waste streams,10
were targeted for flow and characterization study. The chemical characterization included
many conventional parameters,priority pollutants, and several organic chemicals thatare spe-
cific to the waste streamof concern based onthe manufacturing process sources involved. The
sampling of these waste streams constituted sarhpling of 24-hr flow-weighted composite sam-
ples for 1-2 weeks. In cases where flow-based compositing was not possible, time-weighted
samples were taken. Based on the flow and analytical data, chemical losses have been quan-
tified. Specific pollution prevention and waste minimization options are currently being eval-
uated. The next phase of the program involves evaluation of other important solid hazardous
waste streams and air emissions for exploring waste minimization opportunities.
IV. CONCLUSION
The waste reduction program initiated at the subject manufacturing facility is based on TQM
principles. Thereis a strong commitment fromthe CEO of the corporation with a specific goal
to reduce wastesat the rate of 20% every year overthe next 5 years. This goal is currently being
achieved by a team effort at this facility, which involves process changes as well as improved
operations that are supported by employee training. Oneparticular team that worked ona spe-
Application of TQM
Prevention
to Pollution 595
cific project not only helped the facility meet its liquid effluent discharge toxicity limits
also but
saved more than $750,000 over the last 3 years. This team has received a corporate quality
excellence award forits teamwork and successful results. The company is now involved in the
next phase of pollution prevention, demonstrating its commitment to the TQM principle of
“continuous improvement.” Companies with established TQM systems can easily integrate
their pollution prevention and waste minimization programs into TQM. Such integration could
result in reduced waste management costs, increased environmental compliance, reduced lia-
bility, and greater community acceptance.
29
PC Software.for Optimizing
Groundwater Contaminant Plume
Capture and Containment
Richard C. Peralta, Herminio H. Suguino, and Alaa H. Aly

Utah Stare University
Logan, Utah
1. INTRODUCTION
Simulatiodoptimization ( S O ) models canbe used to speed the process of computing desirable
groundwater pumping strategies for plume management. They make the process of computing
optimal strategies fairly straightforward and can help minimize the labor and cost of ground-
water contaminant cleanup.
Differences betweenS/O models and the simulation (S) models currently used
by over 98%
of practitioners are discussed in Section I1 [l], followed by an overview of the two most com-
mon forms of groundwater managementS/O models, their strengthsand limitations, in Section
111. In Section IV, currently available PC-based S/O models are discussed, and the ways in
whichtheywouldbeappliedtorepresentativesituationsareillustrated.Includedis US/
WELLSD,an easy-to-use deterministicmodel that requires minimaldata but will address aqui-
fer and stream-aquifer systems where the analytical solutions of Theis [2] and Glover and
Balmer [3] are appropriate. Also included is US/REMAXB, appropriate for heterogeneous,
multilayer systems.To ease use, that code accepts datain format readableby MODFLOW [4],
the most widely used flow simulation model in the United States today.
These twoS/O models are selected because they are the only ones we are aware of(1)that
are available for use onPCs, (2) include with them the optimization algorithms necessary for
solution, and (3) use superposition. As explained later, these characteristics make them espe-
cially useful for plume management by consultants and water resource managers.
II. COMPARISON BETWEEN COMMONLY USED SIMULATION MODELS

AND SlMULATION/OPTIMIZATION MODELS
A simulatiodoptimization (90)model contains both simulation equationsand an operations
research optimization algorithm. The simulation equations permit the modelto appropriately
represent aquifer response to hydraulic stimuli and boundary conditions.
The optimization al-
597
598 Peralta et al.
gorithm permits the specified management objective to serve as the functiondriving the search
for an optimal strategy. Themodel computes a pumping strategy that minimizes(or maximizes)
the value of the objective function.
Table 1 shows generic inputs and outputs of the generally used simulation (S) model and
those of an S/O model. The normal S models compute aquifer responses to assumed (input)
boundary conditions and pumping values. Using such models to develop acceptable pumping
strategies can be tedious and involve much trial and error. For example, simulated system re-
sponse to an assumed pumping strategy might cause unacceptable consequences. In thatcase,
the user must assume another pumping strategy, reuse the model to calculate aquifer response,
and recheck for acceptability of results. This process of assuming, predicting, and checking
might have to be repeatedmany times. The numberof repetitions increaseswith the number of
pumping locationsand control locations (places where acceptability of system responsemust be
evaluated and ensured).
When using an S model, as the number of possible pumping sites increases the likelihood
that the user has assumedan “optimal” strategy decreases.Also, as the number of restrictions
on acceptable system response to pumping increases, the ability of the user to assume an op-
timal strategyalso decreases. Assuminga truly optimal strategy becomes impractical or nearly
impossible as problem complexity increases. There are too many different possible combina-
tions of pumping values. Furthermore, even if the computation process is automatedin a com-
puter program, the act of checking and ensuring strategy acceptability becomes increasingly
painful as the number of control locations becomeslarge. In essence, it becomes impossibleto
compute mathematically optimal strategies for complicated groundwater management prob-
lems using S models.
Alternatively, S/O models directly calculatethe best pumping strategies for the specified
management objectives and ensure that the resulting heads and flows lie within prespecified
limits or bounds (Table 1). The upper and lower boundsreflect the rangeof values that the user
considers acceptable for cell pumping rates and resulting heads. The model automatically con-
siders the bounds while calculating optimal pumping strategies. The user might choose to use
lower bounds on pumping at currently operating public supply wells. Hehhe might choose to
limit pumping at the upper end of the range, depending on hardware availability or legal re-
strictions. The user might impose lower bounds on head, at a specific distance below current
water levels or above the base of the aquifer. Upper bounds might be the ground surface or a
specified distance below the ground surface.
Assume, for example, a situation in which a planning agency is attempting to determine
the least amount of groundwater pumpingneeded to capture a contaminant plume and the lo-
cations where it should be pumped, i.e., the spatial distribution of the withdrawals and injec-
tions. If a pumping strategy isnot implemented to achieve capture, the contaminant will reach
public supply wells, resulting in litigation and undesirable costs.
Table 1 ComparisonBetweenSimulationandSimulatiodOptimizationModels
Model type values Computed
Input values
Simulation (S) boundary
Some flows boundary
Some flows
SomeboundaryheadsHeadsat“variable”head cells
Pumping
Simulatiodoptimization (90) Someboundary flows Optimalboundary flows
SomeboundaryheadsOptimalheadsat“variable”head cells
Bounds
pumping,
on Optimal
pumping
heads, flows
PC Software for Optimizing Plume Capture 599
An S/O model can be used to directly calculate an optimal pumping strategy for the goal
of minimizing the pumping needed to capture the plume without causing unacceptable conse-
quences. For example, assume that no injection mounds should reach the ground surface and
that no drawdowns should exceed 2 m. In addition, assume that potentiometric surface gradi-
ents near the plume should be toward the plume source.
The S/O model will directly calculate the minimum total pumping rate needed and will
identify how much should be pumped from each pumping location. The potentiometric surface
heads and gradients that will result from the optimal pumping willlie within the bounds spec-
ified initially (Table 1). In other words, future heads will not reach the ground surface, future
heads will not be more than 2 m below current heads, and final gradients will be toward the
contaminant source. Thus, the very first optimal pumping strategy computed by an S/O model
will satisfy all specified management goals.
111. COMMON S10 MODELING APPROACHES AND LIMITATIONS

Most S/O models employ either an embeddingor a response matrix approach for representing
system (head) responseto pumping [5]. Embedding models contain finite-difference or finite-
element equations embedded directly as constraints. In a finite-difference embedding model,
head and pumping values (or other flows) must be computed for each time step at each cell.
This is a very useful approach for those situationsin which (1) pumping should be a decision
variable at most cells,(2) head must be constrained in a high proportion of cells, (3) andeither
a steady-state strategy should be developed or there need be very few time steps. It is not as
desirable if there are relatively few pumping cells and control pointsor if many time steps are
needed. Thus, embedding models have been mainly used for steady-state regional planning and
for small hypothetical problems.
Response matrix S/O models use linear systems theory and superposition with influence
coefficients (e.g., [6]-[14] and many others). The matrix containing the influence coefficients
and superposition(summation equations) is termed theresponsematrix.Responsematrix
(RM) models use a two-step process. First, normal simulation (analytical or numerical) is used
to calculate system response to assumed unit stimuli. Then optimization is performed by an SI0
model that includes summation equations (discretized forms of the convolution integral).
Response matrix models are ideal for transient management situations. They require con-
straint equations for only those specific cells and time steps at which head or flow (other than
pumping) must be restricted during the optimization. To predict system response to the optimal
strategy at locations and times other than those constrained in S/O the model, an external sim-
ulation model is used after the optimization.
Regardless of the simulation approach used,S/O models share some of the limitations of
standard simulation models. Poor physical system representationor inadequate data will cause
error. One cannot properly optimize management of system processes that one cannot correctly
simulate. Useful simulatiodoptimization modeling presupposes that aquifer parameters are ap-
propriate and that actual boundary conditions are represented adequately within the model.
Both embedding and RM SI0 models generally assume system linearity during at least
some part of their processing operation. Confined aquifers are linear, unless they become un-
confined. Unconfined aquifers are nonlinear, but frequently the change in transmissivity is in-
significant, and they can be treated as if they were linear. Most commonly, system nonlinearity
is addressed by cycling. Cycling involves(1) assuming aquifer parameters (and computing in-
fluence coefficients for RM models), (2) calculating an optimal strategy,(3) recalculating sys-
tem parameters, (4) comparing assumedand newly calculated parameter values, and(5) either
stopping or returning to step 2 and repeating the process (if the assumed parameter values are
600 et Peralta al.
still inappropriate for the problem or if the optimal strategy is still changing with cycling).
Frequently, three cycles are sufficient for this convergence process.Thus, although both types
of models are completely applicablefor confined aquifers, some adjustmentsmust be made to
accurately apply them to unconfined aquifers.
Within S/O models, plume captureis generally achievedby controlling hydraulic gradients
and thus controlling advective transport. Generally, nonlinear transport equations are not in-
cluded. This approach permits the modeler to retain use of the characteristics of linear systems
(superposition, etc.). All of the RM model applications presented below achieve capture via
gradient control.
Concerning data input, SI0 models require all of the data needed by simulation models,
plus information on lower and upper bounds on decision variables (pumping rate, location) and
state variables (head, gradient, etc.). Although the same sort of information shouldbe required
when using an S model, the forced codification of these data as SI0 model input is helpful. It
causes the modeler to specify strategy acceptability criteria earlierthan he/she might otherwise.
Concerning model results, an S/O model might tell a user that the posed problem is in-
feasible. This means that the user has posed a problem for which all the constraints cannotbe
satisfied simultaneously. For example, the user might have instructed the model to cause the
head near an injection cell to reach at least 100 m above meansea level and simultaneously told
it that the upper bound on injection in 50 m3/day. If that injection rate is inadequate to cause
the required change in head, the model will declare the problem to be infeasible. The model
will be unable to determine even one pumping rate that can satisfy both conditions.
Of course, if there is more than one potential injection well, the same problem might be
feasible. In that case, the model can compute an optimal pumpingstrategy (probably the user
would have requested a strategy that minimizesthe total pumping neededto achieve that head).
Fortunately, S/O model users rapidly getbeyond the stage wherein they try to develop im-
possible pumping strategies (force the model to achieve goals that are impossible or mutually
exclusive when considering both the laws of nature and the goals of humans). Experience
brings the S/O modeler great ability to address common management problems.
IV. PC-BASED S/O MODELS AND SAMPLE APPLICATIONS

A. USM/ELLSD for Systems Addressable Using Analytical Solutions
1. ModelBackground
USWELLSD (Utah State extractiodinjection well system for optimal groundwater manage-
ment) is a deterministic version of an RM model. It uses influence coefficients based on an-
alytical equations for potentiometric surface response to pumping and river depletion resulting
from pumping. It is appropriate for systems where those analytical approaches are appropri-
ate-presumably relatively homogeneous systems. (Of course, in the management and con-
sulting arena, suchapproaches are commonlyapplied to heterogeneoussystems,with
acceptable error.)
Characteristicsof US/WELLSDare summarized in Table2. The overviewbelow is derived
from the user’s manual [15].
The objective function of the optimization module in USWELLS is generally applicable
and easily used for a variety of situations. The user can select either a linear or a quadratic
form. The linear objective function is to minimize
2 K
ware PC for Optimizing Plume Capture 601
Table 2 Characteristics of US/WELLSD and USIREMAX~

US/WELLSD USIREMAX~
Systems
addressed
One
Layer,
homogeneous Multilayer heterogeneous
Streadaquifer Streadaquifer
Stream stage not Stream stage affected
affected by pumping by pumping
Management
period
One or two stress periods One or multiple stress periods
of equal or unequal duration of equal duration
Steady stateor transient Steady stateor transient
Can rep. transient
evolutionary era with
terminal steady-state conditions.
Influence
coefficients
Deterministic Deterministic
Based on analytical expressions by Based on finitedifference
Theis and Glover and Balmer simulation (MODFLOW+STR)
Objective
function
Min or max
pumping Min or max pumping
or combination or combination
Time-varying weight for Diff. weight for each
extraction and injection pumping location
Boundsandconstraints g L Ig 5 gLS g Igu
hLSh5hU hLIh5hU
Ah:,, 5 Ahl,2 S AhF2
U
Gt.2 S G1.2 IG . 2
v4.2 5 v1.2 5 vy2

= 1.0
x (Ext)
2 l.x
X (Ij) ' e o
= 1.0
2 1.0
X(Ext)L5 X(Ext)5 X(Ext)'
Notes: Superscripts L and U refer to lower and upper bounds; g = extraction or injection, [L3/T]; h = head.; A h ,
G,.2,V,.2 = head-difference, gradient, and velocity, respectively, between any two locations, [L], dimensionless,
or [UT]; (Ext), H (Inj) = total extractionor injection, [L3/T]; d = stream depletion, [L3/T].
where WE,xand W,,x are the cost coefficientor weight assignedto extraction ( E ) or injection
, time period, [$/(L3.T)] or dimensionless; Ej, and JkJ are extraction ( E ) or
(f) rates in the x
injection (0 rate at well j (or k) in the time period, [L3/T]; and J and K are number of
extraction (J)or injection ( K ) wells.
Potential constraints are the following.
1. Hydraulic gradient between any gradient control pair of wells at any time period must be
within user-specified bounds. This can ensure that wateris moving only in the desired di-
rection. The maximum value can differ for each gradient control pair and time period. This
constraint is useful, for example, when US/WLLSDis used for groundwater contaminant
plume immobilization or for any situation where hydraulic gradient control is desired.
2. Extraction or injection rate at any well must be within user-specified bounds (lower and
upper limits). If the user cannot decide if a certain well should be used for extraction or
injection, he can locate one of each at the same location. The model will then determine
either an extraction or an injection rate, or neither, for that location.
602 Peralta et al.
3. Hydraulichead at any injection, extraction, or observation wellmustbewithin user-

specified lower and upper bounds. For example, a lower bound may be used to maintain
adequate saturated thickness. An upper bound may be used to prevent surface flooding or
to eliminate theneed for pressurized injection. These lower and upper bounds can differ for
different locations. The boundsare the same for both time periods.
4. Total import or export of water can be controlled to be within a user-specified range. The
user canalso completely prevent importor export of water or both. If no importor export
of water is allowed, the total optimal extraction must equal the total optimal injection.
5. Depletion from the river must be within user-specified bounds (lower and upper limits).
This is applicable only if a river exists in the considered system.
6. Constraint 3 is modified such that the probability that the actual change in head at any
point in the groundwater systemis not less than the change calculated by the model or is
not greater than the change calculatedby the model and is at least equal to the reliability
level specified by the user. (This ability is found only in an alpha-test chance-constrained
version of the model, US/WELLSS, which considers the stochastic nature of hydraulic
conductivity. The utilized chance constraint is more accurate than previously reported
formulations.)
Optionally, US/WELLSDcan use a quadratic objective function to minimize
x= I j= 1 j= I k= I
where Hi, is the dynamic lift, the difference between ground surface elevation and optimal
potentiometric head resulting at extraction well j at the end of the xth time period, [L]; and
W,, is the weight assigned to the power used for extraction in the time period, [$/L.T)].
The weighting factors can be used to emphasize differentcriteria and different timeperi-
ods. For example, assume a problem of minimizing the total extraction usingthe linear objec-
tive function. If the second time period is chosen be to much longer than the first time period
and the weights assigned to extraction and injection in the second time period are larger than
those used for the first time period, then the solution will tend to minimize steady-state ex-
tractiodinjection rates, andlessattentionwillbegiven to the short-term transientrates.
Through the weighting factors, US/WELLSD can also be used for maximizing pumping rates
for water supply problems.
2. ApplicationandResults
Here we illustrate the use of US/WELLSDto determine the optimal time-varying sequenceof
extraction and injection of water in prespecified locations needed for first immobilizing and
then extracting a groundwater contaminant plume.In this example, the user specifiespotential
locations of extraction and injectionwellsaroundthecontaminantplume(Figure 1). US/
WELLSD then determines optimal extraction and injection rates for different time periods.
To illustrate model flexibility, four potential extraction wells and five potential injection
wells are considered for placement outsidethe contaminant plume during the first period. In the
second time period, three extraction wells are considered for placement inside the plume (to
extract contaminated water) and five potential downgradient injection wells are considered.
During both periods, the resulting hydraulic gradients (between 10 pairs of head observation
locations) must be toward thecenter of the plume. Alternatively, the user could choose to min-
imize the pumping needed to capture the plume using only internal extraction wells in one or
both periods.
0 Potentlal inlectlon Well

Observation Well
lnltial
I
Groundwater
Gradient
1
0.1 96
1 Contaminated
Plume
6
3 K :75 mlday (isotropic)

I
0
.
X
Figure 1 Hypothetical study area for Example A, addressable with USWELLSD.
Here, the quadratic objective function is used and employs greater weights for the second
time period than the first period. This supports the fact that the second period is much longer
than the first. In addition, neither export nor import of water is allowed-total injection must
equal total extractionin each period. All the above considerationsare incorporated within the
model via the input data [15]. The user also specifies lower and upper bounds on head and
pumping rates.
Figure 2 shows US/WELLSD output, in meters and m3/day. This contains, in addition to
the input bounds(L.Bound and U.Bound), the optimal values of the decision variables (pump-
ing), state variables (head and gradient), and marginal values.
The marginal is definedas the valueby which the objective function will change if a tightly
bounded variable changes one unit. If a variable’s optimal value is not equalto either its lower
or upper bound, its marginal will be zero. That is, the marginal will be nonzero only if the
optimal value of the variable equals one of its bounds. In this case, the marginal shows the
improvement of the value of the objective function resulting from relaxing thisbound by one
unit. Marginals are valid only as long as no other variable also changes in value. Thus they
might be valid for only a small range of change in the bound.
To illustrate, the output file (Figure2) shows that the marginal of the optimal injection rate
in the firsttimeperiod at injectionwell 3 is -45.3. Theobjectivefunctionvaluewas
334,668.1. If the upper bound on injection in the first time period is relaxed by one unit at the
mentioned well (that is, the new upper bound 901isinstead of W),one would expect the value
of the objective function to change by about -45.3 to 334,622.8. If this change is actually
made and the model is rerun, the resulting change in objective function value is -45.4.
Marginals are useful in determining how to refine an optimal strategy. They help one to
decide which bounds or constraints shouldbe looked at more closelyand perhaps relaxed. They
also indicate the trade-off between that bound and objective achievement. They showhow
much one is giving up in terms of objective attainment to satisfy that restriction.
604 Peralta et al.
MODEL STATUS : OPTIMAL SOLUTION FOUND

VALUE OF OBJECTIVE FUNCTION 334668.1
OPTIMALEXTRACTIONRATES
FIRSTTIMEPERIOD
Well No L.Bound Optimal U.Bound Marginal
1 0.00 745.42 900.00 0.000
2 0.00 447.60 900.00 0.000
3 0.00 448.71 900.00 0.000
4 0.00 747.86 900.00 0.000
5 0.00 0.00 0.00 0.000
6 0.00 0.00 0.00 0.000
7 0.00 0.00 0.00 0.000
SECONDTIMEPERIOD
No Well Optimal
L.Bound U.Bound Marginal
1 0.00 0.00 0.00 81.955
2 0.00 0.00 0.00 81.627
3 0.00 0.00 0.00 81 -605
4 0.00 0.00 0.00 81 -913
5 0.00 426.53 900.00 0.000
6 0.00 883.77 900.00 0.000
7 0.00 428.90 900.00
"""""""-""""""""""""""""""""""""""""""
......................................
0.000
OPTIMALINJECTIONRATES
FIRSTTIMEPERIOO
L-BOund
Optimal
No Well U.Bound Marginal
l 0.00 211 -66 900.00 0.000
2 0.00
900.00 328.89 0.000
3 0.00 900.00900.00 -45.342 < = = = eMdnedin text
4 0.00 900.00 900.00 0.000
5 0.00 900.00 49.04
0.000
SECOND T I M E PERIOO
Well No L.Bound
Optimal
U.Bound Marginal
1 0.00 0.00 900.00 132.584
2 0.00 900.00293.53 0.000
3 0.00 900.00 900.00 -4.3E+2
4 0.00 545.67 900.00 0.000
5 0.00 0.00 132.583900.00
......................................
~~~~~~"""~~""""""""~""~""""""""""""
OPTIMAL HEADS AT OBSERVATION WELLS
FIRSTTIME PERIOO
Well No L. Bound Optimal U.Bound Marginal
1 -
30 00 35.69 40.00 0.000
2 30.00 35.54 40.00 0.000
3 30.00 35 -60 40.00 0.000
4 30.00 35.55 40.00 0.000
5 30.00 35.70 40.00 0.000
6 30.00 35 -79 40.00 0.000
7 30.00 35.92 40.00 0.000
8 30.00 35 -88 40.00 0.000
9 30.00 35.84 40.00 0.000
10 30.00 35.77 40.00 0.000
11 30.00 35 -65 40.00 0.000
12 30.00 35 -60 40.00 0.000
13 30.00 35.65 40.00 0.000
14 -
30 00 35.79 40.00 -
0 000
15 30.00 35 -88 40.00 0.000
16 30.00 35.77 40.00 0.000
Figure 2 US/WELLSDoutput file for Example A.

PC Sofmare for Optimizing Plume Capture 605
SECOND TIME PERIOD
NoWell L. Bound Optimal Marginal

U.Eound
1 35 30.00 -62 40.00 0.000
2 30.00 35 -62 40.00 0.000
3 30.00 35-68 40.00 0.000
4 35.62 30.00 40.00 0.000
5 35 30.00 -63 40.00 0.000
6 35.66 30.00 40.00 0.000
7 35.75 30.00 40.00 0.000
a 30.00 35-74 40.00 0.000
.00 9 35-71 40.00 0.000
0.00 10 -64 40.00 0.000
40.00 11 35.56 30.00 0.000
40.00 12 35.54 30.00 0.000
13 30.00 35.S6 40.00 0.000
14 0.000
40.00 15 35.74 30.00 0.000
16 40.00 0.000
"""""""""""""""""""""""""""""""""""""-
_""""
OPTIMAL HEADS AT EXTRACTION WELLS
FIRST TIMEPERIOO
Well No L. Bound Optimal U.Bound Marginal

1 30.00 35-09 40.00 0.000
2 30.00 35.29 40.00 0.000
3 30.00 35.29 40.00 0.000
4 30.00 35.09 40.00 0.000
5 30.00 35.61 40.00 0.000
6 30.00 35-62 40.00 0.000
7 30.00 35.61 40.00 0.000
SECONDTIMEPERIOD
Well No L.Bound Optimal U;Bound Marginal

1 30.00 35.69 40.00 0.000
2 30.00 35.72 40.00 0.000
3 30.00 35.73 40.00 0.000
4 35.70 30.00 40.00 0.000
40.00 5 35.24. 30.00 0.000
6 30.00 34-90 40.00 0.000
7 30.00 35.25 40.00 0.000
...........................................................................
OPTIMAL HEADS AT INJECTION WELLS
FIRSTTIMEPERIOO
Well No L.Bound Optimal U.Bound Marginal

1 30.00 35-90 40.00 0.000
2
40.00 36.03 30.00 0.000
3 36.46 30.00 40.00 0.000
40.00
4 36.47 30.00 0.000
5 30.00 35.a3 40.00 0.000
SECONDTIMEPERIOO
Well No Optimal
L.Bound U.Eound Marginal
1 30.00 35-65 40.00 0.000
2 35-88 40.00 0.000
3 30.00 36.33 40.00 0.000
4 30.00 36.08 40.00 0.000
5 30.00 35.67 40.00 0.000
Peralta et al.
OPTIMALHYDRAULICGRADIENTS
FIRSTTIMEPERIOD
From To L. Bound Optimal U. Bound Marginal

1 -> 11 0.D0000 0.00055 0.01D00 0.000
3 -> 12 0.00000 0.00003 0.01000 0.000
5 -> 13 0.00000 0.00019 0.01000 0.000
6 -> 14 0.00000 0.00000 0.01000 1.17E+7
7 -> 14 0.ooooo 0.00157 0.01000 0.000
8 -> 15 0 .ooooo 0.00000 0.01000 3.26E+7
9 -> 16 0.00000 0.00087 0.01000 0.000
10 -> 16 0.00000 0.00000 0.01000 1.17E+7
SECONDTIMEPERIOD
From
To L. Bound Optimal U. Bound Marginal
1 -> 1 1 0.00000 0.00082 0.01000 0.000
3 -> 12 0.00000 0.00241 0.01000 0.000
5 -> 13 0.00000 0.00027 0.01000 0 IO00
6 -> 14 0.00000 0.00014 0.01000 0.000
7 -> 14 0 .ooooo 0.00115 0.01000 0.000
8 -> 15 0.00000 0.00000 0.01000 2.88E+8
9 -> 16 0.00000 0.00081 0.01000 0.000
10 -> 16 0.00000 0.00000 0.01000 0.000
Figure 2 Continued.
B. US/REMAXBfor Heterogeneous Multilayer Systems

1 . Model Background
For optimizing management of complex heterogeneous systems, one would rather useUS/
REMAXB [l61 than US/WELLSD.This is the basic version of the Utah State response matrix
model. To develop influence coefficients, it uses code modified fromMODFLOW, a modular
finite-difference groundwater flow simulation model [4], and STR, a related stream routing
module [17]. The physical system data neededby US/REMAXDcanbeinputin the same
format as is used by MODFLOW and STR. Internally, US/REMAXB also uses a portion of
PLUMAN, a decision support system for optimal groundwater contaminant plume manage-
ment [18], and other code.
The optimization model formulation capabilities are similar to those of US/WELLSD (Ta-
ble 2). For steady state, the generic objective is to minimize
J K
where Wjis the weight assigned to pumpingin cellj, dimensionless or [$.T/L3].US/REMAXB

can employ constraints 1-3 of US/WELLSDfor multiple layers. Similar to the US/WELLSD
constraint 4, US/REMAXB can force total extraction to exceed, equal, or be less than total
injection. Again, via the sign on the weighting coefficients, one can perform maximization.
One can also achieve multiobjective optimization by the weighting method. Whereas in US/
WELLSD the same weight must be applied to all extraction wells in a time step (and a different
weight can be used for injection wells, but the same must be applied to all such wells in a
particular time step), in US/REMAXB eachwell can employ a different weight.
PC Software
Capturefor
Plume
Optimizing 607
2.Application andResults
Introduction. For illustration, we discuss addressing a contaminant plume in a representative
study area. First, the study area is describedand the results of continuing current management
are predicted, using MODFLOW+STR for flow simulation and MOC [l91 for transport sim-
ulation. Then an approach to developing an optimal strategy is discussed, the S/O model is
applied, and an optimal strategy is computed. Next, the system response to implementing the
optimal strategy is verified using MODFLOW+STR and M W . Finally, slight variations in
themanagementgoal or situation areassumed andnew optimalstrategiesaredeveloped.
Computed optimal strategies are compared. Suguino [20] first addressed this study area using
PLUMAN. Some of the discussion below follows his development.
Study Area Description and Situation. The area (Figure 3) measures about 4.3 km by 4.3 km.
It is bounded on the north by a large saltwater body; on the south, east, and northwest by
impermeable material; and on the west by a lake. A river transects the area from south to
north. Aquifer parameters of this example study area were obtained from ranges reported by
Todd [21].
For the unconfined upper layer (layer l), parameters are as follows.
Hydraulic conductivity:
1stzone: 45 d d a y (coarsesand)fromlaketocontaminantspillarea(columns 1-36and
57-58)
2nd zone: 30 d d a y (medium sand) in irrigated area (columns 51-56)
3rd zone: 450 &day (fine gravel) in contaminant spill area (columns 37-50).
Specific yield:
1st zone: 0.27 (coarse sand)
2nd zone: 0.28 (medium sand)
3rd zone: 0.25 (fine gravel)
Figure 3 Finite-difference grid for the area addressable with US/REMAXB.

608 Peralta et al.
Recharge by deep percolation and/or irrigation:

1.167 X d s e c in nonirrigated
area
1.928 X d s e c in irrigated area
In the confined lower layer (layer 2):
Transmissivity: 0.1564 m*/sec
Saturated thickness: 30.0 m
Storage coefficient: O.OOO1
Finite-difference modelsare to be used in this study. This requires systemdiscretization.
The resulting block-centered cell grid (Figure 3) has 58 columns and 39 rows. Cell side lengths
range from 3 to 400 m. Because MOC will be used for transport simulation near the plume,
cells of uniform size are specified for that region. The resulting 17 row by 20 column region
(subsystem) near the plume has squarecells of 15.2 m (50 ft) side length.
A conservative (nonreactive) contaminantis assumed to be spilled in the top aquifer layer
(layer 1) of cell (22, 18) or (ll,, 3,). (The subscript “S” after a cell row or column index in-
dicates that the cell is in the subsystem.) This cell is treatedas a continuous source during the
management period.
Initially, pumping for water supply occurs in two cells between the plume and the river.
One well is in layer 1 of (23, 15) or (12s, 15,). The other well is in layer 2 of (18, 18) or (7,,
18,). There is immediate concern about the potential for contamination reaching the supply
well in layer l .
Nonoptimal System Response Determination (Step 1). Before one attempts to develop an op-
timal strategy, one usually demonstrates the need for such a strategy. This requires predicting
system response if no optimal strategy is implemented. Frequently, simulation models are used
for this action. Here, MODFLOW+STR computes the potentiometric surface that will result
from assumed steady-state conditions (Figure 4).
Because of the gradient, the contaminant will tend to migrate toward the supply wells.
M W is used to quantify the migration resultingin the subsystem from the steady flow. Figure
5 shows the 210 ppb contour expected to result 60 days after contamination begins. Further-
more, concentrationin the cell containing the drinking well (12,, 15,) reaches 3 17 ppb 8 months
after the spill. We assume that this concentration level exceeds the health advisory for human
consumption and that developing a plume capture strategy is desirable.
Management Goals Specification and SI0 Model Formulation for Scenario l (Step 2). The
assumed goal is to minimize the steady pumping (extraction and injection) needed to capture
the plume. Plume capture will presumably be achieved when hydraulicgradients, just outside
the plume boundary, all point toward the plume interior. We also want the head at extraction
wells not to drop too far (to avoid reducing saturated thicknessby more than about 10%)or the
head at injection wells not to rise to the ground surface. These criteria identify the example
problem termed Scenario 1 .
The SI0 model formulation for this scenario is shown below. The model computes the
pumping strategy that minimizesthe value of the objective function, subject to the stated con-
straints and bounds. Locations of potential injection and extraction wells to be considered by
the model are shown in Figure. 5. Figure 6 identifies head difference (gradient) control cell
pairs and shows the direction that will be imposed on the hydraulic gradient by any computed
optimal strategy. Theseare placed to enclose the plume projected to exist by day 60.A modeler
can select potential well locations on the basisof practical experience.For example, the closer
the injection wells are to the head gradient control locations, the less pumping is needed to
PC Sofnvare for Optimizing Plume Capture 609
I
H
Figure 4 Nonoptimal (unmanaged) steady-state potentiometric surface contour map for the study area
of Scenario 1 (meters above MSL).
Js
1 2 3 4 5 6 7 8 9 1 0 1 1 1 2 ~ 1 1 5 1 5 ~ 1 8 1 9 2 0 legend
12
l3 unmanaged wen
14 [ I 1 layer 1
U [ 2 ) layer 2
16 potential managed
l7 injection well
18 potential managed
8 19 extraction well
‘S
9
10
20
21
22
’ contamlnantsource
B 210 ppb concentration
11
12 23 contour
l3 24
14 25 meter
K 26 0 K30 45
16 27
28
5
17
16ll79 21 23 25 27 29 31 33 35
J
Figure 5 Subsystem discretization, potential well locations for Scenario 1, and 210 ppm contour, 60
days after contamination begins.
610 Peralta et al.
J*
1 2 3 4 5 ' 6 7 8 9101112l314lSl617181920
Legend:
1 12
2 13 unmanaged wen
3 14 ( 1 1 layer 1
4 Is ( 2 1 layer2
5 l6 potential managed
6 l7 lnJectionwell
7 #) (upper bound on head)
8 19 Q potential managed
9 2o I extraction well
'S ta 21 (lower bound on head)
11 22
l2 23 contaminant source
l3 24
14 25
+ gradient canstraint
15 26 0 IS 30 45 m
16 27
l7 28 tS¶
16 17 l9 2321 25 2927 31 33 35
d
Figure 6 Head-difference constraint locations applied within the S/O model in Scenario 1.
satisfy the head-difference constraint. Thus, the modeler might want the model to consider
pumping sites near the location where heads need most to be affected.
The model objective is to minimize the value of Equation (3), using weights of 1, sub-
ject to
Gb 2 0.01, for B = 1, . . . , 22 (4)
hp 2 15.0, for 2 = 1, . . . ,6 (5)
h* I25.0, for 2 = 1, . . . , 25 (6)
where GBis the difference in head between a pair of cells, the first located farther from the
plume. A positive value denotes a higher head farther from the plume, [L]; ha is the hydraulic
head just outside the casingof pumping well P located in the center of a pumping cell, [L]; 6
is the index denoting pair of cells head-difference (gradient) control pair; and 6 is the index
denoting pumping well at the center of cell j or k. Here j = 6 and k = 25.
Note that identifyingthe location of potential extraction and injection wells forthe model
(Figure 5 ) does not mean that the model will choose to pump at those locations. Via the op-
timization process, the model might choose to pump at only a few of the potential sites. The
computed strategy will require less total pumping than any other strategy possible forthe spec-
ified potential well locations and imposed bounds and constraints.Furthermore, since this isa
steady-state problem, steady-state system responseto implementing the strategy computedby
the model will satisfy all those bounds and constraints. This is verified in the next step.
Optimal Strategy Computation and Verificationfor Scenario I (Step 3). The optimal strategy
computed for Scenario 1 is shown in Table 3. Because the model is minimizing pumping only
for plume containmentin layer 1, no extraction is shown for layer 2. The original unmanaged
pumping does continue from original supply wellsin both layers (Figure3) but is not included
in Table 3 because the model is not optimizing that pumping.
ware PC Capturefor
Plume
Optimizing 611
Table 3 Pumping Results for the Sample Scenarios

g(eW
b(inj.) (g + b) total
Constraints
Scenario (@m) Layer 2nd1st Layer
(m’lsec)
~~~ ~
1 onconstraint
Gradient 0.01338 - 0.03358
0.02020
samethe located
on
heads (212.05) - (320.13)
(532.18)
layer, head constraint on
injection and extraction well.
2 constraint:
pumping
Added 0.01702 - 0.03404
0.01702
extraction
of
sum
total = total (269.74) - (269.74)
(539.48)
sum of injection.
3 heads
Gradient
constraint
on 0.00300
0.00329
0.03786
0.04415
same
and
located
theon on (47.54)
(52.14)
(600.03)
(699.69)
different layers, head constraint
on injection and extraction wells.
Figure 7 shows the locations of wells that will pump, according to the optimal strategy. It
also shows the head-difference constraints [Equation (4)] that will be tight. Tight constraints
are those that are satisfied exactly. The other gradient constraints are also satisfied, but the
model had no difficulty in doing so. These latter head-difference constraints are “loose” (there
is more than0.01 m difference between the heads at the two cells coupledby an arrowin Figure
6 but not shown at all in Figure7). No heads are against their bounds. Therefore neither Equa-
tion (5) nor (6) is tight.
It is appropriate to verify that the computed strategy accomplished its goal of plume cap-
ture. MODFLOW+STR can be used to demonstrate how quickly the optimal steady pumping
%
l 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 1819 20
12 I.egend:
13 unmanaged well
14
( 1 1 layer 1
15
c21 layer 2
16
n activemanaged
18 injection well
19 actiuemanaged
9 20 I extraction well
Is
1contaminant MUI ’ce
10 21
11 22
12 23 + lightgradient
l3 24 constraint
14 25
15 26 meter
16 27 0 63045
ti 28 Ea
16 l7 19 21 23 25272931 33 35
J
612 Peralta et al.
strategy will cause the desired gradients to occur. Transient simulation demonstrated that the
gradient constraintswould be satisfied 30 days after implementing the optimal pumpingstrat-
egy (Figure 8). Figures 9 and 10 show the ultimate steady-state surface resulting from strategy
implementation. Clearly, a groundwater divide has been formed between the plume and the
supply well.
MOC is used to predict the pollutant transportthat would result from strategy implemen-
tation. No contaminant moved past the injection wells.
Theoretical verificationof the optimality of the computed strategyis beyond the scope of
this document. However, many texts onoperations research and linear programming assure the
optimality of solutions to models havinga linear objective function and constraints'.
Alternative Scenarios.
Scenario 2. This scenario differs from the previous in the addition of a constraint forcing
total injection to equal total extraction around plume.
the Again, pumping fromthe two supply
wells is not included in the total.
aquifer optimal a l l gradients check of

contam. punping constraints cont.conc.
beg ins ach i eved
I -I I I
0 60 90 240 days
Figure 8 Time scale of Scenario 1.
J - column
3
0
c
l
H
Figure! 9 Subsystem potentiometric surface resulting from implementing the optimal pumping strategy
for Scenario 1 (meters above MSL).
Well Ips gprn Well Ips gpm

I 1.36 2l.56 6 -3.09 -449.02
2 0.62 9.89 7 5.02 79-58
3
4
-
"0.60
- -EX55
9.69
9.49
9
8 4.46
7.88
'M.67
l2496
S 0.85 13.46 10 -100.00 "158482
Figure 10 Subsystem potentiometric surface resulting after6 months of optimal pumping for Scenario
1 (meters above MSL).
Results in Table 3 show an increase in extraction and a decrease in injection. Total pump
ingneeded for plume containment increased slightly (1.4%). This illustrates the phenome-
non-increasing the number or restrictiveness of constraints does not improve the value of the
objective function.
Although total pumping increased, one less extraction well is used in this strategy than in
the previous (Table 4). The same number of gradient constraintsare tight, but the locations of
the tight gradient constraints differ slightly.
Scenario 3. This scenario demonstrates what might happen if involved managers have
conflicting goals. It differs slightly fromScenario 1. In addition to controlling the plume, the
agency wishes to extract more from layer 2 for water supply. Three new potential extraction
wells are located in cells (19,25), (20, 25), and (21, 25), as if along a nearby road. Pumping
is not permitted to change at the two initial supply wells.
Table 4 Numbers of Managed Wells that Will Pump Under the Optimal
Strategies for the Tested Scenarios
g(extr.1
Scenario Layer
Layer
2nd
1st Hinj.) (g + b) total
l 3 - 6 9
2 2 - 6 8
3 4 3 14 21
614 Peralta et al.
As a result, the objective function is altered

to maximize new extraction from layer
2 while
still minimizing the pumping in layer 1 needed to capture the plume. This is achieved by as-
signing a negative sign to extraction from the supply wells, and minimizing:
I K
Since minimizing a negative number is the same as maximizing a positive number, minimizing
negative extraction in layer2 means maximizing that extraction.
Also added are new constraints imposed on vertical flow in cells (21, 21) and (22, 21).
There, the head in the lower layer is forced to exceed that in the upper layer by 0.01 m, pre-
venting the downward migrationof contaminant.
Figure 11 shows the resulting optimal injection and extraction well locations and tight gra-
dient constraints. The optimal pumping strategy includes seven extraction wells and 14 injec-
tion wells. Although extractionof polluted water decreases, injection increases with respect to
Scenario 1 (Table 3). Extraction of water for public supply increases by 31% above the un-
managed rate.
Although the gradient constraints are all satisfiedby the optimal strategy, subsequent sim-
ulation demonstrated that the vertical gradient is reversed in some plume-containing cells in
which the gradient was unconstrained. This illustrates that one must be careful in placing head
or gradient control in appropriate locations. In practice, another optimization would be per-
formed, using additional vertical head-difference or gradient constraints.
Processing Considerations. It is useful to consider the resources required to address optimi-
zation problems. First, the total computer time needed to solve an optimization problem is of
Js
1 2 3 4 5 ' 6 7 8 9101112I3MlSl6~181920 ~~~d
1
2
l2
l3 B unmanagedWen
3 14 ( 1 1 layer 1
4 15 ( 2 I layer 2
5 16 actiuemanaged
6 n inJection well
7 18
19 actiuemanaged
8 wtraction well
9 20 I
Is 10 21 contaminant source
l1 22
23 c tight grad. wnstr.
l2 (heads on samelaywl
l3 24
++ tight grad.constr.
14 25 (heads ondiff. layer1
15 26 meter
16 27 0 15 3045
17 28 Ea
16 17
9. 21 23 25 27 29 31 33 35
J
Figure 11 h a t i o n of optimal pumping wells andtight head-difference (gradient) constraints for Sce-
nario 3.
PC Software
Capturefor
Plume
Optimizing 615
interest. Table5 illustrates the time neededto address Scenario 1. Included stages useeither the
discussed simulation models or the PLUMAN code on a 386 PC running at 33 MHz and having
4 MB RAM. Time required for US/REMAXB is comparable to thatof PLUMAN, since it uses
many of the same solution procedures.
Clearly, the stage of computing influencecoefficients, arranging the optimization model,
and calculatingan optimal strategyis the most computationally intensive.For this scenario and
stage, two steps can be distinguished. Thefirst involves computing influence coefficients. The
second is model organization and optimization problem solution.
Here, the step of generating influence coefficients requiresby far the most time. This re-
sults because this act essentially involves one simulation of a modified MODFLOW+STR per
potential pumping location. Since thereare 31potential pumpinglocations, 31 simulations are
performed to develop the influence coefficientsneeded for the response matrix. Themore de-
cision variables (potential pumping rates), the more computer time involved in this step.
The step involving model formulation and calculation of the optimal strategy is fairly
short. The time needed to perform the optimization is a function of the number of decision
variables (potential pumping rates) and state variables (heads or gradients that must be con-
strained within the optimization model). The larger these numbers, the more time required.
Second, the size of the optimization problem being solved is of interest. For example,
the special versions of US/WELLSD and US/REMAXB that are released in shortcourses are
limited in the number of nonzero values they can have in the optimization formulation. (Even
optimization algorithms that are not part of water management models are commonly lim-
ited either in the number of nonzeros or in the number of rows and columns in their constraint
equations.)
By way of explanation, there is one row in the response matrix per heador gradient con-
straint equation per time step of constraint. There is one column in the matrix per decision
variable. For a steady-state problem, total matrix size is the product of the number of control
locations andthe number of decision variables.The matrix contains one nonzero coefficientfor
each potential pumping location-head control location pair (per time step of active constraint).
+
For the steady-state Scenario 1, there are 31 X (22 31), or 1643, nonzeros due to in-
fluence coefficients. Thereare also 31nonzeros due to the weighting coefficients (even if they
are 1in value) assigned to decision variables in the objective function. Thus, the optimization
model formulation for Scenario 1employs almost 1700 nonzeros. (That of Scenario A using
US/WELLSD includes919 nonzeros.) This number can be reduced significantly by considering
injection in only every other cell on the plume periphery rather than in each cell. For example,
ifonly 12 injectionwellswere considered, thenumber of nonzeroswouldbeabout
18 X (22 + +
18) 18, or 738. In addition to reducing problem size, this would significantly
reduce computational time.
Table 5 Computer Time Required to PerformEach Activity for Scenario 1

min) Step Time Software used
1 MODFLOW+STR
head) nonoptimal
(compute 5.0
2 MOCnonoptimal
(predict
atransport
solute
potent
surface)
in 35.0
3 PLUMAN (compute influence
coefficients,
formulate
management
model 150.0
and determine optimal pumping strategy)
4 MODFLOW+STR (compute transient
head
response
to
optimal
pumping) 1.3
5 MOC (compute head
and
solute
transport
response to optimal
pumping) 8.0
616 Peralta et al.
Reducing the number of nonzeros below IO00 is important becausethat is theupper limit
on problem size in the inexpensive “special” versions of US/REMAXB and US/WELLSD.If
problem size increases beyond that, software price increases dramatically. The full professional
versions of the software can address problemsof virtually unlimited size.
V. SUMMARY
Use of simulationloptimization modelscan significantly aid managementof groundwater con-
tamination. It can speed the design process and reduce manpower costs. It can improve the
produced remediation designs and reduce remediation costs. It can easily address problems pre-
viously considered very difficult.
S/O modeling methods for groundwater flow management have been well established in
research literature. Now, generally applicable S I 0 models are available for use on Pcs. The
discussed models, US/WELLSD and US/REMAXB, use linear systems theory, influence co-
efficients, and superposition. These models can addressa wide rangeof problems. Easyto use,
they include all simulation and optimization algorithms neededto compute optimal strategies.
US/WELLSD and US/REMAXBare perfectly applicable to linear (confined) aquifer sys-
tems and can be applied to nonlinear systems. The former is most appropriate for fairly ho-
mogeneous aquifer and stream-aquifer systems.The latter can address complex heterogeneous
multilayer stream-aquifer systems.
Increasing use of these PC-based S I 0 models is anticipated, especially as user-friendly
options increase. Even the special versionsof these models (releasedat shortcourses),can solve
important real-world problems.
REFERENCES
1. Peralta, R. C., and Willardson, L. S . , Optimizing ground water planning and management, U.S.
Committee on Irrigation and DrainageNewsletter, AprilIJune 1992, Denver, Colo., pp. 61-65.
2. Clarke, D., Microcomputer Programsfor Groundwater Studies, Elsevier, New York, 1987.
3. Glover, R. E., and Balmer. G. G., River depletion resulting from pumping a well near a river,
Trans. AGV, 35(3), (1954).
4. McDonald, M. G., and Harbaugh, A. W., A modular threedimensional finite-difference ground-
water flow model, inTechniques of Water-Resources Investigations,U.S. Geological Survey, 1988,
Chapter Al, Book 6.
5. Gorelick, S. M., A review of distributed parameter groundwater management modeling methods,
Water Resources Res., 19(2), 305-319 (1983).
6. Morel-Seytoux,H. J., A simple case of conjunctive surface-ground-water management, Ground
Water, 13(6) (1975).
7. Verdin, K. L., Morel-Seytoux, H. J., and Illangasekare, T. H., Users Manual for AQUISIM: FOR-
TRAN N Programs for Discrete Kernel Generationand for Simulation of Isolated Aquifer Behavior
in 2 Dimensions, HYDROWAR Program, Colorado State Univ., Fort Collins, Colo., 1981.
8. Heidari, M., Application of linear systems theory and linear programming to groundwater man-
agement in Kansas, Water Resources Bull., 18(6), 1003-1013 (1982).
9. Illangasekare,T. H.,Morel-Seytoux, H. J., and Verdin, K. L., A technique of reinitialization for
efficient simulation of large aquifers using the discrete kernel approach, Water Resources Res.,
20(11), 1733-1742 (1984).
10. Danskin,W. R.,and Gorelick,S. M., A policy evaluation tool: management ofa multisystem using
controlled stream recharge, Water Resources Res., 21( 1l), 1731-1747 (1985).
11. Lefkoff, L. J., and Gorelick, S . M.,AQMAN. Linear and Quadratic Programming Matrh Gener-
ator Using lbo-Dimensional Ground-waterFlow Simulation for Aquifer Management Modeling,
U.S.Geological Survey Water-Resources Investigations Rep. 87-4061, 1987.
oftware PC Capture
forPlume
Optimizing 617
12. Reichard, E. G., Hydrologic influences on the potential benefits of basinwide groundwater man-
agement, Water Resources Res., 23(1), 77-91 (1987).
13. Ward,R. L., andPeralta,R.C.,EXEIS-ExpertScreeningandOptimalExtractionllnjection
Pumping Systems for Short-Term Plume Containment, Rep. ESLTR-87-57, Air Force Engineering
and Services Center, Tyndall AFB, Fla., 1990.
14. Willis, R., and Finney, B., Optimal control of nonlinear groundwater hydraulics: theoretical devel-
opment and numerical experiments, Water Resources Res., 21(10), 1476-1482 (1985).
15. Aly, A. H., and Peralta, R.C., USIWELLSD, Extractionllnjection Well System for Optimal Ground-
water Management: User’sManual, Biological and Irrigation Eng. Dept., Utah State Univ., Logan,
Utah, 1992.
16. Peralta. R. C., Aly, A. H., Suguino, H. H.,Belaineh, G . , and Miyojim, M., USIREMAX’, Utah
State Model for Optimizing Management of Stream-Aquifer Systems Using the Response Matrix
Method: User’s Manual, Version f.05,Biological and Irrigation Eng. Dept., Utah State Univ., Lo-
gan, Utah, 1992.
17. Prudic, D. E., Documentation of a Computer Program to Simulate Stream-Aquifer Relations Using
a Modular, Finite-Difference, Ground-water Flow Model, U.S. Geological Survey, Open-File rep.
88-729, 1989.
18. Suguino, H., and Peralta, R. C., PLUMAN A Decision Support System for Optimal Groundwater
Contaminant Plume Management: User’s Manual, Version 1.0, Software Eng. Div., Dept. Biolog-
ical and Irrigation Eng., Utah State Univ., Logan, Utah, 1992.
19. Konikow. L. F., and Bredehoeft, J. D., Computer model of two-dimensional solute transport and
dispersion in ground water, in Techniques of Water Resources Investigations,USGS, Washington,
D.C., 1984, Book 7, Chapter C2.
20. Suguino, H., A decision support system for optimal groundwater contaminant plume management,
Ph.D. dissertation, Dept. Agricultural and Irrigation Eng., Utah State Univ., Logan, Utah, 1992.
21. Todd, D. K., Groundwater Hydrology, Wiley.NewYork, 1980.
ADDITIONAL READING
Colarullo, S. J., Heidari, M., and Maddock, T.,111 (1984). Identification of an optimal groundwater
management strategy in a contaminated aquifer, Water Resources Bull., 20(5), 747-760.
Gharbi, A, (1991). Optimal groundwater quantity and quality management with application to the Salt
Lake Valley, Ph.D. Dissertation, Dept. Agricultural and Irrigation Eng., Utah State Univ., Logan,
Utah.
Peralta, R. C., Killian, F? J., Yazdanian, A., and Kumar,V. (1989). SSTAR UsersManual; Rep. IIC-8913,
International Irrigation Center Utah State Univ., Logan, Utah.
30
Horizontal Wells for Subsurface
Pollution Control
George Losonsky
Eastman Christensen Environmental Systems
Houston, Texas
Milovan S . Beljin
University of Cincinnati
Cincinnati, Ohio
1. INTRODUCTION
Horizontal wells are emergingas a new technology for solving problems in the environmental
industry. Horizontal wellscreen orientation complements typical aquifer geometry, ground-
water flow patterns, and common site logistics. Soils are naturally stratified, and individual
aquifers or water-bearing zones are much wider than they are thick. Contaminant concentra-
tions are often highest directly beneath buildings, landfills, and other obstacles to remedial op-
erations, so treatment facilities are constructed tens or hundreds of feet away from the target
zone of remediation. Despite the dominance of the horizontal direction in aquifer shapes and
groundwater flow, the predominant tool for extracting contamination from subsurface sources
is a vertical well. However, in many environmental remediation scenarios, a horizontal well
offers a better matchof form and function than a vertical well. The tabular geometry ofmany
aquifer zones renders horizontal wells more productive than vertical wells. The specific ca-
pacity ratio of horizontal-to-vertical wells increases with decreasing aquifer thickness.
Extraction of contaminated groundwater is often more efficient with horizontal Flow
wells.
characteristics ofmany aquifers create elongated contaminant plumes. A horizontal well placed
through the coreof a plume can recover higher concentrations of contaminants at a given flow
rate than a vertical well. Hydraulic barriersare most efficiently created using horizontal wells
oriented perpendicular to groundwater flow direction.
Logistical advantagesof horizontal wells are obvious. Horizontal wells avoid theneed for
installing wellheads inside buildingsor in the midst of complex manufacturing or process fa-
cilities. Landfills, spoil mounds, and landfill liners needbenot penetrated to extract leachateor
other underlying contaminants.
Fractures in an aquiferare commonly vertical. Because fluidor vapor recovery from frac-
tured zones requires penetration of numerous fractures, a horizontal well oriented normally to
vertical fractures is the optimal tool for pump-and-beat or soil vapor extraction systems in ver-
tically fractured zones. By analogy, vertical wells are efficient in highly stratified soils with
619
620 Losonsky and Beljin
little vertical communication between strata, where fluid or vapor recovery from many thin
layers t h u g h a single wellbore is required.
Injection of groundwater is part of some remediation systems, either to create a water table
mound or to reinject treated effluent from a manufacturing plant into the subsurface. Water
table mounds can help to control flow of contaminants toward recovery wells or trenches, or
they can serve as hydraulic barriers. Manufacturing plants can avoid high sewer discharge costs
if their treated plant .effluent can be reinjected into a non-drinking water aquifer. Reinjection
can cause mounding, but the mounding can be minimized by using horizontal wells.
II. DRILLINGTECHNOLOGIES
Various technologies can be used for installing horizontal wells for subsurface pollution con-
trol. Such wells are typically installed in unconsolidated soils 10-200 feet deep. Selection of
drilling technique depends on surface access, well placement and completion requirements, and
subsurface hydrogeology.
Jetting and moling are the most common techniques used to create horizontal brings in
shallow, unconsolidated soils. Both are mechanically simple and require minimal labor, using
small tubulars that can be handled by one person. Small trucks can carry the hardware for both
techniques.
Moling employs a rotating bit, compressing soil into the hole wall. This requires a soft,
compressible soil. Directional control is limited andrelies chiefly on trial-and-error targeting
methods. Holes are only a few inches in diameter, limiting completion options. No drilling
fluid is used, and no cuttings are generated. Clayey soils may become “damaged” (i.e., their
permeability may be reduced) because the cuttings are not removed from moling boreholes.
Jetting employs an off-axis, high-pressure water jet to fluidize the formation. Downhole
transmitters anda walk-over receiver are used for surveying thewell location and determining
jet orientation. The operator can steer the system accuratelyin unconsolidated, homogeneous
soils. Jetting requires that there be no interference sources between the surface receiver and
downhole transmitter.The transmitter must not be located deeper than25 ft below the surface.
Drilling fluid lubricates the drill string. Cuttings mixed with drilling fluid enter the soil for-
mation along the wellbore, which may cause formation damage as with moling.
Rotary drillingemploys a stabilized assembly allowing control of well path inclination but
no horizontal directional capability. Thedrilling rig must be large enough to providerotating,
push, and pull forces. The technique is used for oil and gas recovery and for installing utility
lines under rivers. Low drilling fluid flow rates are used in utility line installation, where the
fluid serves only to carry cuttings throughthe hole wall to keep it open and lubricate
to the soil.
High fluid flow rates are used in hydrocarbon recovery to remove cuttings from the wellbore
and thereby preserve formation permeability. A large radius of curvature is required in rotary
drilling to prevent failure of tubulars. The larger the tubular diameters, the larger the curve
radius required to prevent failure of tubulars. Surveying toolsare similar to those used for mag-
netic and gravitational orientation surveys. These tools work at any depth, but only in the ab-
sence of magnetic interference.
Positive displacement steerable motor technology offers vertical and horizontal directional
control. The radiusof curvature is small compared to that of rotary drilling, because the drill-
string rotation is minimal. Penetration rates are high because ofrapid bit rotation. Drilling
fluid forms an impermeable layer on the borehole wall, preventingfluid and cuttings from en-
tering the formation, as with rotary drilling. The impermeable layer also prevents hole collapse
by maintaining positive fluid pressure within the wellbore. The impermeable layer must be re-
moved following installation of the screened casing, to expose undamaged formation. Drilling
Horizontal Wellsfor Pollution Control 621
fluid must remove cuttings from the wellbore. Viscosity and turbulence of the drilling fluid
allow it to clear the wellbore. By comparison, vertical wellbores rely solely on viscosity. Tur-
bulence prevents cuttings from accumulating along the bottom of the wellbore. Since turbu-
lence increases with decreasing viscosity, ideal drilling fluid balances both factors. Thixotropic
gels are well suited as drilling fluids. lbrbulence is also maintained with the help of central-
izers, which provide a uniform annulus around the tubulars [l].
Percussion and vibration drilling techniques use air as a drilling fluid. These techniques
are particularly suitable for drilling through heterogeneous soils containing bouldersor coarse
gravel or through highly fractured rock formations. The wellbore remains dry, so fluid loss is
avoided. However, percussion and vibration drilling techniques currently lack well-developed
steerability and directional control.
111. HORIZONTALWELLHYDRAULICS
Recently, due to increased interest in horizontal wells for oil production, a large number of
papers have been published regarding the reservoir engineering aspects of horizontal drilling
and reservoir simulation[e.g., 2-41. In the groundwater industry, thefirst theoretical analysis
of groundwater flowto horizontal drains (collector wells) can be traced back the to early 1960s
[ 5 ] . In the last few years, there has been renewed interest in horizontal wells for subsurface
remediation [6-81 and for groundwater monitoring [9]. Langseth [lo] performed a numerical
analysis of horizontal well performance and comparedinstallation and operation costs of hor-
izontal and vertical wells.
A.Steady-StateFormulas
Whereas a vertical well drains a cylindrical volume, a horizontal well of length L drains an
ellipsoid. The zoneof influence is elliptical, with endpoints of the well constituting the foci of
the ellipse. The area of the drainage ellipse, A
, is
A, = n Reva (1)
where R,, is the effective drainage radius
of a vertical well in the same aquifer, anda is half the
major axis of the ellipse [ll]:
a =
In order to compare the drainage area of a horizontal well with that of a vertical well, the
drainage radius of a horizontal well, R,, measured in the horizontal plane that contains the
well, is defined suchthat the corresponding circular areaA, equals the elliptical drainage area
A, of the well:
2
A, = A, = n Rch (3)
Combining Equations (1H3) and solving for a ,
0.5
a = (1512)[ O S + J0.25 + (We&)4]
A formula forestimating steady-state flow to a horizontal well in a homogeneous and iso-
tropic aquifer is given as [12,13]
2nKBAs
(5)
where Qh is the flow rate, [L3iT]; As is the drawdown, [L]; L is the length of horizontal well,
[L]; r, is the well radius, [L]; K is the hydraulic conductivity, [ m ] ; and B is the aquifer thick-
ness, [L].
The specific capacity of a horizontal well, Jh = Q,,/&, is usually greater than that of a
comparable vertical well, J , = QJAs, except in relatively thick and highly permeable aqui-
fers. In Figure 1, the ratio of the specific capacityof a 500-ft-long horizontal well,Jh, to that
of a fully penetrating vertical well, J,, is plotted as a function of the hydraulic conductivityK
(gpd/ft2) for three different aquifer thicknesses(B = 5 , 20, and 100 ft). The figure reveals that
the ratio of the horizontal to vertical well specific capacity (productivityratio) is the greatest
for relatively thin aquifers with low hydraulic conductivity. Thus, horizontal wells are most
effective in thin, low-permeability aquifers where vertical wells commonly fail to produce sig-
nificant volumes of groundwater.
B. Anisotropy Effect
When the vertical conductivity,K,, is different from the horizontal conductivity,Kh, the flow
rate to a horizontal well can be computed as follows:
where = .
l0O0?
Aquifer Thickness:
mmmmmm~ b=20ft
*M*UUVU b=lOOft
.001 .01 .l 1 10 100 1000

K [gpdlft2]
Figure 1 Productivityratiovs.hydraulicconductivity.
Wells Horizontal for Pollution Control 623
Figure 2 plots the specificratio of a 500-ft horizontal well

as a functionof the conductivity
contrast and the aquifer thickness. In the case of anisotropic aquifers, the specific capacity ra-
tios of horizontal to vertical wells increase if the hydraulic conductivity ratios, K,,/K,, de-
crease. This increase is inversely proportional to aquifer thickness.
C. Formation Damage and Effective Well Radius

During drillingof a well, drilling mud can invade the aquifer and change its permeability in the
vicinity of the well and cause formation damage or skin effect. The thickness of the “skin
zone” will depend not only on drilling technology but also on the permeability of the aquifer.
High-permeability aquifers exhibit a larger skin zone than low-permeability aquifers. However,
the reduction in permeability is smaller in a high-permeability zone than in a low-permeability
zone. The additional drawdown due to the change in permeabilityand the turbulent flow around
the well is calledwell losses. Because of lower flowrate per unit screen length, horizontal wells
show smaller well losses due to drilling mud invasion than vertical wells.
Van Everdingen [l41 defined a dimensionless “skin factor” S as
s = [ ( W - 11log(rirw) (7)
where r, is the radius of the skin zone with permeabilityk, in an aquiferof permeability k, [L2].
The effective radius of a well,rk, is defined as the theoretical radius of the well required
to match the observed pumpingrate and drawdown. The effective radiusof a hypothetical ver-
tical well that pumpsat the samerate as a horizontal well canbe computed using the equation
1000 3
100 Aquifer thickness:
10
Figure 2 Productivityratiovs. anisotropy.

The following formula relates the skin factor, S, and the effective radius of a well, rk:
rk = r, exp(-S) (9)
Renard and Dupuy [l51 gave the following solution for computing flow rate, Qh, from a
horizontal well with the skin factor S:
2nKBAs
Qh =
cosh”(2a/L.) + (B/L)log(B/23crb) + S
If the length of a horizontal well greatly exceeds aquifer thickness,

L % B , or if well length
is small compared to drainage radius, R,, Equation (5) reduces to the well-known Thiem’s
equation,
with the effective well radius being equalto one-fourth of the horizontal welllength, rk = L/4.
D. Off-Center Horizontal Well

All solutions presentedso far have assumed that the horizontal well is located at midheight in
the aquifer cross section. The distance, 6, from aquifer mid-height to the horizontal well is
called the eccentricity of the well. The flow rate of an eccentric horizontal well can be calcu-
lated using the formula
2nK#As
Qh =
1% [
a+-
L12 ] -k log [ +
pBrJ2 ]
(pB/2)2 p2a2
As long as thehorizontal well eccentricityis relatively small, 6 < 2 B/4, the performance
of a horizontal well is not significantly affected [16].
IV. TRANSIENT SOLUTION

Gringarten et al. [l71 used source and Green’s functions to solve a problem of transient flow
into a well with a single vertical fracture. For the uniform-flux fracture, i.e., a fracture with
uniform fluid entry along its length, the pressure distribution is given by
where S, is dimensionless drawdown;rD is dimensionless time;,x = x/xf; yo = y/xf;xf is half

fracture length, [L]; x is thedistance measured fromthe well center along the fracture, [L]; and
y is the distance perpendicular to the fracture, [L].
The concept of uniform flux and infinite-conductivity fracture can be applied to a hori-
zontal well by assuming that the horizontal well is a vertical fracture with a width equal tothe
radius of the well [16]:
where LD = [ W 2 B ] m ; rwD = 2rJL; XD = YD = 2yIG Z, = zIB;

zWD= z JB; and z, is the vertical distance from the aquifer bottom, [L].
For a long horizontal well,the summation termin Equation (14) approaches zero, and the
horizontal well solution reduces to the fracture solution, Equation (13).
V. EXAMPLEAPPLICATIONS
A. Case 1: Texas Gulf Coast Industrial Landfill Site
Before the advent of horizontal wellbore technology, vertical wells were used to recover con-
taminated groundwater under landfills. In aquifers with high hydraulic conductivity, vertical
wells placed along the periphery of a landfill can influence the aquifer below the landfill. If the
size of the plume is small comparedto the size of the landfill, migration of contaminants from
the coreof the plume below the landfill to vertical extraction wells along the periphery spreads
the contamination. Low hydraulic conductivity requires placement of vertical wells within the
landfill, penetrating the landfill liner. Long-term sealing of the liner around the vertical well
casing cannot be guaranteed. Horizontal wells avoid these problems by placing a production
screen directly in the plume without penetrating the landfill.
In 1991, a horizontal well was installed beneath an RCRA facility on the Gulf Coast of
Texas to recover contaminated groundwater. The landfill occupies an area approximately 900 ft
by 900 ft. Its depth is 30 ft, and the slope along its sides is 27" from horizontal (Figure 3).
Numerical modeling prior to installation predicted that a single horizontal well wouldbe hy-
RED-BROWN CLAY
GRAY-TAN SILTY CLAY
RED-BROWN CLAY
FINE SAND
""""""""""""I""""""""""""""""""""""""""".
GRAY CLAY
Figure 3 Texas Gulf Coast landfill-cross section with horizontal well path.
draulically more efficient than a vertical well system [18]. The single horizontal well replaces
five vertical recovery wells. Fewer pumps and a lower volume of recovered water save oper-
ation and maintenance costs of the remediation system.
1. Hydrogeology
Interbedded, 20-30 ft-thick reddish brown clay and gray and tan silty or sandy clay charac-
terize the subsurface from0 to 98 ft depth, corresponding to 26 ft above mean sea level(MSL)
to 72 ft below MSL (Figure 3). The uppermost silty clay layer and the top of the underlying
reddish-brown clay layer have been excavated to accommodate the landfill. Tan fine sand oc-
curs at 100-128 ft depth from the surface,or 70-95 ft below the base of the landfill. Blue-gray
and black-gray clay underlies the sand. The silty or sandy clay layers and the sand layer are
saturated. The reddish-brown clays are aquicludes or aquitards. The tan sand layer is the target
of the remediation effort. The hydraulic conductivity, K, of the sand is 30 ftlday, and stora-
tivity, S, is 1 X lo-', indicative of a confined aquifer. There is no significant potentiometric
gradient in the absence of pumping.
2.
Well Specifications
Sixty feet of 65/-in. slotted stainless steel screen was installed beneath the landfill at a total
vertical depthof 114 ft. This depth is 4.7 ft below mid-height in the aquifer, givingthe well an
eccentricity of 4.7 ft. The wellhead protrudes at a 41 S " angle, 20 ft from the edgeof the land-
fill. The horizontal displacement from the wellhead to the beginning of the screen is 248 ft,
reflecting a radius of curvature of 275 ft. The curved sectionof the well was cased with 10 -in.
of high-density polyethylene liner to isolate soil zones during drilling and to provide structural
support for the inner stainless steel casing.
3.DrillingProcedure
Drilling commenced with augering of a 16-in. wellbore to a measured depth of 37 ft, which
corresponds to the kickoff point forthe curved section of the wellbore. A steel conductorpipe,
14 in. in nominaldiameter, was cemented in the 16-in. wellbore. The cement was allowed to set
for 12 hr. The curve drilling assembly then drilled and simultaneously caseda 13-in. borehole
with an effective drilling radius of 275 ft to a measured depthof 272 ft. The curved sectionwas
drilled using a 13-in.wing bit. High-densitypolyethylenecasing 10 in.thickwasthence-
mented intothe curved section of the wellbore. After the cement had set, the horizontaldrilling
assembly drilled an 8%-in. wellbore to a measured depth of 352 ft, with a final inclination of
90.5" from vertical. The horizontal section was drilled using an 8%-in. rock bit. Schedule 40,
3 16 SS ERW stainless screen casing, with6Ys-in. outer diameter, was installed along the entire
length of the wellbore. Only the60-ft section of stainless steel casing installed withinthe target
zone was slotted. Slot size was 0.02 in. 'henty-foot sections of stainless steel casing were
welded together, increasing installation time. Six 1 0 4 sections of prepacked screen were in-
stalled inside the stainless steel screen in the target zone. The prepacked screen was attached
directly to an electric submersible pump oriented horizontally within the unscreened stainless
steel casing. Well development required 18 hr,after which clear water was recovered. Residual
drilling fluids were flushed out of the well with a submersible waterjetting tool.
Drilling, installation, and well development required approximately 10 days. Duringdrill-
ing, continuous updatesof inclination and tool faceorientation were provided to ensure proper
wellbore placement. TruTracker surveys were taken as needed, at least once every 20 ft, to
provide actual bit locations with respect to the proposed well path direction. The horizontal
wellbore remained within a 4-ft vertical target range, thus exceeding the required accuracy of
k 5 ft (Figure 3). The well remained within a 20-ft-wide horizontal target zone (Figure 4).
Approximately 18,000 gal of cuttings, drilling fluids, and cement returns were generated dur-
Target Zone
Figure 4 Texas Gulf Coast landfill-plan view of horizontal well path.
ing the installation of the horizontal well. Nearly half of that volume was generated during
installation of the curved section of the well.
4. WellPerformance
The well produces upto 7 gpm of water, creating drawdown of 1-2 ft at distances of upto 300
ft radially from the midpoint of the well. The drawdown created by the horizontal well is con-
sistent with results of analytical modeling shown in Figure 5 (distances are given in feet, and
the contour interval is 0.1 ft). The model assumes steady-state flow in a homogeneous, iso-
tropic aquifer. Less than 100 ft from the well, the potentiometric surface defines an elliptical
0 200 400 600 800 1000
Figure 5 Texas Gulf Coast landfill-horizontal well drawdown contour map.

trough of depression. Beyond 100 ft, potentiometric surface contours are circular. The model
indicates that drawdown along the well is 2.7 ft at a pumping rate of 7 gpm.
The specific capacityof the horizontal well is only 1.16 times that of a comparable verti-
cal well with fully penetrating screen. Therefore,the primary advantageof this horizontal well
is not hydraulic, but logistical. The risks involved in penetrating an existing landfill liner,
whichwould be requiredfor vertical wellinstallationin this scenario, outweigh the cost
difference.
B. Case 2: Industrial Chemical Plant in Southern Louisiana

Contaminated clayey soils beneath industrial plantsare commonly excavated to prevent migra-
tion of contaminant5 into underlying aquifers. Low hydraulic conductivities of such soils re-
quire close spacing of vertical wells, but dense wellfields are difficult or impossible to install
because of logistical obstructions such as underground utility lines and overhead steel struc-
tures. Furthermore, drilling vertical wells in the midst of active operating facilities raises con-
cerns about worker health and safety as well as plant productivity losses. Recently, several
horizontal wells have been installedas an alternative to excavation in sandy clay soils beneath
petrochemical complexes alongthe Mississippi River in the industrial corridor between Baton
Rouge and New Orleans, Louisiana. Two such wells were installedat a petrochemical complex
located southof Baton Rouge. The wells were installed to recover dissolved ethylene dichloride
and monochlorobenzene from shallow silty clay soils.
1. Hydrogeology
Clay and silt dominate the subsurface to a depth of 60 ft at thesite. Eight soilstrata have been
identified. The top 8-10 ft consists of dark brown to gray clay and orange, green, and brown
to gray silty clay. Below that is a 10-ft-thick orange and gray to brown clayey silt, which is
underlain by alternating clay and silt.The 10 ft of silt isthe target of the remediation effort. Its
hydraulic conductivity is 1.7 Wday in the vicinity of the contaminant plume. Vertical perme-
ability in the clayey soils aboveandbelow the silt is approximately 3 X fffday. The clay
sediments behave likeaquitirds. The potentiometric gradient in the 10 ft of silt is 0.002 east-
northeast.
2.Well Placement
The shallower of the two wells (Well A)was installed at a total vertical depth of 12 ft beneath
an existing superstructure. The overheadstructures and the concrete foundation below ground
level containedactive unit process equipment.The horizontal section of the well is 356 ft long,
and it was installed alongthe midline of a 20-ft-wide corridor bounded by 60-ftdeep concrete
and wood pilings. A vertical well was located only 5 ft away from the wellpath, demanding
high placement accuracy. The deeper well (Well B) was installedat a total vertical depth of 14
ft beneath an existing concrete road, along a pipe rack and. railroad loading dock. The hori-
zontal screenof the well is 400 ft long, and it was installed between pilingssupporting the pipe
rack on one side and a freshwater drainage ditch onthe other side.
3. Well Specifications
The curved section of Well A (Figure 6) is constructed of 10%-in. -high-density polyethylene
casing cementedin a curved 12!4-in. wellbore. The curve ends at a measured depth (measured
along the wellbore) of 80 ft. The horizontal section is completed with 65h-in. highdensity
polyethylene slotted liner (slot size is 0.02 in.) installed within an 8Ya-in. wellbore. The hor-
izontal section ends at a measured depth of 436 ft. Blank (unslotted)highdensity polyethylene
ells Horizontal for Pollution Control 629
CROSS SECTION
100 200 300 400

DISTANCEIN FEET
Figure 6 Louisianachemicalplant-horizontal well path, well A.
casing is installed inside the loyein. curved casing, rising to the wellhead. An electric sub-
mersible pump, rated at 10 gpm, was placed inside the @&in. casing at the bottom of the
curved section of the well. Stainless steel wire-wrapped prepacked screen was installed inside
the horizontal high-density polyethylene casing and attached the to pump to filter silt-sized for-
mation material. Horizontal displacement between the wellhead and the beginningof the screen
is approximately 70 ft. The horizontalsection remains withina 3-ft tolerance envelope, ranging
in total vertical depth from 11.8 to 14.9 ft. Horizontal accuracy is within 2 ft of the planned
termination point. Well B is constructed similarly to Well A (Figure 7), with total vertical
depth ranging from 12.4 to 17 ft.
Four undisturbed horizontal core samples were extracted during drilling-three from the
shallower well and one from the deeper well. Eachcore is 5 ft long and 2 in. in diameter. Cor-
ing is accomplished by setting a hydraulic coring tool (Figure8) into the soil at the end of the
PLAN VIEW
20 ' l
100 200 300 400

DISTANCE IN FEET
Figure 7 Louisianachemicalplant-horizontal well path, well B.

Figure 8 Hydrauliccoringtool.(Source:EastmanChristensenEnvironmentalSystems.)
wellbore with a moderate amount of pushdown force to isolate the inner barrel from the drilling
fluid and contaminated soiland groundwater. Pressure is hydraulically appliedto create a con-
stant load on the outer tubeof the coring device.An accumulator located on the drillingrig is
plumbed in parallel with the drill string circulation path to maintain a constant punch force.
Pressure is raised to the calculated punch release force, which breaks shear pinsand acceler-
ates the inner tube into the formation. Pressure is maintained in the system to hold the outer
tube against the formation to prevent the drilling medium from coming into contact with the
sample as it is pulled back into the outer barrel. The core barrel is then retrievedto the surface
for recovery of the undisturbed sample. The sample is contained within a disposable plastic
liner. The core barrel requires a radiusof curvature of at least 100 ft to pass through a 5Vi-in.
borehole.
The total groundwater recovery of the two wells is 23 gpm, which is comparable to over
50 vertical wells in the same water-bearing zone. Vertical wellsas far as 70 ft away from the
horizontal wells exhibit drawdown causedby pumping from the horizontal wells.
4. AnalyticalModeling
Results of analytical modeling of capture zones that develop in response to groundwater re-
covery from the two horizontal wells are shown in Figure 9. Recovery of the contaminant
plume in the vicinity of thetank car unloading areas, process sump, and glyoxal unit, shown in
Figure 9, canbeachievedwith two 400-ft-long horizontal wells placed within the water-
bearing silt zone.The southern well would be placed 30 ft north of the glyoxal unit,as shown
-horizontal screen
capture zones:
-
0 4years
400 FT 8 years
Figure 9 Louisianachemicalplant-groundwatercapturezones.
Wellsfor Pollution
Horizontal Control 631
in Figure 9. Shaded areas indicate 4-year and 8-year capture zones of the two wells. The cap-
ture zones are calculated using a groundwater code called PAT [19], which assumes a homo-
geneous, isotropic aquifer. The assumed aquifer parameters, input data, and the results are
listed in Table 1.
Results of analytical modeling of aquifer response to groundwater recovery fromthe two
horizontal wells are presented in Figure 10 (distances are in feet and the contour interval is 1
ft). The shaded region represents the chlorobenzene (MCB) plume. Groundwater recovery rates
are calculated using W E L L , an analytical model [20].
Aquifer response tothe two proposed horizontal recovery wellsis estimated by simulating
each horizontal well by a series of closely spaced vertical wells with total pumping rate equal
to that calculatedby W E L L . This method provides a good estimate of drawdown curves gen-
erated by more complex, numerical methods, and hence it is a good tool for predicting actual
drawdown contours.The model used for this simulation is a modified version of THWELLS
[21], which solves the Theis equation for multiple wells and accounts for unconfined aquifer
conditions. The model assumes non-steady-state conditionsin a homogeneous, isotropic aqui-
fer with infinite areal extent and with a hydraulic gradient of 0.002. Time elapsed since the
onset of pumping is 100 days. The analytical models suggest thatthe two horizontal wells in-
stalled at the plant could capturethe plume during an 8-10-year period if the total pumpingrate
were only 5 gpm. Actual recovery rates are over four times that amount, so closure levels of
contaminant concentrations may be achieved sooner.
VI. CONCLUSIONS
Horizontal wells offer significant advantages over vertical wellsin environmental remediation
and protection in many hydrogeological scenarios. These include thin and/or low-permeability
aquifers, where many closely spaced vertical wells are replaced by a single horizontal well.
Current high installation cost of a horizontal well compared to a vertical well is offset by op-
eration and maintenance cost savings. New developments in horizontaldrilling technology will
further reduce the cost of installing horizontal wells, and subsurface pollution control with hor-
izontal wells should become as common as vertical wells.
Table 1
Input data
Hydraulic conductivity 1.67 ft/day
Storage coefficient 0.05
Flow rate of horizontal well 2.5 gpm
Time of pumping (capture zones) 4and8yr
Time of pumping (drawdown contours) 100 days
Aquifer thickness 8 ft
Horizontal well length mft
Wellbore radius 0.7 ft
Radius of influence of horizontal well 330 ft
Horizontal well eccentricity 2 ft
Regional flow gradient 0.0021
Results
Half the major axis of drainage ellipse 361.9 ft
Specific capacity, horizontal well 68.34 gpdft2
Drawdown in absence of flow gradient 7.04 ft
1000
500
Figure 10 Louisianachemicalplant-aquiferresponsetohorizontalwells.Potentiometricsurface
contours interval is 1 ft. Distance scale isin ft. Initial potentiometric surface elevation is 10 ft at origin
(SW comer).
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15. Renard, G . I., and Dupuy, J. M., Influence of formation damage on the flow efficiency of hori-
zontal wells, Presented at the Formation Damage Control Symposium, Lafayette, La., Feb. 22-23,
1990.
16. Joshi, S. D., Horizontal Well Technology, Pen Well Books, 'hlsa, Okla., 1991.
17. Gringarten, A. C., Ramey, H. J., Jr., and Raghavan, R., Unsteady-state pressure distributions cre-
ated by a well with a single infinite-conductivity vertical fracture,SPE J . , August 1974. pp. 347-
360.
18. Speake, R. C., 'Itpjan, M.. and Wang, Z. Z., Modeling the performanceof a horizontal ground-
water recovery well, Proc. Outdoor Action Conf., Las Vegas. Nev., Natl. Ground Water Assoc.,
1991, pp. 399-415.
19. Kinzelbach, W., and Rausch, R.,PAT: Pathlines and Traveltimes Groundwater Model, Kassel, Stutt-
gart, Germany, 1990.
20. Beljin, M. S . , and Losonsky, G., HWELL a horizontal well model, Solving Ground WaterProb-
lems with Models, NGWNIGWMC Conference, Dallas, Texas, 1992, pp. 45-54.
21. van der Heijde, P. K. M., THWELLS, International Ground Water Modeling Center, Holcomb Re-
search Institute, Indianapolis, Ind., 1991.
Part V
CONTROL
INDUSTRY-SPECIFIC POLLUTION
31
Pollution Control and Waste
Minimization in Military Facilities
Merrit l? Drucker
Army Management StaffCollege
Fort Belvoir, Virginia
1. INTRODUCTION
Military facilities include a wide range of bases, installations, maintenance facilities, manu-
facturing plants, factories, as well as installations in foreign countries and temporary facilities
established in support of combat operations. Some military facilities are similar to cities and
towns; others are highly specialized facilities producing unique munitions;others resemble of-
fice complexes. Some facilities are rented.
Military facilities present a variety of problems for the environmental engineer. First, mil-
itary bases are generally organized to support a wartime or contingency mission. This means
that environmental considerations may not be as prominent as in municipalities and private
industry, although this attitude is changing rapidly. Second, because of their organization and
function, the waste stream from military facilities is likely to be more complex and, in some
cases, more toxic or hazardous than the waste stream from a comparable civilian facility. Fi-
nally, military facilities are operated undera different budgeting and financial system than mu-
nicipalities and private industry. Environmental engineers employedby military facilities ought
to be aware of these differences and should make themselves aware of the culture, or sociology,
of the military facility where theyare working, the military chainof command, andthe peace-
time and wartime missions of the facility. This is not merely “nice-to-know” information. It
is the essential first step to designing a pollution control and waste minimization strategy for an
installation.
II. MATERIALS AND PROCESS ANALYSIS

The first step in controlling pollution and minimizing waste from a military facility is to find
out how much material and what type of material is being brought into the facility. This in-
formation is not easily obtained, and few if any installations can tell for certain what all their
material imputs are.However, even imprecise estimates of the amountof material brought into
637
638 Drucker
the facility can helpdetermine start points for control strategies. Often, after merely lookingat
what the facility is ordering, substantial reductions or effective substitutions can be made. A
centralized computer system that could identifythe total amount of material coming into the
installation would be a useful management tool. Unusually large orders or inputs of toxic or
hazardous materials are good initial places to look for reductions.
vpically, pollution control and waste minimizationhave been thought of as logistical or
engineering functions.A more effective approachwould require managers at all organizational
levels to know what all of their inputs are (materials, energy, utilities) and to examine their
input stream for reductions. Focusing on first reducing the amount of inputs caneliminate much
waste. Often smaller quantities can be ordered, less toxic material substituted, or some items
eliminated entirely. Working with suppliers can be especially helpful, as suppliers of hazardous
materials are under intense pressure to reduce the hazard level of theirproducts, to reduce pack-
aging, and to accept empty containers for reuseor recycling.
The second step is to examine the various processes at the facility to find economies and
efficiencies. Most industrial and materials processes at military facilities were not designed
with pollution control or minimization in mind until relatively recently. All processes mustbe
continuously evaluatedso they can be made to consume fewer inputs of materials, energy, and
hazardous materials. Process improvement may entail improved housekeeping, better mainte-
nance of equipment, training of employees, replacementof older equipment with newer, more
efficient models, or completely new ways of performing required industrial tasks. Engineers
ought to be especially active in asking employees who actually runthe processes how savings
can be achieved.Often, the employee closest to the process can providethe best suggestions on
ways to make the process less polluting, less energy-intensive, or less expensive.
Nor should relatively inexpensive, simple solutions be overlooked. Actions such as pro-
viding plastic covers for metal drums can prevent contamination from rainwater, thus protect-
ing products stored outside and avoiding large disposal fees.
Since many military installations share similar processes andfacilities, it is often possible
to obtain information fromother facilities on how to improve operations. Informationsharing
and exchange are vital elements in any plan to reduce waste or minimize pollution. Processes
that have been implementedat one installation can often be implemented at another with little
modification. The United States Department of Defence is undertaking a department-wide ef-
fort to reduce the amount of hazardous waste generated. Specialized agencies throughoutthe
department serve as consultantsor centers of expertise for waste reduction and should be called
on for assistance. Environmental engineers assigned to military facilities should aggressively
pursue efforts to replace toxic material with less toxic substances.
It is especially importantfor military facilities to plan and budgetfor pollution control and
waste minimization. These facilities do not have the flexibility of private industry, and pro-
curement times tend to be longer. Installation and organizational plans, both long-term and
short-term, as well as budgets, must include planning and funding for new equipment and fa-
cilities. The military facility’s higher headquarters must be kept fully informed as to the status
of minimization efforts and the need for capital investment.
The third, and final, step is to control and properly dispose of the wastes that are gener-
ated. This requires disposal systems and options, and education of the installation population.
The primary type of disposal of wastes from militaryfacilities should be recycling. Almost all
military facilities have recycling systems, and thereis an accounting system in place to return
profits from the recycling program to the facility. However, recycling could be greatly ex-
panded, resulting in significant cost savings as disposal fees for waste increase. All wastes
should be evaluatedfor recycling before disposal, and consideration should be given to giving
away waste material such as scrap lumber or metal rather than disposing of it as pure waste.
cilities Pollution
Military Control at 639
Recycling programs on military facilities shouldbe fully integrated with the local community.
The military recycling program should be made available to the local community, and those
who live and work on the installation should be encouraged to participate in community re-
cycling programs. It is essential that recycling programs be fully coordinated and integrated
into programs sponsored by other military facilities and the local community, inboth the United
States and in foreign countries.
Current and pending legislation, primarilyat the state level, will require that certain per-
centages of the waste stream be recycled. It is impossible to determine if the military facility
is meeting this goal unless the waste managers have accurate information on both the amount
of material coming into the installation and the amount of waste being generated. This rein-
forces the need for automated materials tracking systems.
There is a considerable amount of technical information available on pollution control and
waste minimization, much of which is readily applicable to military facilities. Employees and
managers at all organizational levels should be required to be on the lookout for alternative
processes and methods and ways to improve existing processes. It is critically important that
waste minimization and pollution controlbe seen as a primary responsibility of those who ac-
tually work with the systems and materials and not the responsibility of the environmental en-
gineer.Pollutioncontrolandwasteminimizationmust be seen as a line, and not a staff,
function; these requirements shouldbe part of efficiency reports and performance appraisals.
While supply personnelare in a critical position, leaders and managers must specify that they
want nontoxic materials whenever possible, and must specify that they prefer products made
from recycled, postconsumer waste.
One extremely valuable, yet sometimes overlooked, resource available to military facilities
is audit capability. Most military facility commanders have professional auditors available to
support them. These auditors can examine all phases of the pollution control, waste minimi-
zation, and recycling program and can assist in achieving considerable savings and efficiencies.
Environmental engineers working on military facilities are encouraged to seek auditing sup-
port. The payoff can be enormous.
111. LEGALREQUIREMENTS
In the United States, federal facilities must comply with local, state, and federal environmen-
tal, public health, and safety laws. Although there are some minor exceptions, the general
thrust of environmental legislation is toward more and stricter regulation; military facilities
are
no exception. For the environmental professional, a detailed knowledge of the law is essential.
Law and technology combine to form an interactive process.As technology improves and al-
lows us to detect and control more pollutants, laws are amended or written to make the tech-
nological ability a requirement.New laws, on the other hand, often contain requirements that
serve as a spur or stimulus to technological innovation. Legal requirements are important and
must be complied with, but they are only a small part of the pollution and waste control effort
at military facilities. Further, focusing only on legal requirements may mask or distract atten-
tion from the possibility for considerable waste minimization and economic savings resulting
from a more systemic, global view of pollution control and waste minimization. Environmental
engineers must be looking for additional ways to prevent or minimize pollution to levels well
below those required by law.
All U.S. military commands have legal staff support availableto them. Environmental engi-
neers are well advisedto bring the legal staff into all environmental engineering early
very
in the
planning stage. Continuous coordination and consultation with the legal staff during all phases of
base operations will help eliminate environmental problems before they become legal problems.
640 Drucker
Military commanders and federal employees can be held both civilly and criminally liable
for violating environmental laws. This makes compliance with the law quite important for mil
itary facilities and increases the importanceof close consultation with supporting legal staffs.
Legal problems with state or federal regulatory agencies have the potential
to delay projects
or military missions. Military commanders are extremely concerned about the possibility of
delay on military missions andwant to be kept fully informed on possible problems or delays.
Engineers working on military facilities should ensure that they have open communications
channels with the installation commander.
IV. MOBILIZATIONANDDEPLOYMENT
A unique military environmental problem is the amount of waste generated
by military mobi-
lizations and deployments. During times of national emergency or war, the population of an
installation can doubleor triple in the space of 2 or 3 days. Industrial and production activities,
such as maintenance and ammunition manufacturing, cango from very low rates to very high
rates in a matter of days. Surging troop populations preparing for overseas deployment dema
all manner of goods and services, resulting in the generation of large amounts of waste of all
types in a short time period. It is difficult to minimize waste during mobilizations, since they
are short-duration, resource-intensive activities. Good planning, however, can prevent pollu-
tion and recover such waste for recycling.
It is important that military facilities be planned and operated in such a way that all en-
vironmental laws and practices followed in peacetime can be followed during rapid wartime
expansion. In most cases, this canbe done if the installation or facility infrastructure has been
properly constructed and if adequate environmental planning has been accomplished. Typical,
specific problems have emerged from past mobilizations and deployments; theseare predict-
able problems that can be prevented by good planning.
Perhaps the single biggest environmental problem during mobilizations is wastewater re-
sulting from increased troop populations. Large flows from troop housing areas, mess halls,
vehicle washing, and industrial operations can quickly overwhelm wastewater treatment sys-
tems. To prevent this, military wastewater treatment systems must be designed to accommodate
the maximum or peak troop population during mobilization. This may seem wasteful or too
expensive; however, the costs of environmental cleanup, fines, and health problems may well
exceed the initial cost of larger capacity wastewater systems.
Vehicle painting operations present another problem. Due to the toxicity of military cam-
ouflage paints, vehicles must be painted in special booths intended to protect worker safety and
prevent the release of toxic fumes to the atmosphere. While a typical facility may haveorthree
four booths, a wartime emergencymay require the rapid painting of hundreds of military ve-
hicles. Unless sufficient booths to accommodate wartime surges have been constructed, the
vehicles may be painted in the open or workers not protected. Environmental planners must
ensure that adequate facilitiesare constructed or that contract arrangementsare made to have
the vehicles painted in appropriate facilities. A more effective long-term solution wouldbe to
design a paint system that does not have toxic components. Painting and industrial coating p
cesses for military equipment (ammunition, weapons, naval vessels, aircraft electronic equip-
ment) tend to present the same types of problemsas vehicle painting, particularly when there
is a surge in production. These “pollution surges” must be planned for in all phases of the
engineering process.
Increased populations will generate substantially more quantities of solid waste, and in-
creased industrial operations will result in the generationof increased quantities of hazardous
waste. These additional quantities can usually be disposed of by expanding existing disposal
ntrol Pollution at Military Facilities 641
contracts for waste disposal and recycling. Should planning estimates reveal that likely mobi-
lization surges will overwhelm existing capacity, arrangements shouldbe made to have “con-
tingency” contractsprepared for immediate implementation when needed. The to keys
effective
waste disposal are good recycling programs, good contracting, and thoughtful planning.
One potentially significant pollution problem resulting from increased military training is
the pollutionof streams and waterways with soil or other material eroded from military training
areas. Large military tracked vehicles, such as tanks and armored personnel carriers, can se-
verely damage the land, making erosion possible. Careful training area management and ap-
propriate revegetation and repair of damaged land must be planned for during mobilizations.
V. WARTIMEOPERATIONS
A time of crisis or war does notmean that environmental standards are discarded. Rather,
peacetime pollution control and waste minimization should continue in domestic facilities as
well as in the theaterof operations. Thiswill present somedifficulty; however, intelligent prior
planning and appropriate discipline in the theater of operations can prevent large amounts of
environmental destruction.
First, logistic support plans should clearly specify what will be done with any hazardous
waste as well as solid waste generated in the war zone.Much of this material will be generated
at fixed, semipermanent, or permanent facilities at rear areas of combat zones, so intense en-
emy interferencewith many support activities will be limited.Waste maybedisposedof
through the system of the host country or retrograded back to the United States for disposal.
Wastes may be pretreated to reduce bulkor hazard. It is essential that waste not be dumped or
abandoned, even if that is standard practicein the country our forcesare in. For legal, political,
ecological, and moral reasons, wastes shouldbe disposed of, whenever possible, in accordance
with existing U.S. standards.
Second, nonhazardous solid waste should,to the greatest extent possible, be made avail-
able to local recyclers. Open burning and burial should be avoided unless otherno
options exist
and the waste becomes a health problem.If possible, engineered landfills shouldbe constructed
and the location and closure plans made available to the appropriate national environmental
agency. Excess supplies or equipment should be returned for reuse or abandoned, butnot
burned or buried.
Third, battlefield cleanup must be plannedfor and conducted as soon as possible after the
cessation of combat. Normally, troop units can remove and dispose ofthe vast majority of bat-
tlefield debris. Specially trained and equipped units willbe required to recover explosives, un-
exploded projectiles, mines, and chemical weapons. Someitems, such as vehicles destroyedby
depleted uranium rounds, may be returned to the United States for secure disposal.
VI. TRAINING
An effective training program is essential if military facilitiesare to minimize waste and control
pollution. Military facilities usually have a diverse work force of military and civilian person-
nel; if the facilityis in another country there
will most likely be employees from the host nation.
All members of the facility will need to be informed on the procedures for recycling, waste
disposal, and pollution control. The best, most expensive, most technologically sophisticated
pollution control or recycling system will be of little use if it is not understood by those who
must use it.
There are a variety of training systems available. The environmental engineer or recycling
coordinatorcanprovideinstruction or information to unitenvironmentalrepresentatives
642 Drucker
through a variety of installation councils and meetings. The unit environmental representatives
can then train the members of their organization and serve as a means of communicating new
information to their organizations.
Many facilities use installation newspapers or periodicals to communicate information
quickly to all members of the installation. This can be a very useful adjunct to a formal training
PWPam.
Some trainingis quite technical and is requiredby federal law. This training mustbe con-
ducted by qualified instructors,and careful records maintainedto ensure that reporting require-
mentsaremet.Militaryfacilitiesinthesamegeneralgeographicareashouldconsider
consolidating this type of training to cut training expenses. All training should be very high
quality, and standards kept high. Training must be repeated periodically, especially for new
members of the installation team. Trainingat facilities in foreign countries must be conducted
in the language of the employees. This is especially important, as many logistics functions for
U.S. forces overseas are performed by foreign nationals.
32
Waste Reduction Strategies
for Small Businesses
Dan A. Philips
Pensacola Junior College
Pensacola, Florida
1. INTRODUCTION
Some historians believe that the 1990s will be rememberedas theenvironmental decade.Even
small businesses cannot remain in operation today without considering the repercussions of
each of their actions on the natural environment, the regulatory environment, and the public
perception of the environment.
The late 1960sand early 1970sbrought aboutmany changes. Hair became longer and skirts
shorter. For any number of reasons, the public consciousness was raised along with hemlines.
One of the major controversiesto arise concerned the role of business in maintaining the ecol-
ogy, includingthe detrimental effects that many industrial processeshave on the integrity of the
environment. By exerting a great deal of political pressure, the public forced government into
the position of “protector of the environment.” The government lived up to its newly estab-
lished role by developing a myriad of bureaucratic agencies, committees, subcommittees, and
review boards to address environmental issues.
The late 1970s brought about concrete, tangible legislation on waste treatment and pollu-
tion prevention. The basic legislation was merely a small snowball balancing precariously on
the edge of a ski slope. Over the years to follow, regulations grew until small businesses were
facing a veritable avalanche of rules, acts, regulations, and amendments.
EPA, DOT, CERCLA, SARA, RCRA, and OSHA are not charitable foundations request-
ing tax-deductible donations.They are regulatory agencies and regulatory acts. The cumulative
results of their efforts comprise an extensive list of emission limits, exposure limits, disposal
limits, etc. Failure to comply with their standards can result in tremendous fines. Onefine from
any of these agencies could translate into bankruptcy for a small business.
Today, small business operators may be confronted by over 10,OOO pages of regulations,
and the number continues to grow. It is estimated that each new page of federal regulations
costs businesses about $10 million. Unfortunately, over 90% of the money, efforts, and regu-
lations focus on end-of-the-pipe wastes. Little emphasis is placed on the nature of the process
443
644 Philips
being regulated, i.e., the beginning of the pipe. Obviously, what goes in directly affects what
comes out.
Most federal andstate environmental funds are spent on pollution control and remediation.
National spending on pollutionand waste control is approximately $70 billion, with two-thirds
of that amount being suppliedby industry. That represents a large sumof money that could be
used for investments, expansions, and capital outlay if the waste stream could be reduced or
eliminated [13.
To make matters worse, the land available for disposal is quickly disappearing, and gov-
ernment regulations on land burial of waste are becoming more stringent. Once a waste is cre-
ated, the creator is responsible forever. Long-term waste liabilitymay be 200 times as costly as
the initial disposal. Obviously, this can drastically affect the cost of doing business.
Approximately 300 million tons of hazardous waste is buried annually in the United States.
Over 7 billion tons of solid waste is generated each year by 72,000 businesses. Such estimates
provide a driving forceto regulate what is happeningto these wastes. The reduction of waste
has been a regulatory requirement for several years, providing a strong motivationto comply;
however, this has traditionally not been sufficient to ensure full compliance with existing reg-
ulations. Businesses generally consider wastes as end products requiring disposal and not as
expenses that need to be reduced. Traditionally, most businesses have preferred to use waste
management techniques such as treatment, incineration, or land burial. Such techniques are
applied strictly to the end of the process[2].
These old techniques pose environmental risks, require meeting costly regulatory compli-
ance standards, and increase future liabilities. Disposal costs will continueto increase as reg-
ulationsconcerningwastebecomemorerestrictive.HalfofallU.S.landfillsarealready
nearing or exceeding their designed capacity. Some government agenciesare already stressing
a zero-discharge philosophy. In meeting these new regulations, companies will need to place a
strong emphasis on source reduction and on-site recycling while shifting away from off-site
recycling or disposal [3].
In 1976, the Resource Conservation and RecoveryAct (RCRA) established a “cradle-to-
grave” responsibility for the generator of a hazardous waste. Theneed for better waste man-
agement was increased by the Hazardous and Solid Waste Amendments (HSWA) of 1984,
which applied even more restrictions. The intent of these laws is to prevent environmental deg-
radation and to protect natural resources. This philosophy is clearly stated in the Pollution Pre-
vention Act of 1990, which reads:
The Congress hereby declares it to be the national policy of the United States that, pol-
lution be prevented or reduced at the source wherever feasible; pollution that cannot
be pre-
vented should be recycled in an environmentally safe manner whenever feasible; pollution
that cannotbe prevented or recycled should be treated in an environmentally safe manner;
and disposal or release into the environment shouldbe employed only as a last result.
The Comprehensive Environmental Response, Compensation and Liability
Act (CERCLA,
or Superfund) was passed in1980, raising the stakes in the waste disposal game considerably.
CERCLA is responsible for repairing environmental damage done because of past and present
improper management of wastes. In 1986, the Superfund Amendments Reauthorization Act
(SARA) was passed. SARA assigned liabilityto the responsibleparties and provided a means
by which to hold the parties financially responsible.The principle of jointand several liability,
upheld in the U.S. Supreme Court decisionU.S. v Stringfellow, makes all parties whose waste
is contained at a Superfund site equally responsible for cleanup costs[4].
The reduction of waste has been a regulatory requirement for several years. However,
there was no common description of what constituted waste reduction, there were few data
Strategiesfor Small Businesses 645
on the extent of industrial waste reduction, and data that were collected were often mea-
sured incorrectly [5].
Under the Clinton-Gore administration, waste reduction will probably receive increased
governmental emphasis. In Vice President Gore’s book Earth In The Balance, he points out
that it will be increasingly important for all companies to incorporate standards of environ-
mental responsibility into their entire operation [6].
By using materials more efficiently, industry can reduce waste. This in turn will allow
greater protectionof human health and the environment while ensuring regulatory compliance.
Other factors are beginning to have a considerable impacton how waste is handled. Of these,
probably the most overwhelming incentive is liability.
The generator of a hazardous waste isultimately and solely responsible for what happens
or has happened to that waste in the past, present, and future. The imminent hazard provisions
of SARA and RCRA affect waste managed on-site as well as waste shipped off-site and can
close down a business as well as imposing heavy fines and penalties. EPA can assess triple
damages (three times the amount of the cleanup) and assess a lien on a business property to
collect [l].
There are many compelling reasonsto minimize waste; Table1 summarizes someof them.
RCRA regulations require that generators of hazardous waste “havea program in place to
reduce thevolume and toxicity of waste generated tothe extent that is economically practical.”
A waste reduction program isan organized, comprehensive, and continual effort to systemat-
ically reduce the generation of waste. It should become part of a company’s everydayoperating
policy. While the main goal is to reduce or eliminate waste, it will also bring about an im-
provement in production efficiency.
Under the more stringent legislation being considered, waste reduction programs would
include all environmental pollutants regardless of whether their disposal is permitted. This in-
cludes solid waste, wastewater, hazardous waste, andair pollutants. Also being consideredare
bills restricting waste reduction options by considering only source reduction or on-site recy-
cling techniques. The strictest legislative packages would not consider off-site recycling or any
treatment separate from the production process within the scope of waste reduction. Although
these proposals have developed support fromcertain congressional quarters and are supported
Table 1 WasteMinimizationIncentives
~ ~~ ~~~~~~ ~
Economics
Landfill disposal cost increases
Costly treatment technologies
Savings in raw material and manufacturing costs
Tax incentives for pollution prevention
Regulations
Certification of a waste minimization program on the hazardous waste manifest
Biennial waste minimization program reporting
Land disposal restrictions and bans
Increasing permitting requirements for waste handling, and treatment
Liability
Potential reduction in generator liability for environmental problems at both on-site
and off-site treatment, storage, and disposal facilities
Potential reduction in liability for worker safety
Public image and environmental concern
Improved image in the community
Concern for improving the environment
446 Philips
by the Office of Technology Assessment, such restrictive legislation is not favorable

to either
manufacturers or the developing recycling industry. Strong efforts by generators to reduce
waste generation are encouragedby the EPA in order to avoid more restrictive regulation[ 5 ] .
II. BARRIERS TO WASTE REDUCTION

Although economic factors often work in favor of pollution prevention approaches, there is
always some resistanceto change of any kind. Waste reduction projects can reduce operating
costs and improve environmental compliance, but they frequently bring out conflicts between
different groups within acompany.
Economic barriers to pollution prevention include the following:
Inaccurate market signals. Sometimes the immediate cost of releasing toxic substances is less
than the cost of implementing a pollution prevention project. This occurs when the long-
range cost of the release is not included in the calculations.
Incomplete accounting. Indirect benefits, such as lower future liabilities and improved public
image, are not commonly considered in a financial analysis.
Fear of lowering quality. This is very common in situations where unused feed materials are
recovered from a waste and recycled back into the process. If not done properly, such pro-
cesses may affect quality.
Workerfear ofjob loss. If employees or labor groups look upon pollution prevention as a
threat to their jobs, these concerns may pose a barrier to new processes.
Fear of losing market share. Surveys suggest that a significant barrier to pollution preven-
tion is reluctance to tamper with proven processes for fear of adverse effects on product
quality [7].
Attitude-related barriers must be overcome before any pollution prevention program is
tried, or it is destined to fail. A prevailing attitude is to maintain the status quo and avoid the
unknown. There is also a fear that a new program may not work as advertised. Without the
commitment of everyone involved, a pollution prevention program is doomed to failure.
The Case of the Proverbial Potato'
In 1986, a coatings manufacturer in Hamburg, Germany hired a bright young process chemist
for one of its factories.The young chemist was involved in preparing a high quality varnish to
be used as a sealer on musical instruments. While reviewing the formula, he was surprised to
see that it called for a potatoto be added after each new ingredient was mixed into the batch.
Curiosity got the best of him. He asked head the chemist what physicalor chemical properties
the potato addedto the batch. The head chemist abruptly told the young man that potatoeshad
been added to the varnish batches for over50 years and reprimanded him for his insolence.
Not easily discouraged, the young chemist began asking other chemists in the lab the about
addition of potatoes. Unable to provide an answer, they too became curious about the use of
potatoes in the varnish batches. One of the older employees on the staff suggested that the
young man contact a retired chemist who lived in a nearby village.
The old chemist had worked at the factory for many years before his retirement. He ex-
plained to the inquisitive young man that during the war years, thermometers had beem very
hard to acquire. Potatoes had been used to tell when the batchhad reached the proper temper-
ature for adding the next ingredient. When this information was conveyed to management, the
use of potatoes was halted at the factory and thermometers were substituted.
'Adapted from Ref. 8.

This story exemplifies our reluctance to change. It also demonstrates that one concerned
individual, through persistence, can make a difference. Of course, a potato is not considered a
hazardous or toxic substance, but it is symbolic. Often, less toxic and equally effective sub-
stitutes are available for a process, but they are not used because “this wayis we’ve
the always
done it.”
When a person does not fully understand the nature of a proposed option and its impact,
a common attitude is that “it just won’t work.” Attitudinal changes are more likely to occur
when people are presented with stimuli that encourage self-persuasion. Techniques of persua-
sion used by others may force the confused individual into a defensive posture. When this hap-
pens, creative options may be dropped before they can be evaluated. Oneway to avoid this is
to use idea-generating sessions (brainstorming), encouraging participants to propose a large
number of options without regardto cost, technology, or barriers. The more impractical ideas
will be dropped anyway, but previously undiscovered problem-solving solutions may emerge.
Many business managers are surprised to discover that waste reduction does not always
necessitate large-scale investments. Significant savings have resulted from such simple, com-
monsense improvementsas better housekeeping, preventive maintenance, balancing inputs and
outputs (inventory control), and minor process changes.
Waste minimization shouldbe viewed as an investment in the company’s future. It begins
with a conceptas simple as “Waste-If you don’t produceit, you won’t haveto dispose of it.”
At first, this statement seems oversimplified and naive; however, upon further review, many
managers have become impressed with how often this principle can be applied.
Waste minimization is a relatively low-cost but effective procedure for reducing liability
and increasing profits. Often, waste minimization processes do not require high technologyor
expensive equipment. In many cases, very simple shop practices and procedures, combined
with low-cost equipment, can greatly reduce the amount of hazardous waste generated. In ad-
dition, 42 states presently offer tax credits or exemptions for companies purchasing pollution
prevention equipment [9].
111. LEVELS OF WASTE MINIMIZATION

There are three major levels in the waste minimization hierarchy. These levels canbe viewed
as steps to improving production processes and savingmoney. The levels, in orderof priority,
are source reduction, recycling, and treatment.
A. Source Reduction
Source reduction involves the minimization or elimination of wastes at their source. It often
includes changesin procedures rather than in technology or machinery, makingit simple, easy,
and cost-effective. Because littleor no wasteis generated, source reduction alleviates the prob-
lems associated with handling and disposing of wastes. It is therefore the most desirable option
in the waste reduction hierarchy.
1. ImprovedOperatingPractices
Operatingpracticesincludeprocedural,administrative,andinstitutionalmeasuresthata
company can useto reduce waste. Many of these measures have been used for decades by suc-
cessful businesses as efficiency improvements and sound management practices. They can of-
ten be implemented with little cost and have a high return on investment. Good operating
practices include
Management and personnel involvement
Material handling and inventory practices
Philips
Loss prevention
Waste segregation
Complete accounting practices
Production scheduling
Management and personnel involvement includes employee training, incentives and bo-
nuses, and other programsthat encourage employees to conscientiouslystrive to reduce waste.
Material handling and inventory practices include programsto reduce loss of input mate-
rials due to improper handling, expired shelf life, or improper storage conditions.
Loss prevention minimizes wastes by such means as avoiding leaks and spills from equip-
ment and preventing evaporation by keeping solvent containers closed tightly.
Waste segregation practices reduce the volume of hazardous wastesby preventing the mix-
ing of hazardous and nonhazardous wastes.
Complete accounting practices involve allocating waste treatment and disposal costs di-
rectly to the departments or groups that generate wasterather than chargingthese costs to gen-
eral company overhead accounts. In doing so, the departments or groups that generate the
waste become more awareof their treatment and disposalpractices, thus providing a financial
incentive to minimize waste.
By judicious production scheduling of batch runs, the frequency of equipment cleaning
and its resulting waste can be reduced. This technique is particularly useful in printing and
painting operations.
Example: Good OperatingPractices-Management. A printing companyreducedpaper
waste by 30% simply by implementing process control measures. Inks, plates, and presseswere
kept at peak efficiency, reducing the need for reprinting.
Example: Good Operating Practices-Material Handling and Inventory. A consumer product
company in California adopted a corporate policy to minimize the generation of hazardous
waste. In order to implement the policy, the company mobilized quality circles made upof
employees representingareas within the plant that generated hazardous wastes. The company
experienced a 75% reduction in the amount of wastes generated by instituting proper mainte-
nance procedures suggestedby the qualitycircle teams. Since the team members were also line
supervisors and operators, they made certain that procedures were followed.
Process changes provide the best opportunities for reducing waste. One way to alter the
process is to use different raw materials. It may be possible to choosea material that allowsfor
a greater percentage of product in the end. A material that is nontoxic, evenif it does become
a waste, will not pose as great a danger to the environment.
Employees’ assignments canbe planned carefully in advance so they are done efficiently
and thoroughly. Putting excessive pressure on workers to complete jobs quickly may mean that
the job will not bedone properly thefirst time because itwas rushed. Consequently, moretime
and materials will be required to correct the mistakes.
Another way to reduce waste is through better housekeeping. Keeping an operation clean
and orderly improves safety, delays deterioration of equipment, reduces breakdowns, and in-
creases efficiency. It will also assist in discovering leaks and spills when they first occur.
Improving inventory control has been found to be a big step in reducing waste. Records
should keep track of which materials are being used and howquickly they are being used. Buy-
ing large quantities of materials just because the unit cost is lower will not save money if a
majority of the material sits on the shelf anddries out or becomes unusable because of chemical
decomposition.
Businesses
Strategiesfor Small 649
To avoid exceeding an expiration date, it is also useful to rotate stock periodically. The
freshest material cango to the back of the shelf, with the oldest moved to the front. Ordering
environmentally safe products greatly reduces disposal costs should a material be stored past its
useful shelf life.
Preventive maintenance will also contribute greatly to waste reduction.If a tool or piece
of equipment is maintained properly, it will last longer and provide a more productive of the use
process for which it was designed.
Many helpful changes that foster waste reduction are more procedural than technological.
Improved operating proceduresdo not have to be elaborateor expensive; they just need to get
the job done.
2. TechnologyChanges
Technology changes are oriented toward industrial process and equipment modifications that
will reduce waste, primarily in a production setting. Technology changes may range from mi-
nor improvements that can be implemented in a matter of days at low cost to new processes
with startup costs that require large capital outlays. These changes include
Alterations in the production process

Changes in equipment, layout, or piping
Use of automation
Changes in process operating conditions, suchas flow rates, temperatures, pressures,and res-
idence times
Example: Technology Changes-Equipment, Piping, or Layout. In many dry cleaning facil-

ities, existing equipment is retrofitted with ventilation
and vapor recovery machinery. It is cost-
effective to invest in modern equipment that can practically eliminate emissions and human
contact with solvents.
Example: Technology Changes-Process. Many companies are installing equipment
to recycle
wastewater by separating the hazardous components from the water, which can then be reused.
Example:TechnologyChanges-Process. A manufacturer of fabricated metal products for-
merly cleaned nickel and titanium wire in an alkaline chemical bath priorto using the wire in
the product. In 1986, the company began to experiment with a mechanical abrasive system.
The wire was passed through the system, which uses silk and carbide pads and pressure to
brighten the metal.The system worked but required passing the wire through the unit twice for
complete cleaning. In 1987, the company bought a second abrasive unit and installed it in se-
ries with the first unit. This allowed the company to completely eliminate the need for the
chemical cleaning bath.
3. InputMaterialChanges
Input material changes accomplish waste reduction by reducing or eliminating hazardous ma-
be made to avoid
terials that enter a production process. Also, changes in input materials can
generation of hazardous wastes within a production process. Input material changes include
material purification and material substitution.
Example:InputMaterialChanges. An electronics manufacturing facility originally cleaned
printed circuit boards with organic solvents. The company found that by switching from an
organic-based cleaning system to a water-based system, the same operating conditions and
workloads could be maintained and the aqueous system cleaned six times as effectively. Thisre-
sulted in a lower product rejectrate and eliminated theneed for disposal of a hazardous waste.
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4. ProductImprovements
Product improvements are performed by the manufacturer of a product with the intent of re-
ducing waste resulting from a product’s use. Product improvements include product substitu-
tion, product conservation, and changes in product composition.
Example: Product Improvements-Product Substitution. In the paint manufacturing industry,
water-based coatings are finding increasing application where solvent-based paintswere pre-
viously used. These products do not have the toxic or flammable characteristics that make
solvent-based paints hazardous.Also, it is not necessary to clean the applicators with solvent.
The use of water-based paints instead of solvent-based paintsalso greatly reduces volatile or-
ganic compound emissions to the atmosphere. In many cases, water-based productsare cheaper
than those based on organic solvents.
B. Recycling
1. Extended Use andReuse
Recycling via use and/or reuse involves either returning a waste materialto the originating pro-
cess as a substitute for an input material or using it in another process as an input material.
Return to original process
Raw material substitution for another process
Example: Reuse-Return to Original Process. A printer of newspaper advertising purchased
an ink recycling unit to produce black newspaper ink from its various waste inks. The unit
blends different colors of waste ink together with fresh black ink and black tonerto create the
new black ink. This ink is then filtered to remove flakes of dried ink. The recycled inkis used
in place of fresh black ink and eliminates the need for the company to ship waste ink off-site
for disposal.The price of the recycling unit was paid off18inmonths based only on the savings
in fresh black ink purchases. The payback period improved to 9 months when the costs for
disposing of ink as a hazardous waste were included.
2. Reclamation
Reclamation is the recovery of valuable material from a hazardous waste. Reclamation tech-
niques differ from use and reuse techniques in that the recovered material is not used in the
facility but is sold to another company. Waste exchanges provide valuable information to link
companies that wish to transfer wastes and those that wish to use them [8]. Materials to be
reclaimed may be processed for resource recovery or processed as a by-product.
Example: Reclamation. A photoprocessing company uses an electrolytic deposition cell to re-
cover silver from the rinsewater from film processing equipment. The silver is then sold to a
small recycler. When the silver is removed from this wastewater, the wastewater can be dis-
charged to the sewer without additional pretreatmentby the company. This unit paid for itself
in less than 2 years due to the value of the recovered silver.
The company also collects used film and sells it to the same recycler. The recycler bums
the film andcollects the silver from the residual ash. Removing the silver fromthe ash renders
the ash nonhazardous.
Many environmental groups focus on recycling as the solution to solid and hazardous
waste problems;however, in most recycling projects, somematerials are lost, contaminated, or
leached into the environment. Evenin Japan, where industries and municipalities have the
world’s most successful recycling program, all of their recycling practices combined reduce
waste by only 65%. Recycling is no substitute for source reduction [l].
C.
Treatment
Treatment shouldbe considered onlyas a last resort when implementing a waste reduction pro-
gram. Waste treatment may involve conversion of hazardous waste to a less toxic form by
chemical, biological,or physical meansor it couldbe as simple and dangerous as placement in
landfills, deep-well injection, or ocean dumping [6].
Treatmentmayinvolvemoreexoticprocessesforcleaningup or usingcontaminated
wastes. Many shop wastes canbe cleaned up using activated carbon filtration, biological treat-
ment, and extraction. Some wastes can be put to good use as a fuel source for on-site heat-
ing units.
Creative processes and ideas can accomplish wonders in reducing wastes. Even though
new ways of thinking and reformulating processes may be required, it is less difficult to im-
prove on waste minimization techniques thanto improve on waste treatment techniques. Some
of the real incentives that waste minimization has going forit are that most of the procedures
that can be carried out are not expensive, save money over treatment costs in the long run,are
not time-consuming, and will help protect business interestsas well as the environment.
IV. ORGANIZING A WASTE REDUCTION PROGRAM

Because a waste reduction program affects many groups within a company, a program task
force should be assembled. This group must include members of any department that has a
significant interest in the outcome of a waste reduction program.
The formalityor informality of a waste reduction program will depend on the nature of the
company. A program in a large, highly structured company will probablybe quite formal, one
in a small company, less formal. Table 2 lists the typical responsibilities of a waste reduction
program task force. The task force draws on the expertise of everyone in a small company.
Even in a small business, several people willbe required to implement a successful waste
reduction program. People with responsibility for waste treatment and disposal, production,
facility maintenance, and quality control should be included on the team. At a small facility, a
single person, for example, an owneror manager, may have all of these responsibilities; how-
ever, even with a small facility,at least two people shouldbe involved to get a variety of view-
points and perspectives.
Some larger companies have developed a system in which assessment teams visit different
facilities within thecompany. Benefits result through sharingof ideas and experiences. Similar
results can be achieved for smaller businesses by visiting other facilities with similar operations.
Table 2 Responsibilities of the Waste Minimization F%mTaskForce

Get commitment and a statement of policy from management.
Establish overall waste minimization program goals.
Establish a waste-tracking system.
Prioritize the waste streams or facility areas for assessment.
Select assessment teams.
Conduct (or supervise) assessments.
Conduct (or monitor) technical/economic feasibility analysesof favorable options.
Select and justify feasible options for implementation.
Obtain funding, and establish the schedule for implementation.
Monitor (and/or direct) implementation progress.
Monitor performance of the option once it is operating.
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Table 3 Attributes of EffectiveGoals

Acceptuble to those who will work to achieve them
Flexible and adaptable to changing requirements
Measurable over time
Motivarioml for all employees
Suitable to the overall corporate goals and mission
Understandable by all employees
Achievable with a practical level of effort
Planning a waste reduction strategy is similar to a big league manager getting his team
ready for baseball season. It is best to
Establish a game plan. Set specific long-term and short-term goals.
Keep your eye on the ball. Concentrate on the worst streams first.
Know your spike zone. Set realistic objectives that center on production activities.
Keep score. Examine possible cost savings for various process changes.
Get the best equipmentfor yourplayers. Do not be afraid to make improvements that will pay
for themselves in the long run.
Remember that expansion teams do not per&orm well early in the season. Invest sufficient
time and effort before evaluating results.
A. SettingGoals
The first priority of a waste reduction task forceis to establish goals that are consistent with
management policy. Waste reduction goals can be qualitative, for example, “a significant re-
duction of toxic substance emissions into the environment”; however, it is better to establish
measurable, quantifiable goals, since qualitative goals canbe interpreted ambiguously. Quan-
tifiable goals establish a clear guideas to the degree of success expected of a program. Other
attributes of effective goals are listed in Table 3.
Waste reduction must be reviewed periodically. As the focus of a waste reduction program
becomes more defined, the goals should reflect any changes. Waste reduction assessments are
not one-time projects. Periodic reevaluation of goals is necessary because changes occur in
available technology, raw material supplies, environmental regulations, and economic climate.
B. Planning a Strategy
The steps involved in planning and organizing a waste reduction program are summarized in
Table 4.
Most small businessesdo not realize how much waste they produce. Ask most managers if
they use all of their raw material,or input, and. they will probably say that they do. What they
actually mean is that they process allof the raw material needed, not that they use the entire
amount purchased. If they feel they are getting their money’s worth, most managers will not
give a second thought to what is lost or wasted.
This philosophy is common in smaller businesses because they often do not have the per-
sonnel, the expertise, or the budget to spend on developing adequate inventory control. The
larger the business, the more resources are available to scrutinize inventory control.
Waste reduction in any size industry can only work if it is embraced by top management.
Small operations often have an advantage here because the owner is usually the immediate su-
pervisor and remains on-site for most of the workday. Through leadership and example, em-
ployees will be motivated to participate in the overall program.
Strategies for SmallBusinesses 653
Table 4 PlanningandOrganizationActivitiesSummary
Setting Up the Program
Get management commitment to
Establish waste minimization as a company goal.
Establish a waste minimization program to meet this goal.
Give authority to the program task force to implement a program.
Starting the Program Task Force
Find a “cause champion” with the following attributes:
Familiar with the facility, its production processes, and its waste management operations.
Familiar with and respected by the employees.
Familiar with quality control requirements.
Good rapport with management.
Familiar with new production and waste management technology.
Familiar with waste minimization principles and techniques and environmental regulations.
Aggressive managerial style.
Getting Company-wide Commitment
Find people who know the facility, processes, and procedures.
Find people from the affected departments or groups.
Incorporate the company’s waste minimization goals into departmental goals.
Solicit employee cooperation and participation.
Develop incentives and/or awards for managers and employees.
Several large corporations, e.g., General Dynamics, Borden Chemical, and the 3M Cor-
poration, have pioneered effective waste reduction programs with procedures thatfit equally
well in smaller operations. These large industries were drivenby upper management pressures,
profit margins,and corporate images. Inherent in each program is a strong waste reduction plan
and direct involvement by employees from all departments [ 8 ] .
Small businesses may not have the capital to spend on expensive equipment or to change
existing processes overnight, but theydo possess a valuable resource in their employees. Cre-
ative ideas and active participationby all employees can translate into unexpected cost savings
and profits for any entrepreneur. Acting on an employee’s recommendation, General Dynamics
was able to eliminate disposal costs of a caustic solution by finding a market for it. Borden
Chemical greatly reduced effluent wasteby encouraging good housekeeping techniques. In the
area of waste reduction, employers should never overlook the obvious and never reject an-
other’s ideas as being too simplistic.
V. THE ASSESSMENTPHASE
A. Selecting a Team
A program task force should be concerned with reducing waste foran entire facility; however,
an assessment team should focus on one particular waste streamat a time if the stream can be
linked to a single process.Team membership should notbe limited to environmental managers
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and engineers. Teams should include all people with direct responsibility and knowledgeof a
particular waste stream or area of a plant.
In addition to internal staff members, assistance from outsiders should be considered, es-
pecially during assessment and implementation phases. These outside people may be trade as-
sociation representatives, consultants, or experts from a different facilityof the same company.
One or more outsiders can bring in new ideas and providean objective viewpoint. An outsider
is more likely to counteract bias brought about by the “sacred cow” syndrome, such as that
encountered when an old process area rich in tradition undergoes an assessment.
Free or inexpensive assistance may be available froma variety of souices, including uni-
versities and community colleges, management associations, state agencies, insurance com-
panies, and retired employees [ 8 ] .
Although their services are expensive, professional consultants bring a variety of experi-
ence and expertise to a waste reduction assessment. Consultants are especially usefulto smaller
companies, which may not have in-houseexpertise in relevant waste reduction techniques and
technologies. Trade associations, community colleges, and public agencies will sometimes
have very knowledgeable p p l e available to provide advice forlittle or no compensation.
Production operators and line employees should not be overlooked as a source of waste
reduction suggestions. They possessfirsthand experience with processes, and their assistance
may be useful in assessing operational changesor equipment modifications thataffect the way
they perform their work.
“Quality circles” have been instituted by many companies, particularly in manufacturing
industries, to improve product quality and production efficiency. These quality circles (some-
times referred to as TQM, total quality management) consist of workers and supervisors shar-
ing ideas on proposed improvements. Qualitycircles are often successful because they involve
production people who are closely associated with the operations and truly appreciate being
part of the decision-making process. Several companies with quality circles have used them
effectively to solicit suggestions for waste reduction that have saved millions of dollars.
B. Collecting and Compiling Data

In order to develop options, a detailed understanding of a plant’s wastes and operations is a
must. An assessment should beginby examining information about processes,operations, and
waste management practices.
There are several questions that need to be answered [lo]:
1. What waste streams does the business generate? How much?
2. With which processes or operations do these waste streams originate?
3. Whichwastes are classified as hazardous,andwhich are not?Whatmakesthem
hazardous?
4. What are the inputmaterials used that generate the waste streamsof a particular process
or plant area?
5. How much of a particular input material enters each waste stream?
6. How much of a raw material can be measured throughfugitive losses?
7. How efficient is the process?
8. Are unnecessary wastes generatedby mixing otherwise recyclable hazardous wastes with
other process wastes?
9. What types of housekeeping practices are used to limit the quantity of wastes generated?
10. What types of process controls are used to improve process efficiency?
Additional types of information for assessing wastes are listed in Table 5.
Strategiesfor SmallBusinesses 655
Table 5 Facility Information for Waste Minimization Assessments

Design information
Process flow diagrams
Material and heat balances (both design balances and actual balances) for
(1) production processes and(2) pollution control processes
Operating manuals and process descriptions
Equipment lists
Equipment specifications and data sheets
Piping and instrument diagrams
Plot and elevation plans
Equipment layouts and work flow diagrams
Environmental information
; Hazardous
waste
manifests
Emission inventories
Biennial hazardous waste reports
Waste analysis
Environmental audit reports
Permits andlor permit applications
Raw materiallproduction information
Product composition and batch sheets
Material application diagrams
Material safety data sheets
Product, utility, and raw material costs
Operating and maintenance costs
Departmental cost accountingreports
Economic information
Waste treatment and disposal costs
Product, utility, and raw material costs
Operating and maintenance costs
Departmental cost accountingreports
Other information
Company environmental policy statements
Standard procedures
Organization charts
C. Site Inspection
Once an assessment team isin place and a specific areaor waste stream has beenselected, the
assessment may continue with a visit to the site. Although collected informationis critical to
gaining an understanding of the processes involved, it is helpful
to witness an actual operation.
In many instances, a process unit is operated differently from themethod described in an op-
erating manual. Modifications may have been made that were not recorded on flow diagrams
or equipment lists.
An assessment team should preparea list of needed information andan inspection agenda
prior to conducting the site inspection. This can bea checklist detailing objectives, questions
and issues to be resolved, andlor further information needed. An agenda and information list
should be given to appropriate plant personnel beforethe visit to allow them time to assemble
the requested information.With a carefully thought-out agenda andchecklist, important points
are less likely to be overlooked during an inspection.
In performing a site inspection, an assessment team should observe each process from the
point where rawmaterials enter to the point where products and wastes leave an area. The team
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should identify suspected sources of waste. Thismay include the production process, mainte-
nance operations, storage areas for raw materials, finished product, and work-in-progress.
Even a plant’s waste treatment area may itself offer opportunities to minimize waste. An in-
spection often results in preliminary conclusions being drawn aboutthe causes of waste gen-
eration. Full confirmationof conclusions may require additionaldata collection, analysis, and/
or site visits.
The following are some guidelines for asite inspection [lo].
1. Prepare an agenda in advance that covers all points that still require clarification. Pro-
vide staff contacts in each area being assessed with an agenda several days before the
inspection.
2. Schedule an inspection to coincide with a particular operation that is of interest (make-up
chemical addition, bath sampling, bath dumping, start-up, shutdown, etc.).
3. Monitor an operation at different times during shifts, especially when waste generation is
highly dependent on human involvement (e.g., painting or parts cleaning operations).
4. Interview operators, shift supervisors, and foremen in an assessed area. Do not hesitate to
question more than one person. Assess operators’ and supervisors’ awareness of waste
generation aspects of their operation.Note their familiarity (or lack thereof) with the im-
pacts their operation may have on other operations.
5 . Photograph an area of interest. Photographs are valuable in the absence of plant layout
drawings. Many details canbe captured in photographs that otherwise would be forgotten
or inaccurately recalled at a later date.
6. Observe “housekeeping” aspects ofan operation. Check for signsof spills or leaks. Visit
the maintenance shop and ask about problems in keeping equipment leak-free. Assess the
overall cleanliness of the site. Pay attention to odors and fumes.
7 . Assess the organizational structure and the levelof coordination of environmental activi-
ties between various departments.
8. Assess administrative controls, such as cost accounting procedures, material purchasing
procedures, and waste collection procedures.
D. Flow Diagrams and Material Balances

Different materials and proceduresare used to execute each process; however, every operation
offers an opportunityto track material flow. Figure1 provides an extremely oversimplified ma-
terial flow chart.
Before a waste reduction plan can be formulated, it is crucialto determine the amount of
waste that the business is already producing. How? Perform a waste audit. What is a waste
audit? It is the direct application of the law of conservation of matter taught in Physics or
Chemistry 101: Matter is neither created nor destroyed. In other words, nothing ever dis-
appears. Everything thatwas here on the first day this planet was created is still with us today,
although it may be in a different form.
Since nothing ever disappears or goes “away,” it must be somewhere. So to find out where
the “matter” is going, a waste reduction team must perform a material balance. In this pro-
cess, a quantitative relationship is established between raw materials, product, and waste. Ma-
terial balances allow for quantifying many losses or emissions that were not previously recorded
by any bookkeeping or inventory system.
In its simplest form, a material balance is representedby the equation
Mass in = mass out + mass accumulated
Strategies for Small Businesses 657
AIR EMISSIONS
SPILLS
Figure 1 Simplified flow chart indicating process components to be included in a material balance
study.
An independent material balance should be made for all componentsthat enter and leave
a process. When chemicalreactions take place in a system, an “elemental balance” should be
performed for specific chemical elements.
Material balances assist in determiningconcentrationsof waste components where data are
limited. Theyare particularly useful when there are points in a process where itis difficult (due
to inaccessibility) or uneconomical to collect analytical data. A material balance candetermine
whether or not fugitive losses are occurring. For example, the evaporation of solvent from a
cleaning tank canbe estimated as thedifference between solvent put into the tank and solvent
removed from the tank.
Characterizing wastestreamsby material balance can require considerable effort; however,
the result is a complete picture of a waste stream. This helps to establish a focus for waste
reduction activities and provides a baseline for measuring performance.
1. Sources of Material Balance Information

Material balance includes materials entering and leaving a process. The following list exem-
plifies potential sources of material balance information:
Samples, analyses, and flow measurements of feedstocks, products, and waste streams
Raw material purchase records
Material inventories
Emission inventories
Equipment cleaning and validation procedures
Batch make-up records
Product specifications
Design material balances
Production records
Operating logs
Standard operating procedures and operating manuals
Waste manifests
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Material balances are easier, more meaningful, and moreaccurate when done for individ-
ual units, operations, or processes. It is important to define a material balance envelope prop-
erly. An envelope should be drawn around a specific area of concern rather than a larger group
of areas or an entire facility. An overall material balance fora facility can then be constructed
from individual unit material balances. This highlights relationships between units and helps to
point out areas for waste reduction.
Several factors mustbe considered when preparing material balances in order to avoid er-
rors that could significantly overstate or understate the waste streams. The precision of ana-
lytical data flow measurements may not allow an accurate measure of a stream. In processes
with very large inlet and outletstreams, the absolute error in measurement of these quantities
may be greater in magnitude than the waste stream itself. Whenever a reliable estimate of a
waste stream cannot be obtained by simply subtracting the quantity of material in a product
from that in a feed, the team must be creative in developing a more advanced methodof quan-
titative analysis.
Time spanis important whenconstructing a material balance. Material balances performed
over the duration of a complete production run are typically the easiest to construct and are
reasonably accurate. Time duration also affects the use of raw material purchasing records and
on-site inventories for calculating input material quantities. The quantities of materials pur-
chased during a specific time period may not necessarily equal the quantity of materials used
in production duringthe same time period. Purchasedmaterials can accumulatein warehouses
or stockyards.
Developing material balances around complex processes can bea complicated undertak-
ing, especialy if recycle streams are present. Such tasks are generally performed by chemical
engineers, often with the assistance of computerized process simulators.
Material balances will often be needed to comply with SARA Title I11 reporting require-
ments to establish emission inventories for specific toxic chemicals. EPA's Office of Toxic Sub-
stances has prepared a guidance manual entitled Estimating Releases and Waste Treatment
Eflcienciesfor the Toxic Chemicals InventoryForm (EPA 560/4-88-02). This manual contains
additional information on developing material balances for listed toxic chemicals [ll].
2. TrackingWastes
By tracking wastes ona regular basis, seasonalvariations in waste flows or single-batch waste
streams are distinguished fromcontinual, constant flows. Changesin waste generation cannot
be meaningfully measured unless the information is collected both before and after a waste
reduction option is implemented. Fortunately, it is easier to do material balances the second
time, and it continues to becomeeasier as more are completed. It is relatively simple and in-
expensive, with today's computer software,to use computerizeddatabase systems to track and
monitor waste streams.
E. Prioritizing Waste Streams and/or Operationsto Assess

Ideally, all waste streams and plant operations should be assessed. Prioritizing waste streams
and/or operations to assess is necessary when available funds, personnel, or time is limited.
Waste reduction assessments should concentrate on the most important waste problems first
and then move to lower priority problems as time, personnel, and budget permit.
Setting priorities for waste streams or facility areas requires a great deal of care and at-
tention, since this step focuses the direction of an assessment activity. Important criteria to
consider when setting these priorities include the following.
Compliance with current and future regulations
Costs of waste management (treatment and disposal)

Potential environmental and safety liability
Quantity of waste
Hazardous properties of a waste (including toxicity, flammability, corrosivity, and reactivity)
Other safety hazards to employees
Potential for removing bottlenecks in production or waste treatment
Available budget for waste minimization assessment program and projects
Small businesses with only a few waste-generating operations should assess their entire
facility. It is also beneficial to lookat an entire facility when thereare a large number of similar
operations. The implementationof good operating measures such as soliciting employee sug-
gestions, awareness-building programs, better inventory and maintenance procedures, and in-
ternal cost accounting changes can be implemented on a facility-wide basis. Many of these
options do not require large capital expenditures and can be put into operation in a relatively
short time.
Performing the mass balance may be the most difficult part of the waste audit, but it will
make the remainder of the waste reduction process easier and more effective.
VI. WASTEREDUCTIONOPTIONS
Once the origins and causes of waste generationare understood, the assessment process enters
the creative phase. Theobjective of this step is to generate a list of waste reduction options for
further consideration. Following the collection of data and site inspections, members of the
team will have begun to identify possible ways to minimize waste in an assessed area. The
identification of potential options relies on both the expertise and creativity of all team mem-
bers. Much knowledge comes from education and on-the-job experience; however, the use of
technical literature, contacts, and other sources is always helpful.
When identifying options, team members should follow the waste reduction hierarchy in
which source reduction possibilitiesare explored first, followed by recycling options. With an
ever-increasing emphasis being placed on zero-discharge and on-site recycling, waste treatment
technology will eventually be phased out ofmany operations. Source reduction is preferred
because it reduces or eliminates waste from the beginning of a process. Recycling should be
considered only when all attempts at performing source reduction have been exhausted, and
then on-site recycling should bethe primary method considered.
A. Methods of Generating Options

The process whereby waste minimization options are generated should occurin an environment
that encourages opennessand independent thinkingby members of the assessment team. While
individual team members will suggest many potential options on their own, the process can be
enhanced,by using some common group decision techniques. These techniques allow an as-
sessment team to identify options that individual members might not have come up with on
their own. Brainstorming sessions with team members are an effective means of developing
options. It is likely that all or most of the options being presented have some merit and some
drawbacks. During a brainstorming session, it is best not to dwell on details but to simply list
as many options as possible.
B. Screening and Selecting Options for Further Study

Several waste reduction options will be identified in a successful brainstorming session. It is
then necessary to identify the options that offer the best potential for minimizing waste and
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reducing costs. Because a detailed evaluation of technical and economic feasibility is often
costly and time-consuming, the proposedoptions should be screenedto identify the ones that
deserve further evaluation. An initial screening will eliminate options that appear unreason-
able, impractical, or inferior without a detailed and more costly feasibility study.
Screening procedures can range from a simple vote by team members to sophisticated
quantitative decision-making formulas. Generally, an informal evaluation utilizes an unstruc-
tured conferencesetting by which an assessment teamor program task forceselects options that
appear tobe feasible. This methodis used most often by small businessesor in situations where
only a few options are practical.
VII. FEASIBILITYANALYSIS
Once the assessment team has agreed to evaluate selected options, a feasibility analysis is
conducted to determine which options are technically and economically practical. The level
of analysis required is directly proportional to the complexity of the option being considered.
Simple options, such as housekeeping improvements, would not require as thorough an eval-
uation as equipment changes[7]. The final product of an assessment phaseis a list of feasible
options for an assessed area. The assessment will have screened out impracticalor unattractive
options. The next step is to determine if remaining options are technically and economically
feasible.
An evaluation should be conductedto determine whether a proposed option will workfor
a specific application. The evaluation of an option should include facility constraints, product
requirements, capital costs, and operating costs.
A fiscal evaluation should consider standard measures of profitability such as payback
period, return on investment, and net present value. Each organization has its own economic
criteria for selecting projects; however, as in any project, the cost elementsof a waste reduction
project can be broken down into long-term and short-term capital costs and operating costs.
All affected groups in a facility should contribute to and review the results of a technical
evaluation. Prior consultation and review with affected groups is needed to ensure the viability
and acceptance of an option. If the option calls for a change in production methods or input
materials, the project’s effects on final product quality must be determined. If, after technical
evaluation, the project appears impossible or impractical, it should be dropped.
VIII. IMPLEMENTING WASTE REDUCTION OPTIONS

The assessment team’s evaluation report should providethe basis for obtaining company fund-
ing of waste reduction projects. Projects should notbe marketed ontheir technical or environ-
mental merits alone. An analytical, fiscally sound description of both short- and long-term
benefits can help edgea proposed project past competing projects for funding. Itis also helpful
to have someone from the manufacturing, purchasing, or accounting section of the facility
present the proposal. This will enlarge the imageof the projectbeyond environmental improve-
ments, to depict the proposed action as a sound business investment.
The presenters of the proposal should be flexible enough to develop alternatives or mod-
ifications. They shouldalso be sufficiently committedto the projectto obtain background data
and support studies and to anticipate potential problems that may be encountered during im-
plementation. Above all, team members should keep in mindthat an idea will not sell if team
members are not sold on it themselves. This is why management and production staff people
should support the concept of waste reduction from the beginning of the process.
Strategies for Small Businesses 661
A. ObtainingFunding
Waste reduction projects generally call for improvements in process efficiency and/or reduc-
tions in operating costs of waste management. These are the points that shouldbe emphasized
in the decision-making process.
An assessment team made up of financial and technical personnel helps to ensure that a
sponsor’s enthusiasm is balanced with objectivity. Even if a project promises a high rate of
return, a small company may have difficulty acquiring funds for capital investment. In this
case, the company should look to outside financing. It generally has two major sources to
consider: private sector financing and government-assisted funding. If the venture is prudent
and cost-effective, many lenders will gladly provide loans for pollution prevention or waste
reduction projects, particularlyif they have already backed the company with other loans. Gov-
ernment grants and loans arealso available for pollution prevention projects. If the project in-
volves a new or unusual approach to waste reduction, the entire proposalmay be funded by a
research grant.
B. Installation
or material changes canbe im-
Waste reduction proposals that involve operational, procedural
plemented as soon as funding has been approved. For projects involving equipment modifica-
tions or new equipment,theteamwill be involvedwithplanning,design,comparisons,
procurement, and construction of thenew equipment.
C. MeasuringWasteReduction
Once a waste reduction project has been implemented, it mustbe monitored to determine how
effective the option actually turns outto be. Projects that do not measure up to their original
performance expectations may require reworking or modification.
One measureof project effectiveness is its payback time. A project should pay for itself in
a reasonable time through reduced waste disposal costs and/or reduced raw materials costs. The
primary goal of the project, however, is to reduce waste. This should be the major consider-
ation when implementing a program.
Accurate measurements must be takento express the extent of waste reduction. The pro-
cess by which the wastes are reduced must be fully understood and compared to previous pro-
cesses to determine the total impact of the new method.
D. AssessingNewProcesses
It is important to avoid trading one waste problem for another. Waste reduction principles
should be applied tonew projects experimentally on a small scale. Iteasieris to observe waste
generation during research and development than to go back and modify a process after it has
already been installed.
With new emphasis on attaining zero discharge and eliminating off-site recycling, com-
panies must strive to implement fully contained systems.
E. KeepingtheFaith
A waste reduction program is an ongoing rather than a one-time effort. Once high priority
streams havebeen assessed and reducedor eliminated, an assessment team should look at low
priority streams. The ultimate goal of the program should be to reduce the generation of waste
to the maximum extent achievable.
662 Phillips
To be truly effective, a philosophy of waste reduction must be developed in the organiza-

tion. This meansthat waste reductionmust be an integral part of the company’s operations. The
most successful waste reduction programs to date have all developed this philosophy within
their companies.
REFERENCES
1. Long, R. E., The problem of waste disposal, Rd. Shelf, 60, 41-48 (1989).
2. University of Tennessee Teleconference,Promote Landfill AlternativesNow. PLAN Booklet, 1992.
3. Council for Solid Waste Solutions, The Solid Waste Management Problem, 1989, pp. 7-10.
4. Marburg Associates, Site Auditing: Environmental Assessments of Property, STP Specialty Tech-
nology Publishing, 1992, Appendix
5. U.S. Office of Technology Assessment,Serious Reductionof Hazardous Waste,Booklet U.S. Con-
gress, Washington, D.C., 1991.
6. Gore, A., Earth In the Balance, Houghton Mifflin, Boston, 1992, pp. 342-343.
7. Theodore, L. and Mffiuinn, Y., Pollution Prevention, Van Nostrand Reinhold, New York, 1992,
p. 170.
8. Philips, D. A., Waste Reduction in Industrial Processes, Florida Dept. of Environmental Regula-
tion,1991,pp.1:16-24.
9. Environmental Information, Ltd., Tax incentives for pollution abatement, Environ. Dig. State Pro-
grams, Minneapolis, Minn., May1992,pp.18-21.
10. Freeman, H. A.,Hazardous Waste Minimization, Mffiraw-Hill, New York, 1990, pp. 77-107.
11. FloridaStateEmergencyResponseCommission, HowToComply Handbook SARA Title III
1990, p. 7.
33
Contaminated Soils in Highway
Construction
Namunu J. Meegoda
New Jersey Instituteof Technology
Newark, New Jersey
1. INTRODUCTION
In 1988, there were approximately4 million milesof roads in the UnitedStates of America, of
which 2.3 million miles were surfaced with asphalt or concrete. Of the surfaced roads, approx-
imately 96%, or 2.2 million miles, had asphalt pavements[l]. More than 95% of the2 trillion
vehicle miles traveled each year occur on asphalt-paved roads. In 1988, expenditures for high-
ways amounted to over $68 billion at all levels of government [l]. During 1988, 500 million
tons of hot mix asphalt (HMA) was produced and placed, and about 250 million tons of HMA
was used for construction, rehabilitation, and maintenance of the highways [l]. The HMA in-
dustry directly employs 300,000 people and indirectly accounts for an additional 600,000jobs
[l]. The hot mix asphalt concrete consists of a combination of aggregates blended and uni-
formly mixed, coated with asphalt cement, and compacted into a dense material. The materials
in HMA consist of (1) coarse aggregates with sizes ranging from 1.5 in.to U.S. sieve No. 4,
(2) fine aggregate or sand with sizes passing U.S. sieveNo. 4 and retained on U.S.sieve No.
200, (3) mineral filler such as crushed stone dust or lime passing U.S. sieve No. 200, and (4)
asphalt cement. A typicalHMA composition consistsof 50% coarse aggregates, 40% fine ag-
gregate, 5% mineral filler, and 5% asphalt cement.
Asphalt cement is obtained by distillation of petroleum crude. The asphalt cements ob-
tained from refineries are classified as AC-2.5, AC-5, AC-10, AC-20, AC-30, or AC-40 based
on viscosity. To obtain sufficient fluidityof asphalt cement for proper mixing and compaction,
both the aggregate and the asphalt cement are heated prior to mixing; hence the product is
called hot mix asphalt (HMA) concrete.
qpically 5-10% waste products such as recycled asphalt pavements, tire rubber, glass,
municipal solid waste (MSW)ash, roofing shingles, polythene waste,fly ash, bottom ash, ore
slug, and petroleum-contaminated soils are addedto HMA without sacrificing its strength and
performance [2-51. U.S. Department of Transportation data [l] suggest that an estimated 25
million tons of industrial waste can be recycled and consumed annually by the U.S. asphalt
663
664 Meegoda
industry, by simply adding 5% waste productsto all HMA mixes. Therefore, all levels of gov-
ernment in the UnitedStates emphasize the inclusion of waste products in HMA. Usually sep-
arate mix designsare not performedto include such waste material. Either the amount of materi
in the original mix is proportionately reduced or waste products replace the mineral filler.
Petroleum-contaminated soil (PCS), one of the industrial solid waste products used in
HMA, is generated from leaking underground storage tanks (USTs), including their piping sys-
tems. During the 1950s and 1960s, the construction of many gasoline stations and chemical
manufacturing and processing facilities led to the installation of millions
of USTs. Several mil-
lion USTs in the United States contain petroleum products. Tens of thousands of these USTs,
including their piping systems, are currently leaking [6].The U.S. Environmental Protection
Agency estimates that there are more than400,OOO leaking USTs with petroleum hydrocarbons.
Many more are expected to leak in the future. Most states vigorously encourage the removal of
all tanks after 25 years of service. It is estimated that the removal of a leaking tank generates
approximately 50-80 yd3 of contaminated soil. In addition, soils that surround petroleum re-
fineries and crude oil wells are contaminated with petroleum products. Since groundwater is a
source of drinking water, federal legislation seeks to safeguard our nation’s groundwater re-
sources. Congress responded to the problem of leaking USTs by adding Subtitle I to the Re-
source Conservation and RecoveryAct (RCRA) in 1984. The current federaland state statutes
require that leaking USTs be removed to prevent further contamination.
Petroleum-contaminated soils consist of mixtures of natural sands, silts, and clays with
petroleum products. A small portion of light petroleum product mixed with asphalt cement
merelyproduces an asphaltcementofslightlydifferentspecification or characterization.
Therefore, it is believedby many involved with the asphalt industry that a small increase in the
quantity of light petroleum substanceswould not damage the HMA. This is, in fact, the basis
for the theory that contaminated soils can be used in asphalt concrete paving. However, the
inclusion of natural soils inHMA and the environmental impact dueto such inclusion require
an in-depth study.
When PCSs are added to HMA, three beneficial actionsoccur: incineration, dilution, and
solidification. Part of the petroleum is used as a fuel and is burned during the production of
asphalt concrete; thus a majority of the contaminantsare eliminated beneficially, which reduces
fuel costs. Since only5-3096 petroleum-contaminated soilis added to virgin aggregates during
the production of asphalt concrete, there is spreading and dilution. The asphalt cement actsas
a binder in asphalt concrete; therefore, the remaining diluted contaminants are solidified and
stabilized in the final asphalt concrete matrix.
Strength or stability, durability, and workabilityare the primary factorsto be considered in
hot asphalt mix designs [7]. The secondary factors are flexibility, permeability,fatigue resis-
tance, skid resistance, and stripping action [7].Since the HMA produced withPCSs is used for
paving, it must satisfy all the engineering and environmental requirements specified by the ap-
propriate federal, state, and local agencies.
In 1990, a major laboratory and field research project fundedby the New Jersey Depart-
ment of Environmental Protection and Energy (NJDEPE) was initiated to investigate the fea-
sibility of using PCSs in HMA. An extensive laboratory and field study was conducted to
evaluate the use of PCSs as an aggregate replacement in the production of hot mix asphalt
(HMA) concrete. In the laboratory and field investigations, petroleum-contaminated soils were
added to HMA, and the resulting asphalt concrete mixes were tested for strength, durability, ,
permeability, and leachability. During the field production of HMA and PCSs, emissions of
volatile organic compounds(VOCs) were also monitored. In this chapter, the engineering per-
formance of HMA with K S s is summarized and the environmental impact of the process is
described in detail.
Soils
Contaminated in Highway Construction 665
Table 1 DataonSixContaminatedSoilsfromNewJersey
Soil 1 Soil 2 Soil 3 Soil 4 Soil 5 Soil 6
classification
Soil Well-graded
Clayey
Silty
sand
Poorly
siltSilty
clay Poorly
sand graded sand
with silt
moisture
In situ 7.3 24.1 14.3 14.4 19.6 10.1
content (a)
qpe andamount
1100 ppm 1200 ppm 6600 ppm 25 ppm 1500 ppm 330 ppm
of contamination
heating
heating
oilheating
oilgasoline
oil gasoline
gasoline
Source: Meegoda et al. [ 8 ] .
II. EXPERIMENTAL PROCEDURE AND RESULTS

A. Engineering Performance of HMA with PCSs
1.SoilClassification
Six contaminated soils providedby NJDEPE from sites identifiedas containing soils with less
than 1% total petroleum hydrocarbons (TPHs) were selected for testing and for characteriza-
tion. Three soils were contaminated with heating oil, and the other three were contaminated
with gasoline. The degree of contamination for oil-contaminated samples was determinedby
the Soxhlet oil and grease extraction method (USPHS standard method for the analysis of water
and wastewater). Table 1 gives the soil classification data and lists the type and amount of
contaminants in each soil.
2. Stability or Strength of HMA with PCSs
All the asphalt concrete samples were designed for New Jersey surface coarse mix (NJ 1-3). A
control mix was designed and tested for comparison. The mix designs to include soils were
prepared for each of the six soils based on the sieve analysis data. (Please refer to Meegoda
et al. [8] for grain size analysis data for soilsand aggregates and the NJ 1-3 specifications.) The
optimum percentages that may be usedin the NJ 1-3 mix based on aggregate blending for
the above six soils wereas follows: Soil I , 35%; soil 2, 10%; soil 3, 20%; soil 4, 15%; soil 5,
10%;andsoil 6 , 15% [8]. These percentages are muchhigherthanthecurrentpracticeof
5% PCSs. Once the maximum amountof PCS that may be added to HMA was determined, the
suitability of such an addition was evaluated.The Marshall stability test was performed using
ASTMD1559.BasedontheNewJerseyDepartmentofTransportation(NJDOT)require-
ments for Marshall strength, bulk density, air voids, voids in mineral aggregates (VMA), and
flow, the optimum asphalt content for each mix was selected. The optimum asphalt contents
based on Marshall test results for the control mix and for the six contaminated soils are shown
in Table 2 [8]. Table 2 also shows the dry density, Marshall stability, air voids, VMA, and
flow values at the optimum asphalt contents for the control as well as for HMA made with
each soil type. The New Jersey specifications for high traffic volume 1-3 mix are also shownin
Table 2.
If an asphalt concrete meets all state specifications and if it is a workable mix, then it is
accepted as a paving material. Exceptfor the control mix and HMA mixed withPCS No. 4, as
shown in Table2, all the HMA mixes with PCS were acceptableas paving materials. The con-
trol mix and the HMA mix with soil No. 4 had low flow values. A higher flow value can be
selected for all three mixes from Marshall test results with higher asphalt contents, but it
will result in lower stability values (lower than 8006 N). If a lower Marshall strength value
666 Meegoda
Table 2 Optimum Properties of Asphalt Concrete with PCSs for NJ 1-3 Mix
Asphalt
concrete
Allowable for
property NJ 1-3 Control
Mix Soil 1 Soil 2 Soil 3 Soil 4 Soil 5 Soil 6
Strength (N) >8006 8006 8228 8450 10229 8450 8317 10452
Flow (0.25 mm) >6.0 4.0 11.0 8.0 7.5 3.5 6.5 7.7
Air voids (%) 2.0-8.0 7.0 7.5 3.0 5.7 8.0 4.0 3.4
VMA (%) >13.0 18.0 17.8 14.0 16.8 18.0 14.7 14.2
Density (W/m3) NIA 24.3 24.8 24.5 24.1 23.4 24.6 24.5
Optimum asphalt 4-8 5.0 4.5 4.5 5.0 4.5 4.5 4.5
content (%)
N/A= not available.
Source: Meegoda et al. [8].
(say 6671N) is acceptable, then the control mix and the HMA made with soil No. 4 are ac-
ceptable as paving materials. Based on the test results shown in Table 2, it can be stated that
the HMA with PCSs produced better asphalt concrete thanthe control. This may be due to the
better blend obtained by adding natural soils.
3. Durability ofHMA with PCS

ASTM D4867 describes the test procedure for determining the effect of moisture on asphalt
concrete mixtures,a factor that is very important for the durabilityof hot mix asphalt concrete.
It has a section on freeze-thaw conditioning of a mixture. However, the freeze-thaw and wet-
dry tests require onlyone cycle eachof freeze-thaw or wet-dry. There was no rationale for the
selection of one cycleof freeze-thaw or wet-dry to evaluate the moisture damage when, in the
real world, asphalt concrete pavements are subjected to several freeze-thaw and wet-dry cy-
cles under service conditions before they are removed for resurfacing. Therefore, an experi-
mental program was designed to evaluate the moisture damage of the control mix and one mix
prepared with PCS No. 3. In this experiment HMA specimens were subjected to several cycles
of freeze-thaw and wet-dry. For this experiment, 18 specimens of control mix and 18 speci-
mens of HMA mixed with PCS No. 3 were used. The experimental test resultsof an extended
freeze-thaw test are plotted in Figures 1 and 2. Figures 3 and 4 show similar data for wet-
dry tests.
In this extended durabilitytest, the control mix and HMA with PCS No. 3 were tested for
one, three, seven, and 14 cycles, with each cycle taking approximately48 hr. Upon completing
14 freeze-thaw and wet-dry cycles, data were collected and graphically displayed. It can be
concluded from thesetest results that as the temperature drops to freezing temperatures for the
freeze-thaw specimen, the asphalt concrete contracts and becomes brittle, creating tiny cracks
on the surface of the sample, which provide entry points for water. Water inside the specimen
causes moisture damage due to strippingand volume expansions during subsequentfreeze cy-
cles. With the increasein the number of freeze-thaw cycles, the cracks get larger,letting more
water into the specimen and eventually leading to the failure of the specimen. The data from
cyclic freeze-thaw tests indicate that the percentage swell increased rapidly during the first
cycle and then gradually reacheda maximum before the specimen failed. It is believed thatthe
specimen reached its maximum percentage swell when it was totally saturated, and stripping
occurred before complete failure. The tensile strength ratio also decreased rapidly during the
first cycle and also began to level off to zero strengthafter 14 cycles. The behavior seemsto be
similar for the control mix and the mix containing PCS No. 3, suggesting comparable durability
Contaminated Soils in Highway Construction 667
.-
c
.............
70- ......................................................................................................
d
5 60-........................................................................................................ ............................................... .............
m PCS#3
c
2 50 -
iz
-.- 40- .............
U)
c 30- .......... " ............ " .. .......
F 20- " .....
10...........................................
0 1 I I I I 1
0 2 4 6 8 10 12 14 ' 5
NUMBER OF CYCLES
Figure 1 Extended freeze-thaw test for control mix and HMA with PCS No. 3-TSR values. (From
Meegoda et al. [9].
100
ap
h 90
v)
t 80 ......................
0
.-
+-
70
-a
.-
U)
C
F
0 T
0 2 4 12
8
6 10 16 14
NUMBER OF CYCLES
Figure 2 Extended freeze-thaw test for control mix and HMA with PCS No. 3-swell values. (From
Meegoda et al. [9].)
values for these two mixes. It also seems that there is a correlation between the percentage swell
and the tensile strength ratio. The data show that most of the strength is lost during the f i i t
cycle, and hence there was no need to test beyond one freeze-thaw cycle as suggested by
ASTM D4867.
The cyclic wet-dry test also indicated that the first cycle was the p i n t where atten-
tion must be focused. For the wet-dry test, the tensile strength ratio declined during the f i t '
668 Meegoda
6-
5 5-
5 - ........................................................................................................... p
..c#
.. .................
4 5-
4 - ................. ........
g 3 5 - ............................................................................................................................................................................
h
ti
-I
W 3-........
... ................
I "
...............................
.
...........
"
........... .....................................................................................
"
..................
"" ..............................
^
................................................ ..................... ............................................

-
" "
...............- .............. "

+
... .......... ...-..............."
" " "."..._..............". ........" " " ....".
0 2 4 6 8 10 12 14 16
NUMBER OF CYCLES
Figure 3 Extended wet-dry test for control mix and HMA with PCS No. 3-TSR values. (From Mee-
goda et al. [9].)
.-
0 2 4 6 8 10 16
12 14
NUMBER OF CYCLES
Figure 4 Extended wet-dry test for control mix and HMA with PCS No. 3-swell values. (From Mee-
goda et al. [9].)
cycle and increased thereafter. This is believed to be due to oxidation of asphalt during the
drying cycle. Therefore, it was concluded that the first wet-dry cycle should yield the critical
conditions.
It can be concluded from these tests that freeze-thaw and wet-dry tests with one cycle
indicate whethera specimen is durable, and a strength lossof more than20% indicates that the
specimen will not withstand harsh weathering conditions.
Table 3 Durability of HMA with PCSs

HMA mix Freeze-thaw
Wet-dry
test
test
82.3Control 91.7
89.0 with soil 1
HMA 98.0
100.0 with soil 2
HMA 89.3
HMA with soil 3 87.2 93.9
87.0
HMA with soil 4 83.8
HMA with soil 5
98.4 93.4
HMA with soil 6 100 100
Table 3 shows the tensile strength ratio (TSR) values of wet-dry and freeze-thaw tests
performed based on ASTM D4867 for the control mix and for the HMA made with six soils.
TSR values for HMA with PCSs were not significantly different from that of the control, in-
dicating that HMA with PCSs produced durable asphalt concrete. Some of the wet-dry and
freeze-thaw test results show that the HMA withPCS are better than theHMA produced with
virgin aggregates.
4. Permeability of HMA Prepared with PCSs
Hydraulic conductivity tests were performed on laboratory-compacted HMA specimens. The
specimens were placed on top of a 100 mm diameter flexible-wall permeameter. A cell pressure
of 50 psi (344kPa), a back-pressure of 30 psi (206 P a ) , and a desired pressure difference
(mainly 1 psi or 7 kPa) were applied to the specimen. Twenty-four hours after the in-flowbe-
came equalto the outflow and when the hydraulic conductivity didshow not further reduction,
the permeability test was stopped. The permeability test was conducted concurrently on three
specimens of HMA made with the same PCS. A bladder accumulator was connected between
the permeameter and the pressure panel to separate the permeant from the distilled water used
in the pressure panel. This procedure eliminated the contaminationof the pressure panel.
At the end of the permeability test, the specimen height was measured. Figure 5 shows
typical permeability test results where the variation of hydraulic conductivity with time is
shown. The average saturated hydraulic conductivities of the control mix and HMA mixes with
PCSs are shown in Table 4.
Table 4 shows the saturated hydraulic conductivity data for HMA with and withoutPCSs.
Only one mix (with PC No. 2) showed a lower saturated hydraulic conductivity value than the
control mix. However, the saturated hydraulic conductivity values of all the HMA mixes with
PCSs werelessthan 2.0 X acharacteristicvaluefor low permeableclay-typesoilsand
hence canbe considered acceptable. Table4 also shows the other parameters of asphalt matrix
that contribute to the saturated hydraulic conductivity. It appears that the combination of air
voids, asphalt content, and dlo size (aggregate size correspondingto the 10% finer fraction in
the gradation curve) control the saturated hydraulic conductivity. With a higher percentage of
air voids, one would expect a higher hydraulic conductivity as a larger fractionof asphalt con-
crete matrix will be porous, allowing fluid to flow through those voids. In geotechnical engi-
neering, it is an accepted fact d,, thatsize controls the hydraulic conductivitysoils,
of with soils
that have higher d l , sizes having higher hydraulic conductivity values. However, since all the
HMA mixes tested in this research were NJ 1-3 mixes, there should not be drastic differences
in d l , size as shown in Table 4; hence its influence here is minimal.
The asphalt content will also play a major role when it is higher than optimum, as the
excess asphalt cement, after coating all the particles, will block the interconnecting voids,
670 Meegoda
; inlet
0 :outlet
......
‘0
Time (hrs)
Figure 5 A typical hydraulic conductivity test result. (From Meegoda et al. [9].)
Table 4 Hydraulic Conductivities and Other Related Parameters of HMA with PCSs
Saturated
hydraulic d,, size inthe
HMA conductivity
mix (cm/sec)
(mm)
mix
voids
Air (%) Asphalt
content (%)
4.75
Control 4.7
2.3E-07 0.18
HMA with soil 1 3.3E-07 4.50 0.21 5.6
HMA with soil 2 1.6E-07 0.13 6.9 4.50
HMA with soil 3 1.6E-06 0.12 7.5 5.00
4.25with soil
HMA 4 6.9
1 .OE-06 0.27
HMA with soil 5 8.3847 4.50 0.14 7.3
HMA with soil 6 4.6E-07 4.50 0.15 6.3
causing a reduction in hydraulic conductivity. However, since all the mixes were tested around
the optimum asphalt content values for the corresponding mixes, its contribution to the test
results are minimaltoo.Therefore,thehydraulicconductivityvaluesshouldincreasewith
the percentage of air voids, and there appears to be a direct correlation between percentage
of air voids with the hydraulic conductivity except for mix having PCS No. 3. We suspected
measurement errors for this mix [9]. Therefore, it canbe concluded that the additionof PCSs
may not change the saturated hydraulic conductivityof the asphalt concrete and the change is
due only to the difference in air voids, dlo size, and asphalt content associated with the mix
design [9].
B. Environmental Impact of Adding PCSs to HMA

1. Leachability Test for HMA with PCS
The increase in the number of organic contaminants being detected in groundwater as well
as in surface water is causing concern because of potential health risks claimed to be associ-
Contaminated Soils
Construction
in Highway 671
ated with human exposure to these substances. Soil contaminated with petroleum product
is a potential threat to both surface water and groundwater; thuskey a issue is whether hydro-
carbonwillleach out from the asphalt mixture when it is mixedwith PCSs andused to
pave roads.
The short-term test conducted by Eklund [IO] on the environmental effects of paving
showed that after allowing a pavement to leach for7 days with distilled water, the amount of
petroleum-based compounds leached out and detected was less than 2 ppm. In another series
of experiments by Eklund [lo] with 6% waste oil with an appreciable lead content in cold
mix asphalts (CMA), when the CMA was leached for a week in an acid rain simulation, the
leachate contained less than 3 ppm of lead. Although short-term tests showed no sign of any
harmful leachate generation, tests should be conducted to determine the environmental impact
of long-term exposure of asphalt produced with contaminated soils on the environment.
A uniform leaching test was used to estimate the quality of leachate that would be pro-
duced by the asphalt mixture. A new leachability test was designedto simulate the rate of re-
lease of contaminants when HMAs mixed with PCSs are exposed to the actual performance
environments when used as pavements. The test methodology and test standards were devel-
oped in cooperation with the New Jersey Departmentof Environmental Protection and Energy
(NJDEPE). The experimental protocol was evolved based on the information and experience of
EPA toxicity characteristics leaching procedure (TCLP) and waste stabilizatiodsolidification
program, the waste solidification program of the U.S.Army Corps of Engineers, and the nu-
clear waste research program at Brookhaven and Oak Ridge National Laboratories.
The uniform leaching procedure gives an indicationof the amount of each organic com-
pound that is leachable under specific experimental conditions. The structural integrity of sam-
plewaskeptinthis test, whereparticlesizereductionwasinappropriate, i.e., inthose
instances where solidification of the waste is needed to meet the best demonstrated available
technology provision of environmentallaw. Grinding may not adequately represent the actual
process. Particle reduction alters the physical charactermany of solidified wastesby destroying
the cementitious property of these wastes in such a way as to show an unrealistically high
leaching rate.
This water-leachability test was based on the EPA draft on Solid Waste Leaching Proce-
dure (SWLP). This document recommends using laboratory reagent wateras the leaching me-
dium. Chemical and physical conditions should be chosen to mimic the environment where the
HMA with PCS is used. The leaching medium in this test was chosenas reagent water with a
pH value of 6.8 at a temperature of25°C (77°F). Since the asphalt mixturesare used as paving
materials, the reagent water should be more representative of the actual environment than an
acidic leaching medium. The reagent water was prepared by boiling deionized water for 15 min.
Subsequently, while maintaining the water at about 90°C (194"F), nitrogen gas was bubbled
through the water for 1 hr. The HMA specimen was treated as a monolithic waste (i.e., the
specimen was not pulverized prior to testing). The asphalt concrete with PCSs were compacted
into a specially designed stainless steel mold 2 in. X 2 in. X 2 in. before being tested. Since
2-in. cubes were needed for this test, HMA could not be compacted to the same densityas in
Marshall tests. However, a loose matrix should produce a higher and conservative leaching
rate. HMA specimens were prepared as for the Marshall test, where the blended aggregates
were heated to 130°C(268°F). Then heated asphalt cement was added to the dry mix and
wet-mixed for 1 min. Then a sufficient quantity of HMA was placed inside the steel molds
and compacted with 50 tamps and the HMA specimen was allowed to cool. The compacted
HMA specimens with PCSs were placed in 480-mL glass containers and sealed with Teflon
septum caps. The volume of the container was at least three times that of the sample,so suf-
ficient space was available in the container and the sample was surrounded on all sides by
672 Meegoda
leaching medium. There was zero headspace to minimize the effects of volatilization. Con-
tainers were placed on an Orbit shaker table at 75 rpm for a period of 96 hr. After the end of
the shaking period, the containers were opened and a 25-mL water sample was immediately
drawn using a gastight syringe. The extracted solutionwas analyzed using an EPA purge-and-
trap method.
The Purge and Trap Method and GC Settings. The analytical system usedin this test was an
ALS 2016 desorber and Tekmar 2000 purge-and-trap concentrator interfacedto a Varian 3400
gas chromatograph (GC) with a high resolution capillary column and a flame ionization de-
tector (FID).
The parameters of A L S 2016 were as follows:
Preheat 2 min
pwe 15 min. helium flow at 40 d m i n
Dry Purge 4 min
Cooldown - 150°C
Desorb preheat 150°C
Desorb 5 min at 180°C
Inject 3 min at 190°C
Bake 10 min at 240°C
The column used for GCFID analysis was a cross-linked 5% phenyl and 95% methyl sil-
icone gum, 50 m long, 0.2 mm in diameter, and 0.5 pm film thickness fused silica-bonded
high resolution capillary column.
Flow rates for the GC were
Hydrogen 30 d m i n
Air 30mUmin
Carrier gas 1 mUmin
Make-up gas 30 d m i n
The GC parameters were
Initial column temperature 40°C

Initial column hold time 5 min
Program 1 final column temperature 65°C
Program 1 column rate 2"Umin
Program 1 column hold time 0
Program 2 final column temperature 190°C
Program 2 column rate 8"Umin
Program 2 column hold time 5 min
Inject temperature 210°C
Detect temperature 250°C
I
Contaminated
Highwuy Soils in Construction 673
Table 5 Method Specifications and Regulatory Limits for Fraction Leached (proposed NJ) in ppb
Compound MDL P f S, CV and concentration Regulatory level
Dichloromethane 0.29 82 f 32% 12.6%112 270
1 ,ZDichloroethane 0.47 76 f 21% 24.8%126 820
l,l,l-TCE 0.39 73 f 28% 2 1.4%18 110
Hexane 0.22 106 f 25% 18.5%18 NIA
Benzene 0.26 88 f 16% 14.3%114 410
Toluene 0.25 94 f 18% 16.8%114 350
F’erchloroethene 0.13 108 f 24% 19.7816 100
Ethylbenzene 0.28 79 f 17% 19.7%/6 360
p,m-Xylene 0.28 95 f 20% 9.6%/5 340
o-Xylene 0.24 91 f 21% 12.6%15 340
N/A = not available.
An external standard was used for the calibration. The standard consistedof a mixture of
targetcompounds in methanol. Theywere dichloromethane.1 ,Zdichloroethane, 1,1,1-
trichloroethane, hexane, benzene, toluene, perchloroethylene, ethylbenzene, p,m-xylene, and
o-xylene.
Calibration and Quantification of Data. To determine the precision of the measurements,
three injections were made for each concentration level, and the results were analyzedto obtain
the mean and the standard deviation. Seven standard samplesof the same concentration were
analyzed to obtain the coefficient of variation (CV)to determine the reproducibilityof his an-
alytical method for each compound.
The detection limit of the method (MDL) is defined as the minimum concentration of a
substance that can be identified, measured, and reported with 99% confidence when the ana-
lytic concentration is greater than zero and is determined from analysisof a sample in a given
matrix containing analytic compounds. In this test, reagent water was used to estimate the
MDL concentration. Standards (analytic in reagent water) at concentrations equal to 1 to 5
times the estimated MDL were used to calculate the MDL. The MDL was reported in con-
centration units as the standard deviation (SD) of the replicates multiplied by the appropriate
Student’s t-value (for a one-tailed test at 99% confidence) for the number of replicates. In this
test, the number of replicates was chosen as seven, so MDL was defined as
MDL = 3.143 X SD
Each day, three or four sampleswere spiked withat least 10% of the samples and analyzed
to monitor and evaluatethe experimental data quality. The percentage recovery was calculated
using the equation
P = 100 (A - B)% / T
where A is concentration after spiking, B is the background concentration, and Tis the known
true value of the spike.
After the analysis of 10 spiked samples,the average percentage recovery( P ) and the stan-
dard deviationof the percentage recovery(Sp) values were calculated and expressed as P f Sp.
Table 5 shows those values.
A major sourceof interference in this test was cross-contamination of samples. To prevent
such cross-contamination, reagent water blankswere run twice before running each sampleto
674 Meegoda
Table 6 Leachate Concentration (ppb) from Monolithic HMA Specimens with Pc&
Compound Pcs 1 Pcs 2 Pcs 3 Pcs 4 Pcs 5 PcS 6
Dichloromethane ND ND 2.% ND ND ND
1 ,2-Dichloroethane ND ND 0.88 0.16 0.18 1S 1
l,l,l-TCE ND ND 8.01 ND 5.43 5.14
Hexane 0.23 ND 6.46 ND 2.43 0.85
Benzene ND ND 3.11 ND 2.19 ND
Toluene ND ND ND ND ND ND
Perchloroethene ND ND 1.19 ND 0.97 ND
Ethylbenzene ND ND ND ND ND ND
p,m-Xylene ND 0.32 0.36 ND 0.33 1.69
o-Xylene ND ND 0.37 ND ND ND
ND=none detected or less than the detection limit.
demonstrate that interferences from the analytical system were under control. The following
procedure was used to clean the vials and glass containers:
1. Wash all the vials and containers thoroughly in hot water using a detergentto remove the
particulate matter and contaminants.
2. Rinsethoroughlyusingtapwater.
3. Rinsethreetimesusingdeionizedwater.
4. Place in a vacuum oven at 105°C for 12 hr to bake all volatile compounds.
5. Cool for 30 min, screw the lids tightly, and store in an area not subject to contamination
by air or other sources.
Test Results. This method can estimate the concentrations of target chemicals up to a min-
imum concentration of around one-tenth of 1 part per billion (ppb). Table6 shows the testre-
sults. Ethylbenzene did not leach out from any of the six mixes. Benzene, toluene, and xylene
concentrations in all the leachates were less than8 ppb. For the HMA mix containing PCS No.
3 with an initial petroleum concentration of 6600 ppm in the soil, the total leachate concen-
tration of 10 keychemicals in leachate from solidified and stabilized HMA with PCS No. 3 was
less than 25 ppb. The experimental results clearly demonstrate that the HMA with PCSs so-
lidifies and stabilizes most of the petroleum contaminants within the asphalt matrix and the
very small concentrations of organic chemicals that may be leaching are from the soil particles
that are not completely coated with asphalt cement.
To further evaluate the long-term leaching of contaminants, three specimens of HMA
made with PCS No. 3 were prepared, placed on top of the shaker, and shaken for durations of
1 day, 1 week, and 1 month. Those test results are shown in Table 7 and are graphically dis-
played in Figure6 . Results do not show any significant increase in contaminant concentrations
with time for any of the compounds tested.
2. Analysis of Air Quality During the Production of HMA with PCS
Czarnecki [4] obtained a permit from the Massachusetts Department of Environmental Quality
Engineering (DEQE) to process petroleum-contaminated soils subjected to the following con-
ditions: It should process 95% virgin aggregate and 5% PCS, and 95% of the hydrocarbons
should be incinerated during the process.To demonstrate the95% destruction, a mass balance
of pure chemicals was performed for the incineration system. The test used sand contaminated
with a 3% concentration of a 50150 blend of xylene and toluene. Three points in the system
Table 7 Leachate Concentration (ppb) with TimefromMonolithic

HMA Specimen with PCS No. 3
eekOne day
Compound
One
2.33
Dichloromethane 1.82 3.12
0.81
1 ,2-Dichloroethane 0.82 1.03
1,l.l-TCE
6.29 5.35 9.43
Hexane 6.32 6.01 6.87
Benzene 2.32 2.19 2.29
Toluene ND ND ND
1.11
Perchloroethene 1.01 1.12
Ethylbenzene ND ND ND
p,m-Xylene 1.65 0.33 1.80
o-Xylene 0.28 0.26 0.30
ND=none detected or below detection limit for each compound.
10 0
g
P
v
"i ." .............- " " ..... ....
" " "
X x
"'B i
Time (days)
30
Figure 6 Long-term leaching test results. (From Meegoda et al. [9].)
were selected for analysis: incoming sand from the conveyer belt before the aggregate dryer,
sand stripped of contaminants from the storage silo, and
air samples from the stack. For three
tests, Czarnecki [4] showed 99% destruction of hydrocarbons. Following are the test results
from this study; the ai+ sample collection method was not documented:
Incoming sand concentration 30,000.0 ppm

Sand coming out from aggregate dryer 0.9 ppm
Air samples from the stack 0.2 ppm
The measurement of volatile organic compounds (VOCs) has become an important aspect
in understanding photochemical reactions and providing an index of hydrocarbons present in
the atmosphere. Knowledge of the levels of such materials in the ambient atmosphere isalso
676 Meegoda
required in order to determine human health impacts. However, the determination of toxic or-
ganic compounds in ambient air is a complex task, primarily because of the wide variety of
compounds of interest and the lack of standards and procedures for analysis. The U.S. Envi-
ronmental Protection Agency (EPA) has developed several standard analytical methods forthe
measurement of volatile organic compounds present in ambient air. Sample collection has been
reported as the weakest link in the analytical chainfor the determination of airborne organics,
which is critical to the accuracyof the results. The sampling methodsused for measurement of
VOCs can be categorizedas adsorption by a solid, cryogenic trapping,or whole air collection.
Adsorption by a solid. The solid adsorbents include(1) organic polymers (Tenax, XAD-
2), (2) inorganic materials (silica gel, florisil), and (3) carbon (activated carbon, carbon mo-
lecular sieves).
In this technique VOCs are collected on a solid sorbent material while the bulk constitu-
ents (e.g., nitrogen, oxygen) are allowed to pass through the sorbent. The VOCs adsorbed are
then desorbed, and the sample is injected in a gas chromatograph (GC). Stripping of the ad-
sorbed analytes from the adsorbent is typically accomplishedby either thermal or solvent de-
sorption. Solvent desorption, although useful in many applications, generally requires sample
preconcentration before analysis.This adds to the complexity of the final method and increases
the sample handling time and the possibilityof contamination. The thermal desorption of an-
alytes has the advantages of reduced sample handling and increasedsensitivity because of the
transfer of all analytes onto the chromatographic column. The main advantages of the use of a
solid adsorbent for organic polymers are that (1) little water is collected in the sampling process
and (2) a large volume of air can be sampled relative to other techniques such as cryogenic
sampling. The analytes adsorbed onto Tenax, desorbed, and analyzed using GC/MS can de-
termine volatile nonpolar organics (e.g., aromatic hydrocarbons, chlorinated hydrocarbons)
having boiling pointsin the range of 80-200°C [1l]. The PUF/XAD-2 adsorption with GC and
HPLC detection can be applied todetermine polynuclear aromatic hydrocarbons. A major dis-
advantage of these materials is the breakthrough of volatile compounds. Degradation products
of the trapping materials are frequently found in adsorbent tubes such as Tenax. Incomplete
desorption is also a problem with these methods.
Inorganic adsorbents includesilica gel, alumina, florisil, and molecular sieves. Thesema-
terials are considerably more polar than the organic polymeric adsorbents, leading to the ef-
ficient collection of polar materials. Unfortunately, water isalso efficiently captured, leading
to rapid deterioration of the adsorbents.
Carbon adsorbentsare relatively nonpolar compared to the inorganic adsorbents, and hence
water absorption is not a significant problem. Carbon tends to exhibit much strongeradsorption
properties than organic polymeric adsorbents, allowing the efficient collection of volatile ma-
terials such as vinyl chloride. However, the strong adsorption of carbon adsorbents can be a
disadvantage. The desorption of target compounds from the carbon tubes is a common prob-
lem. For example, carbon molecular sieves used in EPA Method TO-'2 bind aromatic com-
pounds tightly, and a high temperature (=4OO"C) is required to desorb them. Finally, moisture
affects the trapping and desorption efficiencyof the charcoal tubes. The adsorption on carbon
molecular sieve followed by desorption and GUMS analysis can be used to determine highly
volatile nonpolar organics (e.g., vinyl chloride, vinylidene chloride, benzene, toluene) having
boiling points in the range of - 15°C to + 120°C.
Cryogenic Trapping. The collection of atmospheric organics by condensation in a cryo-
genic trap is an attractive alternative to adsorption or impinger collection. The primary ad-
vantages of this technique include(I) the collection of a wide range of organic materials, (2)
avoidance of the contamination problem associated with adsorbents other and collection media,
(3) the availability of the sample for immediate analysis without further work, and (4) consis-
Soils
Contaminated Construction
in Highway 677
tent recoveries. But the disadvantage of this method is that it is suitable only for volatile and
nonpolar organics having boiling points the in range of - 10°C to +200"C. This technique pro-
vides quantitative concentrations of identified species of lower molecular weights suchas CT
C,, compounds typically observed in ambient air.However, an important limitation to this
technique is the condensation of large quantities of moisture and carbon dioxide and lesser
amounts of certain reactive gases.
Whole Air Collection. Collection of whole air samples using stainless steel canisters,
evacuated glass bulbs, or similar devices is probably the simplest sampling approach. This
approach is most useful for relatively stable volatile compounds such as hydrocarbons and
chlorinated hydrocarbons with boiling points below 150°C. The canister samplers have the
following advantages compared to solid sorbent tubes: (1) Breakthrough does not occur with
canister sampling because the actual air sample is collected; (2) no thermal desorption is re-
quired; (3) canister pressure canbe used as an indicator of correct sampler operation; (4) anal-
ysisof the canister sample can be repeated by using the remainder of the sample in the
canister; and (5) the evacuated canisters can be used for sampling without power in the sam-
pling location.
SUMMA passivated canister sampling with GC was developed by USEPA to determine
semivolatile and volatile organic compounds. The canister is a sampling deviceused to collect
and store whole air samples. It can be pressurized, thereby increasing the volume of the col-
lected air sample. It has been demonstrated that the SUMMA passivation process, in which a
pure chrome-nickel oxide layer is coated on the inner metal surface, increases the stability and
the storage life of many organic compounds. However, certain compounds pose stability prob-
lems associated with storageby the formation of an oxide coating. Selection of an alternative
container material can circumvent these problems in many cases. The most difficult problem
associated with this method is the quantity of moisture collected in the canister. Too much
moisture can clog the cryogenic trap and the capillary interface.
Due to the complexity of ambient air samples, only high resolution (capillary column) GC
techniques are acceptable for most of the above methods. The GC/MS system should be ca-
pable of programing subambient temperatures. Unit mass resolution shouldbe better than 800
amu, and GC/MS shouldbe capable of scanning the 30-440 arnu region every 0.5-1 sec. The
measuring device shouldbe equipped with a data system for instrument controlas well as data
acquisition, processing, and storage.
Impinger bubblershave traditionally beenused for the collection of volatile organics from
air. They are charged with a trapping solvent and require much more sampling time for col-
lecting sufficient amounts of the analyte. The growing demand forgreater sensitivity and time
resolution suggestedthe development of a system based on solid adsorbent sampling and ther-
mal desorption of VOCs followed by gas chromatographic analysis with cryogenic refocusing
techniques.
An air sampling and analysis systemfor monitoring VOCs being emitted from the stacks
of asphalt plants was designed. It was based on solid adsorbent sampling tubes with thermal
desorption GC analysis using capillary column separations with cryogenic refocusing tech-
niques. Air samples were collected using the solid adsorbent Tenax in stainless gas collection
. tubes. Stripping of the adsorbed analytes from the sampling tube was accomplished by thermal
desorption and followed by gas chromatographic analysis.
Preparation of Tenux Cartridges. The following procedure was usedto prepare a 5/8 in. tube
containing Tenax cartridges.
Prior to use, the Tenax resin was subjected to a series of solvent extraction and thermal
treatment steps. The operation was conducted in an area where levels of volatile organic com-
678 Meegoda
pounds (other than the extraction solvents used) are minimal. All glassware usedinTenax
purification and all cartridge materials were thoroughly cleanedby rinsing with water followed
by rinsing with acetone and drying in an oven at 250°C. The bulk Tenax was placed in a glass
extraction thimbleand held in place with a plug of clean glass wool. The resin was then placed
in the Soxhlet extraction apparatus and sequentially extracted with methanol and then withpen-
tane for 16-24 hr for each solvent for approximately 6 cycleshr. Glass wool for cartridge prep-
aration was cleaned in the same manner as that for Tenax.
The extracted Tenax was placed immediately in an open glass dish and heated under an
infrared lamp for 2 hr inside a hood. Care was exercised to avoid overheating the Tenax with
the infrared lamp. The Tenax was then placed in a vacuum oven (evacuated using a water as-
pirator) without heating for 1 hr. Then it was purged with an inert gas (helium or nitrogen) at
a rate of2-3 m u m i n to aid the removal of solvent vapors. Then the oven temperature was
increased to 110°C while maintaining the flow of inert gas for 1 hr. Then oven temperature
control was shut off, and the oven was allowedto cool to room temperature. Before opening the
oven, it was slightly pressurized with nitrogen to prevent contamination with ambient air. The
Tenax was removed from the oven and sieved through a 4 / 6 0 mesh sieve (acetone rinsed and
oven-dried) into a clean glass vessel.
in a clean glassjar with a Teflon-lined screw
If the Tenax was to be used later, it was stored
cap and placed insidea desiccator. The cartridge used for the monitoringof air was packed by
placing a 0.5-1 cm long glass wool plug at the bottom of the cartridge and then filling the
cartridge with Tenax up to approximately 1 cm from the top. Then a 0.5-1 cm long glasswool
plug was placed on top ofthe Tenax. Thecartridges were thermally conditionedby heating for
4 hr at 270°C while purging with an inert gas (helium at 100-200 mumin).
The Desorption and GC Settings. The air sampling and analysis system was based on solid
adsorbent sampling tubes and thermal desorption gas chromatographic analysis. After collec-
tion of air samples, sampling tubes were put into a desorber. Then the VOCs were twice con-
densed in cryogenic trap to improve capillary column resolution. Before cryogenic refocusing,
a purge step served to remove any oxygen that remained inthe tube. This eliminated the prob-
lem of the solid adsorbent reactingwith the oxygen when heated, and it also removed traces of
water from the tube.
Collected air samples in Tenax traps were first desorbed using a Tekmar Model 5010 au-
tomatic desorber connected to a Varian 3400 high resolution capillary GC with a flame ion-
ization detector. The two systems were interfaced to automate the entire analysis.
The desorption conditions are as follows.
Prepurge 5 min at 10 mUmin

Desorb 8 min, 210°C, 10 mUmin
Cryotrap 1 150°C
Cryotrap 2 150°C
Transfer 10 min. 210°C
Inject 0.5 rnin, 210°C
The column used for GC/FID analysis was a cross-linked 5% phenyl and 95% methyl sil-
icone gum, 50 m long, 0.2 mm diameter, and 0.5 pm film thickness fused silica bonded high
resolution capillary column.
Flow rates for the GC were
Hydrogen 30 mUmin
Air 30 mUmin,
Carrier gas 1 mUmin
Make-up gas 30 mUmin
The temperature program was (1) an initial temperature of 15°C for 8 min and (2) tem-
peratures programed up to 210°C at 4"CImin. The detector range was selected as 10. A sche-
matic diagram of the analytical system is shown in Figure 7.
Calibration and QuantificationofData. External standards were used to calculate a response
factor for each compound of interest. The process involvedthe analysis of four calibration lev-
els for each compound during a given day for the determination of the response factor (area/
picomole). The linear least squares fit of a plot of picomoles versus area was used for the
determination of the response factor. If substantial nonlinearity is present in the calibration
curve, a nonlinear least squares fit should be employed. This process involvesfitting the data
to the equation
Y = A + BX + DX2
where Y is the peak area, X is the quantity of the component in picomoles, and the constants
A, B , and D are coefficients to be determined fromthe regression analysis. If the instrumental
response is linear over the concentration rangeof components, a linear equation (D = 0 in the
equation above) can be employed. The systemdetection limit for each component can be cal-
culated from the calibration standards, where the detection limit is defined as
DL =A + 3.3SD
where DL is the calculated detection limit in picomoles, A is the intercept of the regression
analysis equation, and SD is the standard deviation of the samples with replicate determina-
tions of the lowest concentration level.
The standard gas used for calibration consisted of a mixture of chloromethane, hexane,
chloroform, 1,1, l-trichloroethane, carbon tetrachloride, trichloroethene, toluene, trichloroet-
hylene, benzene, mpxylene, and o-xylene. These compoundswere injected into an evacuated
and clean 13-L stainless steel cylinder, and the cylinder was pressurized with zero grade he-
lium. The preparation and analysis of the standard was done by Alphagaz, Edison, New Jersey.
A 2-mL volume sampleloop was used for the GC analysis. When the sample loop wasflushed,
the standardgas mixture passed throughthe sample loop. A three-port valve witha switch was
used to allow helium gas to pass throughthe loop, flushing the standard gas onto a Tenax car-
tridge. The compoundsin the standard gas were adsorbed by Tenax and quantifiedby gas chro-
matography. The following ideal gas equation was used for the calculation of the component
concentrations in the standard gas.
n = PVC/(R/T)
where P is pressure (inatm), V is the volume of the sample loop, C is the concentration of each
compound expressed as a fraction, R is the universal gas constant (0.082), Tis temperature (in
kelvins), and n is the amount of each standard gas injected (in moles).
At 25"C, sample concentration in ppb can be expressed as
area of sample X C X 24.5 X lo9
Sample concentration = area of the xv
680 Meegoda
Automatic Desorber
Tenax trap with contaminants
i IOpsig, I mVmin
and then desorborganics

Printer
t
Computer
t
GC Server 4
A
,
,...,
.~,...
i .,
Air, 6Opsig 30 d m i n
Hydrogen, 4Opsig
30 mVmin
' , - .
. . . .
Nitrogen, 8Opsig
30 mumin ;make up
for capillary column ...........
: * .....................................:
*
High Resolution CapillaryG a s Chromatograph
Figure 7 A schematic diagramof the analytical system usedfor the air quality analysis. (From Me-
soda et al. [g].)
where C is concentration of the compound in standardgas and V is the volume of the sample
in liters. If V is at a different temperature and/or pressure, then the volume of gas should be
converted to that at 25" and a pressure of 1 atm.
The air samples were collected by drawing air through theTenax cartridge, a 5/8 in. stain-
less steel tube packed with 1.5 g of 60/80 mesh Tenax using a vacuum pump. Figure 8 shows
the schematic for extracting air samples from stacks. Samples were drawn at approximately 500
&min.
In this experiment, 10 Tenax blank traps were spiked with known quantities of standard
and then desorbed into the analytical system. The reproducibility can be expressed by the co-
efficients of variation(CV) of the target compounds. The CV andDL values for all the tested
organic compounds are shownin Table 8.
Tenax Cartridge
Meter
L x l
+ Vent
Vacuum
Pump
Valve
Reducing Union . EndCap
I Glass Wool \
/
Swagelok l
Tenax
Metal Cartridge
Fitting
Figure 8 Schematic diagrams of the setup used for air quality analysis. Prom Meegoda et al. [8].)
Test Datu. An air sampling and analysis system was designed to monitor volatile organic
compounds emitting from stacks of asphalt plants. It was based on solid adsorbent sampling
tubes with thermal desorption gas chromatographic analysis and used capillary column sepa-
rations with cryogenic refocusing techniques. Air samples were collected using the solid ad-
sorbent Tenax in stainless gas collection tubes. Stripping of the adsorbed analytes from the
sampling tube was accomplishedby thermal desorption and followedby gas chromatographic
analysis.
were drawn for3 min from the stackin the asphalt plant
During the field study, air samples
while the HMA concrete blended with PCS was prepared.The air samples were drawn through
a filter to remove the dust going into the
Tenax cartridge. The Tenax cartridge was connected
to a vacuum pump. Three air samples were obtained for 3 min for test, and the Tenax samples
were analyzed for concentrations of target organic compounds. Test results (firsttwo soils
day,
withfourdifferentblends;secondday,onesoilwiththreedifferentblends) are shownin
Table 9.
682 Meegoda
Table 8 Method Specifications and Regulatory Limits for Fraction Released (Proposed N.J.) (ppb)
Regulatory level as average flux
(PPW DL Compound CV (mg/m2* day)
270Chloromethane 0.54 20.5%
NIADichloromethane 0.13 9.2%
NIA
Hexane 0.03 11.8%
6 Chloroform 0.44 9.8%
4941,1,1 -Trichloroethane 0.22 10.5%
13.8
Trichloroethylene 0.05 21.4%
16.7 Benzene 0.07 NIA
988Toluene 0.06 6.7%
9.9Tetrachloroethylene 0.03 8.7%
148p,m-Xylene 0.05 7.5%
148o-Xylene 0.06 9.5%
N/A =not available.
Areas of all peaks were added to computethe total nonmethane organic carbon (NMOC)
emissions. A standard propane/heliumgas mixture was usedto obtain the GC calibration curve
for concentration. Various known amounts of the mixture were injected to the GC and the peak
areas were obtain to establish the calibration curve. Then the concentration corresponding to
sum of all peak areas was calculated from thecalibration curve and reported as totalNMOC in
Table 9. Figure 9 shows a comparison of totalNMOC emission from a regular asphalt plant and
that uses PCSs (day 2 test 3 in Table 9).
The concentrations of the target chemicals were less than 1 ppm, and total concentrations
of VOCs were lower than the NJDEPE specification for regular asphalt plants (c250 ppm).
Table 9 AirQualityTestResults
Concentration in ppb
otal
Cs
Hexane
0-Xylene
Xylene
P&M
Toluene
No. Test
8 Day581 Test 1 52 52
1 2 Day 1 Test
3 Day 1 Test
4 Day 1 Test 90 69 53
14,880 11
2 Day
2 Day 99155,230 283
2 Day
Conc. levels
plant 2,650
after 149 4
11 2
stopped
Background
ant around conc. 25 2 0 1,210
Stack conc.
from an ordin.
24 16 6 0 26,700
HMA plant
without PSCs
Source: Meegoda et al., 1992 [9].
Soils
Contaminated
Highway in Construction 683
NMOC
100 I
80
60
40
20
n
"
Normal HMA IIMA with PCSs
= PPmC I b Carbonlhr
Figure 9 Comparison of non-methaneorganiccarbon (NMOC)emission by aregularasphaltplant
of carbon per hour. (From Meegoda
and one that uses PC%. Solid bars, ppm carbon; hatched bars, pounds
et al. [ g ] . )
Furtherdetailscan be fohndinthe 1991 report to NJDEPE ontheuseofpetroleum-

contaminated soils in construction material production [ 121.
111. SUMMARY AND CONCLUSIONS

Leaking underground storage tanks (USTs) are one of the primary sources of groundwater con-
tamination in the United States. The soils contaminated by leaking USTs are treated as solid
waste. The quantities of such soils are projected to increase substantially over the next few
years. In this report the feasibility of using petroleum-contaminated soil (PCS) in the produc-
tion of asphalt concrete is discussed. When F'CSs are used in asphalt production, three bene-
ficial actions occur: incineration, dilution, and solidification.
An in-depth laboratory study was performed to determine the feasibility of producing
HMA with PCSs. For the heating oil-contaminated soil used in this study, it was possible to
include upto 35% PCS based on the total weight of the aggregates in the HMA mix. This value
is much higher than any reported in the literature. The impact with respect to strength and du-
rability of asphalt concrete dueto the additionof PCS to HMA was also evaluatedby perform-
ing the Marshall stability test. The test results showed that HMA with PCS produced a much
better paving material than the control. The extended durability test showed that one cycle of
freeze-thaw and wet-dry was sufficient to evaluate the durability of HMA with PCS. The du-
rability of HMA produced with PCS was found to be the same as that of the control mix,
684 Meegoda
suggesting that there are no harmful effects from the addition ofPCS. The hydraulic conduc-
tivity of HMA with allPCSs produced asphalt concrete with hydraulic conductivities less than
2.0 x
A new leachability test was designed for the monolithic sample. The leachability of hy-
drocarbons based on the EPA purge-and-trap method showed that maximum release was less
than 25 ppb after the specimens were immersedin analytical water and subjected to4 days of
vigorous shaking. To further evaluate the leaching of contaminants, a long-term leaching test
was performed. The test results show no significant increase in contaminant concentrations
with time for all the compounds tested.
An extensive field studywas conducted to demonstrate the applicabilityof this process. An
air sampling and analysis system was designed for monitoring volatile organic compounds
being emitted from asphalt plant stacks. It was based on solid absorbent sampling tubes with
thermal desorptiongas chromatographic analysis using capillary column separations with cryo-
genic refocusing techniques. The concentrations of the target chemicals were less than1 ppm,
and the concentrations ofVOCs were lower than the NJDEPE specification for regular asphalt
plants (<250 ppm).
be given to this
On the basis of these results it is recommended that much greater attention
process because it is a highly cost effective recycling technology.
1. USDOT, Selected Highway Statistics and Charts, Federal Highway Administration, U.S. Dept. of
Transportation,1988.
2. Collins, R. J., Assimilation of waste and by-products into the highway system: status report and
regulatory influences, Second Interagency Symp. Soil Stabilization, New Orleans,La., November
1992, Section 7, pp.3-11.
3. Flynn, L., Recycling: will roads become “linear landfills?,” Roads Bridges, October 1992, pp.
65-70.
4. Czamecki, R., Making use of contaminated soils, Civil Eng., December 1988, pp. 72-74.
5. Czamecki, R., Hot mix asphalt technology and cleaning of contaminated soils, inPetroleum Con-
taminated Soils, Vol. I1 (€?Kostecki and E. J. Calabrese, ed~.),Lewis, Chelsea, Mich., 1989, pp
267-277.
6. Fairweather, V., U.S. trackless leaking tanks, Civil Eng., 6 0 , 46 (1990).
7. Asphalt Institute, The Asphalt Handbook. College Park, MD, Asphalt Institute, MS4, 1989.
8. Meegoda, N. J., Huang, D. R., DuBose, B., and Mueller, R. T.. Use of petroleum contaminated
soils in asphalt concrete, in Hydrocarbon Contaminated Soils, Vol. I1 (I?T. Kostecki, E. J. Cala-
brese, and M. Bonazountas, eds.), Lewis, Chelsea, Mich., 1992, Chapter 31,. pp. 529-548.
9. Meegoda, N. J., Huang, D. R., DuBose, B. H., Chen, Y.,and Chuang, K. Y., Use of Petroleum
Contaminated Soilsin Construction Material Production, Second Report to N.J. Dept. of Environ-
mental Protection and Energy, Div. Sci. Res., Submitted by the N.J. Inst. Technology, Newark, N.J.
January1993.
10. Eklund, K., Incorporation of contaminated soils into bituminous concrete,in Petroleum Confami-
mted Soils, Vol. I (P Kostecki and E. J. Calabrese, eds.), Lewis, Chelsea, Mich., 1988, pp 191-
199.
11. Tsuge. S., Matsushima, Y., Watanabe, N., Shintai, A., Nishimura, K., and Hoshia, Y., New au-
tomated thermal desorption system for gas chromatographyof volatile componentsin environmental
and polymeric samples, Anal. Sci. 3, 101-107 (1987).
12. Meegoda, N. J., Huang, D. R., DuBose, B. H., and Chen, Y.,Use of Petroleum Contaminated
Soils in Construction Material Production, Interim Report to the N.J. Dept.of Environmental Pro-
tection, Division of Science and Research, submitted by N.J. Inst. Technology, Newark, N.J., Au-
gust 1991, pp.1-80.
34
Management of Waste
Compressed Gases
Dan Nickens
Earth Resources Corporation
Ocoee, Florida
1. INTRODUCTION
Professionals in the field of hazardous waste management are increasingly faced with problems
associated with waste compressed gases. The problems stem from the specialized hazards
posed by pressurized materials. The commonuse of gases increases the likelihood of encoun-
tering this type of waste.
Gases, in compressed or liquefied form, are prevalent in industrial and governmental a p
plications. These materials are also commonly used in many households (e.g., propane cylin-
ders for outdoor gas grills). Gasesare required in hospitals for medical purposes (i.e., oxygen
and anesthetic gases), and agriculture employs gases on a routine basis (i.e., anhydrous am-
monia for fertilization of crops). Cutting and weldingare most commonly completed by using
compressed gases.
A compressed gas is defined by the American Society for Testing and Materials (ASTM)
as any material or mixture having an absolute pressure exceeding 40 psi at 70°F.Regardless of
the pressure at this temperature, a compound that has a pressure exceeding 104 psi absolute at
130"F, or any liquid flammablematerial having a vapor pressure exceeding40 psia at 100°F is
classified as a compressed gas (ASTM Test D-323).
There are two major categories of compressed materials: compressed gases and liquefied
compressed gases. Liquefied compressed gases condense at normal ambient temperatures under
pressures of up to 2500 psig.
In addition to these major classes, gases can be generally divided into groups related by
common origins, properties, or uses. These include atmospheric gases, gases produced through
fractionation (argon and the rare gases), fuel gases, refrigerant gases, and poison gases.
Options available for management of waste gases are more limited than for almost any
other type of waste. Constraints on safe management techniques become even greater for gas
cylinders that are in poorcondition.Proceduresandtechnologiesthathaverecentlybeen
685
686 Nickens
developed offer increased capabilities and important improvements over historical practices
for
safe and proper management of these wastes.
II.HEALTH AND SAFETY CONSIDERATIONS

Waste compressed gas cylinders pose special hazards that are peculiar to these materials. The
potential hazards include all those that are associated with other chemical wastes, and in ad-
dition there are hazards associated with the energy of compression and the mobility of the ma-
terials when released.
Many compressed materials exhibit chemical hazards that must be taken into consideration
in managing their disposition. These hazards include characteristics of ignitability, reactivity,
corrosivity, toxicity, and combinations of these characteristics. It is extremely important to
identify the contents of compressed gas cylinders to determine the nature of the risks posed by
the wastes.
The very nature of compressing these compounds generates physical hazards from possible
rupture or other uncontrolled release. A 1 S-ft3 cylinder pressurized to 2000 psig contains an
energy equivalent to 1.4 lb of TNT. If cylinder failure occurs, this energy is released in an
uncontrolled and extremely dangerous manner.
Many gases that are not otherwise hazardous can present the danger of asphyxiation. Any
gas capable of displacing oxygen offers a potential hazard from asphyxiation. This is most
common in confined environments with limited air circulation.
The asphyxiation hazard posed by some gases is reduced by their good warning properties.
For example, any worker entering an environment that contains high levels of ammonia will
immediately recognize its presence. Other gases, however, are more insidious. Nitrogen is par-
ticularly hazardous because of its poor warning properties and its common use in enclosed
areas. Other gases that tend to accumulate in low-lying areas (e.g., sulfur hexafluoride) can
displace oxygen in these areas.
Other characteristics of compressed gases have more direct dangers. Many gases can
be extremelytoxic to humansthroughinhalation or contactwiththeskin or eyes.Some
gases can be hazardous simply because of cryogenic temperatures or cooling associated with
volatilization.
Many toxic gasesare used in commercial applications. Examplesof these extremely toxic
gases include arsine, phosphine, germane,and diborane, which are used in the electronics in-
dustry. Injuries and fatalities have resulted from accidents involving these gases. The extreme
toxicity of some gases is illustrated by exposure limits establishedas low as 0.001 ppm.
Toxic gases affect humans primarily through respiration. When released from pressurized
cylinders, toxic gases can rapidly reach lethal concentrations in surrounding areas. Liquefied
toxic gases suchas chlorine are of particular concern due to the sheer volume of material that
can be stored as a liquefied compressed gas.
Flammable gases that present both fire and explosion risks are some of the most common
gases (e.g., propaneand acetylene). Flammable gases must be isolated from sources of or heat
ignition. Leaks of flammable gases can traverse long distances to sources of ignition, resulting
in explosions and fire.
Reactive materials are often present in compressedgas cylinders. These include powerful
oxidizers suchas fluorinated compoundsand oxygen. Oxygen can cause an explosion when the
released gas contacts organic materials. Fluorine is even more reactive and can ignite metal in
otherwise inert environments. Many gases usedas rocket fuels (suchas hydrazines and chlorine
trifluoride) are capable of explosive reactions at very low initiation energies.
Management
Compressed
of Waste Gases 687
Corrosive gases form another classification of hazardous gases. Examples include anhy-
drous hydrogen chloride and hydrogen fluoride. On exposure to moist air, many gases will react
to form acids.
Some unstable gases are inherently hazardous due to their potential for exothermic poly-
merization. These include such gases as hydrogen cyanide, ethylene oxide, and acetylene. The
handling of a cylinder containing unstabilized hydrogen cyanide resulted in an explosion that
destroyed windows several blocks removed from the blast site in Texas. Acetylene in its free
state is known to explosively decompose at pressures above 15 psig (it is also shock-sensitive
in the liquid and solid states).
Ordinarily, reactive mixtures of gases are not stored in a single cylinder. Manifolding of
cylinders can result, however, in the creation of potential bombs. Such a cylinder containing
silaneandnitrousoxidedetonatedduringhandling,killingthreeworkers inNewJersey.
The resultant fii destroyed the laboratory building and forced evacuation of the surrounding
neighborhood.
Hazards are often associated with materials stored in compressed gas containers even
though they may not be pressurized. A tragic example was an accident involving cylinders at
a waste disposal facility. Residual contentsof “empty” devalved cylinders exposed several un-
protected workers to lethal vapors.
Compressed gas cylinders are commonly used to stored a variety of hazardous nonpres-
surized materials. The hazards associated with this situationare illustrated by a fatal accident.
A lecture bottle containing pentaborane (a liquid at ambient temperature and pressure) was re-
moved from a sampling device by an unprotected worker. Even though there would have been
no indication of residual pressure, volatilization killed the worker and a bystander and injured
others in the vicinity, including rescue workers.
Even though the original material may have been introduced in the gaseous phase, poly-
merization or other degradation reactionsmay result in the formation of liquids or solids in the
cylinder.
Other hazardous materials storedin cylinders include radioactive gases. Biological agents
have also reportedly been stored in cylinders. Almost any material that should be isolated from
the environment for some reasonmay be contained in a cylinder.
All of these hazards mustbe addressed to safely manage waste compressedgas cylinders.
When the contents of a cylinder are not positively identified, it must be assumed that any of
these hazards may be present.
111. REGULATORYCONSIDERATIONS
The management of waste compressed gas cylinders is governed by federal, state, and local
regulations. Federal regulations apply to the interstate movement and filling of cylinders. Haz-
ardous waste management and air pollution regulations may be applicable. Local buildingand
fire codes also apply to cylinder use and storage.
Federal Departmentof Transportation (DOT) regulations govern the transportation and re-
filling of compressed gas cylinders. Under these regulations (found in 49 CFR), appropriate
containers must be used for eachgas or liquid.
DOT regulations require that each cylinder be stamped to indicate information concerning
the rating and manufacture of the cylinder. High pressure cylinders have DOT ratings of be-
tween 900 and 6OOO psig. Low pressure cylinders range from 240 to 500 psig. Acetylene cyl-
inders are included in a special classification (the container is filled with a porous material and
the gas is dissolved in acetone).
688 Nickens
In order to be refilled, cylinders must meet DOT requirements forstructural integrity. Pe-
riodic hydrostating of the vessel is required. Standardshave also been developedfor corrosion.
Conditions thatmay makethe cylinder unsafefor transport include extreme corrosion, bulging,
or damage to the vessel or its valve.
Prior to transportation, a cylinder must be carefully inspected to ensure that it is suitable
for safe shipment. A leaking cylinder cannotbe legally transported and should be handled only
by professionally trained workers. Support can be obtained fromthe owner of the cylinder if the
owner is a major gas supplier.
An exemption inthe regulations allowing the shipment of laboratory samples has been mis-
used to move unknown gases in lecture bottles. The exemption applies only to the quantity of
material necessary for analysis. Since analysis of gases can be accomplished with extremely
small volumes, the exemption does not apply to lecture bottle quantities.
The Resource Conservation and Recovery Act (RCRA) specifically includes compressed
gases in its definition of solid wastes. A waste gas is classified as a hazardous waste if it has
a listed characteristic (ignitability, reactivity, or corrosivity) or if its components are listed as
hazardous.
Historically, there hasbeen a differentiation betweenthe handling of compressed gas cyl-
inders that are owned by gas suppliers and thoseowned by a generator. If a gas supplier rents
the cylinderto the user, it can be returned when it is no longer needed. The suppliers treat any
residual gases as part of their manufacturing process under operating (air discharge) permits.
This hasbeen used as a vehicle for avoiding having to treat residual gasesas hazardous wastes.
Where title to the cylinder and its contents is transferred to the user, the user may be sub-
ject to RCRA regulations for disposition of residual waste gases. Under these regulations, a
container approaching atmospheric pressure is considered tobe empty and need not be handled
as a hazardous waste. Only those cylinders with residual pressure must be treated as a haz-
ardous waste.
Even though the regulations may not cover cylindersat atmospheric pressure, the contents
may still be hazardous. Improper handling of these materials can result in injury or death.
Waste compressed materials subject to RCRA regulations must be disposed of at a per-
mitted facility. Appropriate disposal options include incineration and chemical treatment.
Very few options presently exist in the United States for disposal of compressed gases at
permitted facilities. The listof gases that can be disposed of at these facilities does not include
all compressed gases.
One commercial disposal facility handling compressed was gasesclosed by state regulatory
offkials in 1991. The Aquatech facility in Greer, South Carolina nowisa Superfund site. A New
Jersey facility specializingin waste compressed gases closed in1986 after a worker was killed.
To accept a compressed gas for disposal, the contentsof the cylindermust be identified and
the valve mechanism must bein operable condition. No commercial facility can legally accept
gas cylinders whose contentshave not been positively identified.
Because of the limited disposal options, some users have previously obtained permission
for disposal by detonation of the cylinders at remote sites. For this operation, shaped charges
are attached to the cylinder and detonated. This may also include ignition of fuel surrounding
the cylinder to bum flammable gases. This procedure is not effective with many hazardous
gases. Its use has been severely curtailed by responsible regulatory officials.
The risks associated with detonation of unknown cylinders as a disposal optionhave been
illustrated on many occasions. For example, several unidentified gases were detonatedat a re-
mote site. In one case, the charges failed to completely sever the cylinder. The resulting ex-
plosion rocketed portions of the cylinder over several hundredyards, releasing a toxic gas over
a broad area.
Management of Waste
Compressed Gases 689
Even if hazardous waste management regulations are inapplicable, air discharge regula-
tions may cover management of a compressed gas. An example is sulfur dioxide. mically,
state air regulations apply to emissions, or potential emissions, without regard to treatment
systems.
Local building and fire codes often apply to Compressed gases.These may cover the stor-
age of cylinders. Some local regulations now include aspects of storage such as emergency
containment and treatment. Codes developed by associations such as the National Fire Protec-
tion Association may be adopted by local agencies for compressed gas cylinders.
IV. IDENTIFICATION OF CYLINDER CONTENTS

Where identification of a compressed gas is necessary, safety of the sampling effort becomes
a critical concern. Because of the chemical characteristics of some gases, fire or explosion or
other release of toxic gas may occur during sampling. When cylinders or valves have deteri-
orated, it is very possible to have failures resulting in uncontrolled release of the contents.
Procedures and technologiesthat have historically been usedfor management of cylinders
in poor condition have not always met adequate safety standards. These techniques have in-
cluded uncontrolled release, valve removal, and uncontained tapping.
Uncontrolled release has historically been the methodology employed for problem cylin-
ders. This includes penetration of the cylinder shell with projectiles or explosives. Variations
have provided this penetration in conjunction withfire pits. None of these provide for protec-
tion of the environment and rely upon distance for protection of personnel.
One proposedvariation of this technique involves explosive detonation inside a “gastight”
bomb chamber. With some gases., however, the energy released by the detonation can easily
exceed the maximum rating of any chamber that can be built.
Valve actuation insidea containment unit canbe accomplished ina foreign-designed over-
pack vessel. This procedure is ineffective where the valve is blocked, defective, damaged, or
failed in a closed position. Experience has also raised concerns over failures associated with
gases passing through dynamic seals of the containment unit. Major compressed gas companies
with this type of equipment will not permit its use with many hazardous gasesor for unknown
cylinders.
In a variation of this technique, the valve may be removed rather than actuated. It is pos-
sible, however, for the valve to break off or for the cylinder orifice to be completely blocked.
Either of these problems will result in a much more hazardous situation following the attempt.
One often proposed technique involves cold or hot tapping of the cylinder. A similar tech-
nique is used for low pressure gas lines. Guidelines developedby the American Petroleum In-
stitute (API) clearly demonstrate, however, that it is inappropriate and highly dangerous in
situations involving high pressure cylinders with unknown contents.
Guidelines for tapping are publishedinAPIPublication 2201 (third edition, October
1985). Bum-through prevention cannot be ensured unless base metal thicknessis greater than
3/16 in. Very few cylinders meetthis requirement. The procedure requiresthat the base metal
be free of laminations, corrosion, and other imperfections.
Further, hot tapping cannotbe done where cylinder contentsmay contain oxygen-vapor-
air mixtures in an explosive range; hydrogen, acids, chlorides, peroxides, or chemicals that
may explosivelydecompose(includingacetylene); caustic soda or amines; or unsaturated
hydrocarbons (e.g., ethylene). Unless the contents and pressure are absolutely known, this pro-
cedure cannot be used.
The cold tapping proceduremay be used for known low pressure gases. It is crucial, how-
ever, that the cylinder contentsbe known with certainty. For example,a high pressureinert gas,
690 Nickens
often used with some liquefied gases, could overpressure the device. Because of the tenuous
nature of the gasket seal, a suitable surface must be prepared. As with any extraordinary pro-
cedure, provision must be made for emergency containment and response.
A proposed variation of this procedure is installation of a new valve in the body of the
cylinder. Along with previously cited technical objections, this is hazardous because the cyl-
inder shell may have been weakened by corrosion.
A major problem with these techniques is graphically demonstrated by reactions involving
strong oxidizers. Even in an inert environment, exposure of bare metal to fluorine gas will re-
sult in an ignition that destroys the cylinder shell and any associated appurtenances.
Adequate records and labels documenting the origin and use of cylindersbemay sufficient
for identification of cylinder content. If, however, there is a potential for mixing of different
gases (e.g., by common manifolding) or other reason to suspect the accuracy of records, fur-
ther efforts to obtain confirmatory identification are necessary.
Prior to developing a sampling approach it is desirable to obtain as much information as
possible as to possible contents. Inventory records, usage history, and personnel interviews
may be useful. This typeof information may allow the investigationto be focused on probable
contents.
After background information has been obtained, the cylinder should be inspected. De-
pending upon the circumstances, personal protective equipment, including supplied air and en-
capsulating suits,may be required. A high level of protection is appropriate when the cylinders
potentially contain hazardous materials (this mustbe assumed unless adequate information to
the contrary exists) and if the cylinders are stored in an enclosed area.
The inspection should be conducted in a manner that minimizes disturbance of the cylin-
ders. Cylinders in poor condition may either fail or begin to leak if moved. Simply moving
cylinders with unstable contents (e.g., unstabilized hydrogen cyanide or tetrafluorohydrazine)
can cause detonationof the contents.
It is especially important to avoid manipulation of the cap or valve until it has been de-
termined that the cylinder is stable and emergency response procedures are in place.
The personconductingtheinspectionshould be familiarwithcompressedgases and
cylinders.Theinspectorshould be sufficientlyexperiencedtoevaluatethepotentialhaz-
ards associated with these containers and their contents. As with other potentially hazard-
ousoperations,theinspection should not be completed without experienced, professional
assistance.
Labels can be used for preliminary indicationof contents. The labels will typically be ap-
plied to the body or shoulder of the cylinder. Unfortunately, these are not indestructible and
may no longerbe either readableor even present. Labeling may also be misleading whereit has
not been updated or contaminants have been introduced.
Some cylinder information is stamped into the body of the cylinder. DOT requires that the
cylinder type,service pressure, serial number, test date, and manufacturer by identified on the
body of each cylinder. Although these are usually preserved, in some cases corrosion can ob-
scure this information.
DOT has developed specifications for cylinder types based on classes of gases.DOT has
also adopted recommendationsof the Compressed Gas Association for valve typesto be used
with most gases.
An example of the information obtained from valve type is shown by identifying a cyl-
inder as a DOT 3AAwithaCGA 580 valve.Thesecylinderandvalvetypes are speci-
fied for inert gases such as nitrogen. It should not, however, be assumed that this will always
be the nature of the contents. It is not uncommon for cylinders to be filled outside of these
guidelines.
Gases
Management
Compressed
of Waste 691
These conventionsdo not applyto cylinders of lecture bottle size. These cylinders contain
only small volumes (less than 112 L liquid volume).
In recent years a color code has been adopted and used for medical gases. Color of the
cylinder is typically not, however, a reliable indicator of contents. Most manufacturers have
different color codes, and these may not have been historically uniform.
Some “experts” offer cylinder identification based solely on visual inspection. Relying on
this type of identification is risky and negligent. The technical director for the Compressed Gas
Association has written that these consultants are like “snake oil salesmen.”
The general appearance of the cylinder is important to developing a safe sampling plan.
The overall condition of the cylinder should be noted, especially with respect to denting or
corrosion. Evidence of exposureto fire may be presented by burn marks. If possible the valve
should be examined without unduly disturbing the cylinder.
If the possibility of radioactive gases cannot be eliminated, the initial inspection should
include a scan for external radiation. Any detection of radioactivity shouldbe cause to develop
appropriate protective procedures.
Evaluation of information obtained during the inspection will permit preparation of a suit-
able sampling plan. The sampling approach is largely dependent upon the degree of certainty
with which the cylinder contents can be deduced and the potential hazards associated with a
release.
Only cylinders in good condition shouldbe considered for sampling through the cylinder
valve. Handling should be minimized in any case until the contents have been identified.
Safely obtaining a suitable sample is the principal challenge in the identification process.
The degree of hazard is largely dependentupon the contents of the cylinder. If there is no in-
dication of the contents, a worst-case approach must be used. As with samplingof other types
of unidentified pressurized wastes, sampling must be completed using remote techniques with
an explosion-resistant barrier [see regulations promulgated by the Occupational Safety and
Health Administration, 29 CFR 1910.120(j)].
Cylinder carts or forklifts with suitable attachments are useful for moving larger cylinders.
During any handling the cylinder should be monitored for any temperature increases associated
with polymerization of unstable gases.
Unless the natureof the cylinder contents canbe determined with reasonable certaintyat
this stage, remote sampling procedures are required. The mere operation of a cylinder valve has
been known to result in detonation. Incidents of this type have included gases suchas hydrogen
and ethylene oxide and mixtures suchas a mixture of deuterium and oxygen.
Accessing the cylinder valve may pose a potential problem. It is common for the protective
cap to corrode to such an extent that it cannot be unscrewed.
Upon removal of the valve cap, the valve itself shouldbe carefully inspected. To be con-
sidered for the remote valve sampling operation, valve threads must be in good condition with
an adequate sealing surface. Discoloration, excessive valve corrosion, or damaged threads are
cause for discontinuing the operation.
The construction of sampling apparatus mustbe compatible with the expected gas.If the
contents are unknown, universal compatibility is required. This typically includes the use of
stainless steel, passivated steel,or Teflon that has been cleanedof all contaminants. The Com-
pressed Gas Association (CGA) specifies cleaning procedures for use in oxidizing environ-
ments(oxygen or fluorineservice).Further,allcomponentsmust be capableofsafely
containing the maximum pressure that may be exerted by the compressed gas.
It is critical that the atmosphere within the sampling system be inert. Exposure of pyro-
phoric gases (gases that can be ignited at mom temperatures) to air can result in combustion or
explosion.
.
692 Nickens
Figure 1 Valve sampling system. (Courtesy of Earth Resources Corporation, Ocoee, Florida.)
Obtaining a minimal sample quantity at less than atmospheric pressureis desirable. This
can be accomplished by using appropriate controls. Should leakage occur during sample trans-
port, it will be into the sample container.
Provisions should be made for response to valve failures during sampling. It is not un-
common for leakage to occur following valve actuation, especially with packed valves. Treat-
ment or containment options should be provided for this eventuality. It is also possible for a
valve to fail during opening, preventing closure. Roughly 1-3% of sampled waste cylinders
have experienced some typeof valve failure.
For the remote operation to provide protection against potential explosive reactions that
could occur during sampling, the cylinder must be isolated. This canbe accomplished by erect-
ing barriers such as sandbags or a containment chamber. An example of a mobile sampling
system is shown in Figure 1.
A valve opening mechanism consisting of a pneumatically actuated wrench has been de-
veloped. The wrench contains adaptersto allow it to fit various types of valves. The control is
operated from a remote location outside the protective barrier.
Valve movement does not always indicate that the cylinder contents have been accessed.
This must be verified by positive means. It is possible that there is internal blockage or the
valve stem has broken inside the valve body.
The remote valve opener should be constructedto permit maximum application of toque
without overstressingthe valve. If this mechanism is incapable of actuating the valve, it cannot
be safely opened.
Cylinders or valves that are in poor condition requirespecial handling procedures. These
procedures are also required where the valve is inaccessible or cannot be operated.
Management
Compressed
of Waste Gases 693
A patented device has been developed for sampling under these circumstances-the Cyl-
inder Recovery Vessel (CRV). This equipment permits remote release of the gas in an inert
contained environment. Figure 2 shows the key components of this sampling system.
The Cylinder Recovery Vessel was designed to control and contain all common com-
pressed gases and liquids. The system provides for remote release and recontainerization of
pressurized gases and liquids in a completely contained inert environment.
The CRV is an ASME-rated pressure vessel.The waste cylinder can be pierced by a drill-
ing mechanism housed within the vessel. Priorto drilling, a vacuumis obtained andan atmo-
sphere of inertgas is introduced. All internal components are hydraulically actuated, removing
possible sources of ignition.
The interior of the vessel and its associated systems are composed of passivated steel,
stainless steel, or Teflon. All hydrocarbons and other reactive materials are excluded from
possible contact with cylinder contents. The hydraulic fluid used for CRV components is an
inert fluid.
A secondary containment chamber housesthe CRV and its systems. This reinforced steel
chamber issealed to contain any release from the primary system. All of the equipment in the
chamber is suitable for operation in a Class I, Division I1 explosive environment. Ports are
attached so that any released gases can be withdrawn and treated in the unlikely instance of a
leak in the primary system. Temperature inside the chamber be cancontrolled by a heating and
cooling unit.
All operations are controlled from a panel located outside the trailer. In this manner per-
sonnel are isolated from the sampling operation.
After contents of the cylinder are released inside the CRV, a sample can be withdrawn
through a port extending to the exterior of the trailer. An evacuated sample cylinder attachedto
the port is opened to obtain a small volume of the contents for analysis. On-site analytical
equipment provides an identification of the contents within minutes.
The CRV provides for recontainerization of both gasesand liquid cylinder contents. The
cylinder contents are transferred to a new DOT-approvedcylinder for subsequent disposal. The
contents can also be transferredto an appropriate treatment system.
Appurtenances to the vessel include a cylinder clamping and locking mechanism and a
roller mechanism for rotating liquid cylinders. Diaphragm compressors complete the purging
and recontainerization process.
Included in the operation are controls to verify the functioning of the equipment. The en-
tire operation is monitoredby a remote video camera that shows the interior ofCRV. the Pres-
sure and temperature are monitored at numerous points in the process system. These systems
allow the operator to effectively control the process.
When the cylinder processing has been completed, the empty target cylinder is removed
from the chamber. The cylinder is then cut into halves with a power saw. Any solid residue
inside the cylinder isremoved and containerized. The clean, empty remains of the cylinder is
containerized and staged for disposal.
Analyses of gases canbe completed with a variety of instrumentation. m i c a l techniques
used include mass spectroscopy (MS), Fourier transform infrared spectroscopy (FTIR), gas
chromatography (GC), and wet chemical testing.
Gas chromatography is useful when the identity of the gas is known or suspected. The
technique provides for selective absorption and elution in a column. m i c a l l y a standard of the
test gas is required.
The mass spectrometer (or residualgas analyzer) is a vacuum analyzer that will measure
total pressure and partial pressure. The analyzer is typically capable of separating the ions
694 Nickns
Management
Compressed
of Waste Gases 695
formed in an electron impact source according to their mass-to-charge ratio. The signal col-
lector may be either a Faraday cup or a secondary emission multiplier.
The FTIR can be used for identification of unknown gases based on absorbance spectra.
The infraredspectrumcontains characteristics thatpermitidentificationofthefunctional
groups or “working parts” of molecules. Through the use of an interferometer, infrared wave-
lengths are passed through a sample simultaneously.
After obtaining the sample transmittance, the spectrum is mathematically converted to ab-
sorbance. The absorbance spectrum is then compared to spectra contained in various libraries.
This can be accomplished through computer programs.
Wet chemical methods can also be used. ’ZLpically this will involve reaction with a variety
of reagents and calorimetric materials. These are inexpensive procedures that can be used if the
gas is known. With unknown gases the methodology can be extremely hazardous.
Information generated in the analytical process may be insufficient to provide an identi-
fication of the cylinder contents. Inmany cases it is necessaryto have associated observations
to reach a reasonable interpretationof the results.
A typical problem in obtaining an analysis is related to the reactivity of the sample gas.
Many gases will react during the sampling or analytical process to form other compounds. The
analysis will generally show the reaction products and not the cylinder contents.
An example of the problems associated with obtaining a sample of a reactivegas is illus-
trated by fluorine. Because of its extreme reactivity, it is likely that the sample will react with
some contaminant (residual wateror air or unpassivated surfaces) during the process. The gas
can similarly react within the analytical equipment, evento the point of damaging the instru-
ments. Analysis may show reaction products such as hydrogen fluoride.
Most analytical libraries of spectraare incomplete with respectto compressed gases. Fur-
ther, depending upon environmental conditions, the spectramay appear to be different. Com-
plicating the analysis are the many potential mixtures that may be present. This can lead to
some ambiguity in interpretation.
After tentatively identifying a compound, it is importantto relate it back to the physical
characteristics observed during sampling. For example, it is easy to confuse the varietyof hy-
drocarbon spectra. If significant pressure was noted during sampling, hydrocarbons with lowa
vapor pressure can be eliminated. The same conclusion cannot, however, be reached where
there are additional components indicated (e.g., metal anhydridesmay be dissolved in an or-
ganic solvent).
All of the observations made during the analytical process should be combined with ex-
perience with compressed gases and cylindersto reach a reasonable interpretation.
The sampling and identification process is fraught with potential hazards for the unsus-
pecting. It is crucial that those involved with the sampling be professionals with extensive ex-
perience in handling compressed gases.
Unfortunately there have been examples of contractors misrepresenting their experience
and capabilities. Given the ramifications and liabilities associated with an accident, careful
screening of contractors is imperative.
V. EXAMPLEMANAGEMENTPROGRAMS
The Los Alamos National Laboratory is a research facility operated by the University of Cal-
ifornia for the U.S. Department of Energy. Since its inception1942, in the laboratory has han-
dled a variety of hazardous materials, including compressed gases. In 1990 a facility-wide
program was undertakento manage compressed gases considered to be in excess of their users’
requirements.
696 Nickens
The objective of the program was to identify and properly manage cylinders containing
compressed gases. The need for this service was originally identified by the Waste Manage-
ment Group (HSE-7). This group has accumulated approximately 400 waste compressed gas
cylinders at a secure storage location. The cylinders of concern were those owned by the lab-
oratory. Cylinders thatwere leased by the laboratorycould, in many cases, be returned directly
to the vendor.
Historically, compressed gas users at the laboratory had purchased cylinders for their
use. Under waste regulations, the laboratory became responsible for dispositionof the waste
gases.
Rather than adopta piecemeal approach,HSE-7 decided to attack the entirety of the prob-
lem. A contract was let for a single source outlet to collect, sample, identify, and dispose of
these materials. Concurrently, notices were sent to the technical groups at the laboratory ad-
vising users of the collection program.
A preliminary listing of the gases believed to be present at the storage location indicated
the potential range of hazards. These gases included extremely toxic gases (suchas arsine and
nickel carbonyl), reactive gases (fluorine and chlorine trifluoride), unstable gases (tetrafluo-
rohydrazine), pyrophoric gases (silane), radioactive gases (tritium), and corrosives (hydrogen
fluoride and hydrogen chloride).
Most of the cylinders were in good condition. A significant number, however, were in a
deteriorated condition. Some were nonstandard containers that did not meet DOT container
specifications.
A primary concern for proper management of the cylinders was identification of the con-
tents. For most of the cylinders, this required sampling.
Facilities were established ina remote area of the laboratory for processingthe cylinders.
These facilities included a vapor containment structure, cylinder sampling equipment, and an
on-site laboratory. Sampling and analysis of the gases began in August 1990.
The vapor containment structure was central to the processing effort. This structure con-
sisted of a large temporary building (approximately 30 ft by 100 ft and 15 ft in height). Cyl-
inders were staged inside the structure for processing. Activities within the structure were
monitored by several cameras.
The structure included several emergency treatment systems. A liquid impinging scrubber
and activated carbon scrubber/molecular sieve adsorbent canisters were provided to treat the
atmosphere insidethe structure in the event of a release. The vapor containmentstructure could
be sealed to capture and contain accidental releases.
Incorporated intothe vapor containment structure was a valve sampling room. Inthis area,
those cylinders in good condition with operable valves were remotely sampled.
The valve sampling setup was similar to that shown in Figure 1. The cylinderswere placed
into a containment chamber and attachedto a remotely operated valve actuation mechanism.
Cylinders in poor condition or with inoperable valves were sampled using the patented
Cylinder Recovery Vessel (CRV). This equipment also provided recontainerization capabilities
for containers not meeting specifications.
An on-site laboratory was located adjacent to the vapor containment site. The laboratory
was equipped for radiological analysis and chemical identification.
Chemical analysis of cylinder contents was accomplished using a combination of tech-
niques. The primary methods were Fourier transform infrared spectroscopy and mass spec-
troscopy.
Following identification using these techniques, a small sampleof the gas was dissolved in
a compatible solvent. The solvent was placed in a liquid scintillation counter for detection of
low levels of radioactive materials.
Management of Waste Compressed Gases 697
The initial task required in the management processW= inspection Of the CYlinders- The
purpose of the inspection was to categorize each cylinder accordingto its condition and SUS-
petted contents. This task was assignedto a cylinder inspection team consisting of a cylinder
specialist, a health physics technician, andan emergency coordinator.
Categorization of the cylinders was based on external characteristics and information
SUP-
plied by the users. The four general categories used W e r e
1. Unrestricted. Standard DOT containers in good condition whose contents have’been cer-
tified by the user
2.’ Restricted.Labeledcylindersingoodcondition
3. unknown. Cylindersthat are suitablefortransportationbuthavenoindicationof
contents
4. Unstable.Cylindersinpoorcondition or with unstablecontents
Contents of unrestricted cylinders were identified based upon certifications of theTOusers.
be acceptable for certification, several criteria had to be met:
1. The user had to have personal knowledge as to its contents.
2. The purchase and usage history of the cylinder had to be documented.
3. The cylinder could not have been used in applications with other commonly manifolded
gases.
4. The cylinder must not have been connected to a process in a manner in which it could
become contaminated.
Initially only a few cylinders were certified. As a cost-saving measure, a laboratory task
team was organizedto work with the users to document cylinder contents. In the latter stages
of the project .a significant perciintage of the cylinders were accepted under this classification.
If the cylinder configuration and labeling was consistent with its certified contents, the
cylinder was taken directlyto a storage area for direct disposition. Because of inconsistencies
between labeling and analyses, however, the laboratory decided to sample a representative
number of the certified cylinders.
In addition to visual classification of cylinder condition, the exterior was scanned for ev-
idence of radioactivity. The health physicist completed a radiation survey and obtained a sur-
face “swipe” for analysis.
Because the facilitiesat Los Alamos are spread out over a large area, the cylinders had to
be collectedand moved to the processing facility. Fortunately, the transportation routes did not
extend outside of laboratory-controlled areas. Regulatory prohibitions would have prevented
transportation of unidentified gases over public roadways.
Transportation was accomplished using a specially modified truck. An emergency re-
sponse crew accompanied the truck throughoutthe short trip to the processing facility.
More than 1500 cylinders were sampled during the courseof the one-year program. The
variety of cylinder types and gases encountered posed significant challenges for both sample
collection and analysis.
Of those sampled, most were accessible through the cylinder valve. A total of 1316 cyl-
inders (84% of the number sampled) were processed in this manner. Approximately 2-396 of
the attempts to sample in this manner were unsuccessful owing to valve failure.
The valve sampling system provided a mechanismfor sampling all standard valves [those
designated by the Compressed Gas Association (CGA)]. Because of the higher potential for
failure, those cylinders with petcock valves (discontinued CGA 110 type)were not sampled in
this manner. Cylinders with multiple valves were also excluded because this configuration
could have resultedfrom failure of the primary valve.
698 Nickens
In some cases cylinder valves were found to be leaking upon removal of the dust cap pro-
tecting the connecting threads. Because the caps were removed by workers using totally en-
capsulating suits with supplied air, there was no exposure to hazardous gases. Further, sampling
was completed inside the vapor containment structure, which was designed to contain any re-
lease to the environment.
Failure of the cylinder valve to open was a typical problem. Although the maximum rec-
ommended torque was applied, some valves would not actuate. Even when the valve handle
rotated, there were cylinders whose contents could not be accessed. Because of the obvious
safety concerns, an important part of the sampling operation was verifying that there was free
access through the valve to the interior of each cylinder.
As expected, an incredible variety of gases were identified. Analytical results proved the
prudence of the sampling program. At the midpoint of the project, a survey showed more than
45% of labeled cylinders contained different or additional constituents. Ten percent increased in
hazard classification based on sampling results.
Several extremely hazardous cases illustrate the problem posed by inadequate labeling
of cylinders. An oxygen cylinder with a standard medical post valve was found to contain
radioactive tritium. Some cylinders configured for inert gases contained either poisonous or
reactive gases.
Many of the cylinders and valves failed to follow standards of the Compressed Gas Asso-
ciation. For example, the CGA 540 oxygen valve was frequently found on cylinders containing
a variety of other gases.
By the conclusion of the project, a total of 262 cylinders were processed through the Cyl-
inder Recovery Vessel. Because of the relatively slow processing rate, CRV operations ex-
tended beyond valve sampling by several months.
Without the capabilities of the CRV, more than 16%of the cylinders could not have been
handled. Only the CRV was capable of managing the extremely powerful oxidizing gases com-
monly used at Los Alamos. The unique ability to manage these gases in a remote, contained
process was crucial to the success of the project.
Some of the cylinders were found to contain air or inert gases at atmospheric pressure.
Cylinders that were not reusable were decommissioned and disposed of in a landfill. Many of
the cylinders were reclaimed by the gas plant at the laboratory for reuse.
Gases that were typically used by the laboratory were likewise recycled by the gas plant.
These were generally common, innocuous gases such as nitrogen or argon.
Originally a permitted hazardous waste incinerator was slated for use for disposal of waste
gases. Developmental and operational difficulties, however, delayed the facility in accepting
most of the gases except for freons and inert gases.
A specialty gas manufacturer was approved for purchase and recycling of cylinders. This
option was deemed viable for most commercially available gas except radioactive gases.
The cylinder management program was predicated upon principles of safety and environ-
mental protection. The variety of hazardous gases and condition of cylinders posed significant
challenges to these goals.
Engineering controls were instrumental in providing adequate safety for workers. As pre-
viously discussed, critical sampling operations were completed remotely.
Engineering controls were also in place for preventing accidental releases. All of the sam-
pling apparatus had some manner of secondary containment. Further, the entire operation oc-
curred inside a vapor containment structure with emergency treatment equipment.
The effectiveness of these controls was clearly demonstrated in one of the two safety in-
cidents that occurred in the course of the project. A cylinder that may have contained residual
oxygen difluoride was removed from the CRV. When monitoring systems detected an atmo-
Management of Waste Compressed Gases 699
spheric contaminant inside the structure, emergency treatment systems were activated. Exterior
monitoring of the structure found no detectable release to the atmosphere. Personnel who had
been working inside the structure in protective equipment were sent to the hospital as a pre-
cautionary measure, Examinations showed that there was no evidence of exposure.
One other safety incident of note involved radiological analyses. During sample prepara-
tion, phosgene apparently degassed from a small vial of scintillation fluid. The laboratory was
evacuated as a precautionary measure. Although there was no hazardous exposure to person-
nel, procedures were modified to provide for complete isolation of scintillation fluids.
The management of hazardous gases at the Los Alamos National Laboratory was a major
step in dealing with problem materials that had accumulated over 50 years of operation. The
procedures demonstrably accomplished the goals of worker protection and environmental
protection.
In August 1991 the project was suspended for lack of funding. Despite its premature ter-
mination, significant progress was made toward identifying the full scope of the problem and
acceptable means of managing it.
Procedures for management of these materials were thoroughly tested and evaluated in the
course of the project. The lessons learned and the success of the operation provide standards
for handling compressed gases at other laboratory, governmental, and industrial facilities.
VI. ABANDONED WASTE SITES

The techniques described in the preceding sections have been tested on several sites with a
variety of gases. The project sites have included abandoned Superfund sites such as the Fike
Chemical site in Nitro, West Virginia and the Chemical Control Corporation Superfund site in
Elizabeth, New Jersey.
The Fike Chemical site in Nitro, West Virginia was a chemical manufacturing operation
that was abandoned and taken over under the Superfund program. Approximately 60 cylinders
in varying conditions remained at the site during the remediation.
The cylinders at the Fike Chemical site were found at various locations throughout the
facility. Initial cylinder reconnaissance was completed by the EPA's technical assistance team
(TAT). TAT provided Earth Resources Corporation (ERC) with the locations of the cylinders
on the site. The cylinders were then inspected by ERC personnel to determine if they would be
valve sampled or processed in the CRV. Cylinders were also checked for labels, markings, and
leakage and to determine if they were safe for transport to the vapor containment building.
Cylinder processing at the Fike site was accomplished using both the remote valve sam-
pling device and the CRV. Cylinders that could be valve sampled were processed first. A total
of 36 cylinders were sampled using the remote valve sampling technique. Cylinders that could
not be sampled with the valve sampling device were processed with the CRV. Twenty-one cyl-
inders were processed using the CRV.
Of the cylinders processed in the CRV, 62% contained air or constituents of air. The re-
maining 38% contained one or more of the gases 1-butane, boron trifluoride, hydrogen chlo-
ride, hydrogen bromide, and hydrogen sulfide.
Contents of cylinders processed in the CRV were treated on-site. Some of the cylinders that
were valve sampled were returned to the manufacturer after analysis (provided the cylinder met
appropriate shipping requirements). Those cylinders that were valve sampled but were of un-
known origin were treated on-site.
The Chemical Control Superfund site in Elizabeth, New Jersey was a former waste dis-
posal facility that burned in 1980. Thousands of drums and many cylinders were removed dur-
700 Nickens
ing an initial remediation. Approximately 200 cylinders remained at the site, however, in se-
verely deteriorated condition after exposure to thefire and weathering. In 1987 the cylinders
were placed in protective overpacks and staged at the site.
Because the cylinders at the Chemical Control site were contained in overpacks, part
of the work required handling these materials outside of the CRV containment structures. TO
provide for emergency containment in the event that a leak occurred during one of these
p e s s e s , a temporary vapor containment structure was erected at the site. This structure
also contained the principal treatment systems. The general site configuration is illustrated by
Figure 3.
Various treatment systems were established in conjunction with the operationto provide
for the disposalof the compressed gases. These systems included molecular sieve and activated
carbon adsorbents, a liquid impinging scrubber,and a flare unit.
The initial task of operations required that the overpack cylinders moved be into the con-
tainment structure. Once inside the structure, the overpacks were attached to a sampling and
treatment system. Samples of the overpacks were obtained using a vacuum system that was firs
purged with an inert gas.
Each of the overpacks was initially sampled.The purpose of this sampling was to deter-
mine whether the cylinder inside had failed during storage. The first overpack sample indicated
a pressure of approximately 30 psig and an explosive mixture of hydrogen and air.The presence
of hydrogen and air was a pattern to be repeated in approximately 70% of the overpacked
samples.
Since the cylinders contained in these overpacks were intact and contained other gases, it
became clear that the hydrogen must have been generated from a different source. It is hy-
pothesized that the hydrogen was generated through a reaction involving residual water and
+
iron: Fe H,O + Fe0 + Hz.
The presence of an explosive mixture of hydrogen and air around potentially incompatible
cylinders greatly increased the risks associated with the work. In handling the overpacks, it w
determined that the hydrogen could be removed through a controlled venting procedure. Excess
pressure in the overpack was allowed to exhaust through theflare stack without burning. After
equalization of pressure, a vacuum was created inthe overpack, and it was exhausted through
the flare stack. This procedure was followedby purging with inert gas.
During this process, eachof the overpacks was carefully grounded. This procedure related
to the potential for building up a static charge through the passage of gas in the lines. Any
sparking with the mixture in the overpack would havebeen disastrous.
Of the 181 overpacks, only 10 (6%) contained gases that originated from leakage through
failure of the cylinders. The gases in the overpacks included hexafluoroethane, monomethyla-
mine, ethane, propane, isobutane, acetone, 2-methyl propanethiol, nitrous oxide, and methane.
In the 26% of the overpacks that did notshow a potentially explosive mixture, there was,
however, some enrichmentof hydrogen. It appears that these overpacks did not have the same
atmosphere or moisture available to generate the hydrogen. Additionally, in those overpacks
where leakage occurred from the original cylinders, hydrogen was not detected.
Of the cylinders removed from the overpacks, approximately 10%were clearly perforated.
These cylinders were sent directly to the cylinder rinse area after determination through in-
spection that they contained neither a solid nor a liquid. After immersion in the rinse tank, the
cylinders were removed and cut intotwo pieces for subsequent disposal.
Most of the cylinders that were intactat the time of processing proved to contain onlyair
or water. These cylinders did not exhibit a significant pressure increase upon release into the
CRV. It is possible that these cylinders failed during thefire or subsequent weathering.
Management of Waste CompressedGases 701
I
702 Nickens
'Ilventy-two percentof the intact cylinders containeda variety of materials. These included
flammable gases, reactive gases, toxic gases, and pyrophoric liquids and solids.
Flammable gases encountered at the site included cyanogen (one cylinder), ethane (two
cylinders), and ethylene oxide (one cylinder). Flammable gases were readily treated through
the flare stack. These gaseswere introduced to a flame in a controlled manner. Air monitoring
using organic vapor detectorswas employed during the treatment process. Air was monitored
at both upwind and downwind locations to detect any differences from background.
One of the flammable gas cylinders processed createda particular problem for waste dis-
posal. An acetylene cylinder that was drilled contained solid material that was determined to
be an asbestos fiber. Asbestos is a common filler for cylinders of this type.
The CRV was decontaminated usinga HEPA filter vacuum. The cylinder and the recov-
ered asbestos were packagedin disposal bags for subsequent handling.Air monitoring follow-
ing the procedures demonstrated thatthe vessel had been effectively decontaminated.
A variety of potentially toxic gases were encountered during the operations. Among the
particularly hazardous gases were cyanogen [threshold limit value (TLV) of 10 ppm], phosgene
(TLV of 0. l ppm), and iron pentacarbonyl (TLV of 0.1 ppm).
Several reactiveor corrosive gasesand other materials were found in the cylinders. These
included anhydrous hydrogen chloride and hydrogen fluoride. Among the most difficult ma-
terials to deal with were reactive organometallic compounds.
The reactive materials were treated using the liquid impinging scrubber. A caustic solu-
tion was used as the reagent in the scrubber for the acid gases (e.g., anhydrous hydrogen
chloride).
The Fike Chemical and Chemical Control Corporation Supefind sites illustrate the suc-
cessful employment of conservative methodologies for handling difficult waste management
problems. The projects were successful intesting all of the cylinder contents and disposingof
the materials on-site. This was accomplished without releasing the materials to the environ-
ment or exposing workers and the general public to hazards associated with them.
The gases encountered during these projects support the selection of this conservative
methodology over others that had previously been proposed. In retrospect, it is evident that
rejected off-site transportation and disposal techniques would have been inadequate for the
materials at these sites. Transportationof the materials would have been extremely hazardous,
as the cylinders were in poor conditionto begin with and itis possible that a release couldhave
occurred.
One of the alternatives investigated for the cylinders was detonation in a remote area.
Some of the materials encountered at these sites, however, would not have been destroyed by
an uncontrolled explosion. Many of the materials would have been released and would have
subsequently presented hazards to workers and the environment.
Detonation of the acetylene cylinder containing asbestos would have generated a major
problem of airborne asbestos. Othermaterials, such as the nonvolatile organometallics,would
also have been spread into the environment in an uncontrolled fashion. Nonpyrophoric gases
such as hydrogen fluoride and chlorine would simply have been released in an uncontrolled
fashion and would not have been affected by the detonation or consumed by fire.
VII. CONCLUSION
Compressed gases have been an area of increasing concern for waste managers. Although these
materials have been widely used, applicationof management regulations has progressed slowly
in comparison with other types of waste.
Management
Compressed
of Waste Gases 703
Compressed gas wastes and their containers pose significant hazards and potential liabil-
ities. The number and typesof accidents and the closure of disposalfacilities have highlighted
the necessity of a conservative managementphilosophy.
Procedures and equipment have been developed to greatly increase the safety of handling
waste compressed gases. Demonstrated success on major projects has increased the acceptance
of these as standard practices. As more regulatory attention is focused on these wastes, the
expediency of these practices will become more apparent.
35
Pollution Control in the Dairy Industry
T.Viraraghavan
University of Regina
Regina, CaMda
1. INTRODUCTION
The dairy industry occupies an important place in the food supply in many countries. In the
United Kingdom the dairy industry provides24% of the protein content of the nutritionaldiet
[l]; in some countries, e.g., New Zealand, it earns a sizable portion (approximately 20%) of
the foreign exchange [2]. Major categories of dairy products are (1) fluid milk products, (2)
butter, (3) cheese, (4) ice cream and frozen desserts, and(5) condensed and evaporated prod-
ucts. In some cases, several types of dairy products are produced at a single facility. Figure 1
shows a flowsheetof an integrated dairy process.
II. DAIRYPLANTWASTES
Dairy wastesare generally dilutionsof milk or milk products resulting from product losses
dur-
ing handling and transport together with detergentsand sanitizers from intensive washingo p
erations. The following operations contributeto the major product losses 131:
1. Sludge discharges from clean-in-place (CIP)clarifiers
2. Start-up, shutdown, and changeover in high temperature, short time (HTST) pasteurizers
3. Evaporatorentrainment
4. Bottleand case washing
5. Tank,can, piping, and other equipment washing
6. Breakage and spillage in packaging equipment
7. Production changeover in filling machines
Cheese and butter making processes produce whey and buttermilk, respectively. These
are high strength wastes that increase the organic waste load if discharged accidentally or
intentionally.
705
706 Viraraghavan
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Pollution Control in the Dairy Industry 707
Table 1 Summary ofConversionFactorsRelatingDairyProduct

to Milk Equivalents
~~~~ ~
equivalent
Product
Milk
(Ib) to 1 Ib product
Butter 21.3
lk Whole cheese 9.9
Evaporated 2.1
Condensed 2.4
milk Whole 13.5
Cottage 7.12
milk Non-fat dry 12.5
Whey 1.1
Dry whey 17.6
eam Whey 40.7
Dry 249.0
Ice cream' 2.67
~~~~
%e gallon of ice cream weighs 5.4 lb.

Source: Environment Canada [3].
Table 2 Water Usage in theCanadianDairyProductIndustry

Total water usage (Llkg ME)'
~~~~
Commodity Range Median
Fluid milk products 3.90 1.21-9.15

Butter products 1.30 0.82-3.21
Cheese products 0.79-5.90 2.75
Ice cream and frozen desserts 1.78 0.33-4.23
Condensed and evaporated products 1.45 0.37-2.59
'ME = milk equivalent.
Generally water useand process effluent loadings are relatedto the throughput in terms of
milk equivalents. Table 1 provides a summary of conversion factors relating actual product to
milk equivalents. Table 2 provides a summary of water use in the Canadian dairy product in-
dustry by commodity segment. The raw waste loads by commodity segment for the Canadian
dairy industry are included in Table 3. The data for the American dairy industry are summa-
rized in Table 4. Tables 3 and 4 show that waste loads in Canadian and American dairy plants
are similar.
The strengthand volume of the wastewater from any dairy plant will depend upon the pro-
cesses employed, the volume of milk handled, the commodity produced, the condition and type
of equipment, the waste reduction practices, the attitudeof the management and staff, and the
amount of water used in cooling and washing[5]. The chemical oxygen demand (COD) the of
dairy wastewater is saidto vary from less than100 mg/L to more than 20,000 mg/L depending
on the dairy product [6];biological oxygen demand (BOD) varies from40 mg/L to over 10,OOO
mg/L, and wastewater flows vary from542 U1000 kg milk equivalent to 900 WlOOO kg milk
equivalent [7]. Table 5 summarizes the characteristics of dairy wastewaters in the United States.
Milk product losses typically range from 0.5% in large advanced plants to in excess of
2.5% in small old plants [3]. Many of the water-saving and waste control changes specific to
the dairy industry include a number of steps[3], some of which are outlined below.
708 Viraraghavan
Table 3 Summary of Raw Waste Loads from Canadian Dairy Products Industry
~ ~~
BOD (kg/lOOO kg ME) TSS (kg/lOOO kg ME)

Range
Commodity Median Range Median
Fluid milk products 3.8 0.75-7.430.59-2.42 1.4
Butter 0.53-8.78 1.4 0.5 0.19-1.45
Cheese 5.1 2.12-8.48
0.72-2.51 1.3
Ice cream and frozen desserts 6.4 0.85-21.31
0.22-11.05 2.4
Condensed and evaporated products 2.2 0.99-4.40 0.6 0.08-1.40
*ME = milk equivalent; TSS = total suspended solids.
Table 4 Summary of American Dairy and Milk Processing Plant Effluent Characteristics
Waste vol.
coefficientb
BOD
coefficienf
No. of
Avg Product
Avg Range plants
Milk 6 0.1-5.4 3.25 0.2-7.8 4.2
Cheese 3 1.63-5.7 3.14 1.0-3.5 2.04
Ice cream 6 0.8-5.6 2.8 1.9-20.4 5.76
Cond.milk 2 1.0-3.3 2.1 0.2-13.3 7.6
Butter 1 - 0.8 - 0.85
Powder 2 1.5-5.9 3.7 0.02-4.6 2.27
Cottage cheese 3 0.8-12.4 6.0 1.3-71.2' 34.0
Cottage cheese and milk 19 0.05-7.2 1.84 0.7-8.6' 3.47
Cottage cheese, ice cream, and milk 9 1.4-3.9 2.52 2.3-12.9 6.37
Mixed products 5 0.8-4.6 2.34 0.9-6.95 3.09
Overall 56 0.1-12.4 2.43 0.2-71.2 5.85
'Volume: kg wastewaterkg milk (or milk equivalent) processed.
%OD kg BOD/1000 kg milk (ormilk equivalent) processed.
Whey included; whey excluded from all other operations manufacturing cottage cheese.
Source: Harper and Blaisdell [4].
1. Complete drainage of all tanks and pipes before rinsing

2. Recovery of low-volume, concentrated initial rinsesof tanks, cans, and equipment
3. Automatic shutoff valves on all hoses
4. Recovery of solid material such as fruit and cheese curd prior to discharge to a sewer
system
5. Removal of defective containers from bottling lines
6. Installation of control systems on all equipment where overflow might occur
7. Use of drip savers for milk car unloading in small plants
8. Routine inspectionof all lines, valves, and pumps to eliminate leakage, especially CIP
in
lines
9. Adequate temperature control coolers
in or burn-on lead-
and heaters to prevent freeze-on
ing to excessive product loss and water consumption during cleaning
10. Drip shields to prevent spilled products from entering the sewer system
11. Adequateentrainmentcontrolequipment on evaporatorsequippedwithbarometric *
condensers
Pollution Control in theDairy lndustry 709
Table 5 Characteristics of Wastewaters from

Dairy Plants in United States
Value"
Characteristic Range Mean
-
BOD 40-48,ooO 2300
COD 80-95.000 4500
ss 24-4500 820
Total solids 135-8500 2500
Nitrogen 1-180 64
Phosphorus P-2 10 48
Carbohydrate 250-930 520
PH 4.4-9.4 7.2
Temperature ("C) 18-55 35
'All values except pH and temperature are in mg/L.
Source: U.S. EPA [8,9].
12. Use of postcleaning rinses as make-up water for sanitizing and/or cleaning
13. Control or collection of leakage from damaged product containers
14. Collection and recovery of valuable by-products, especially whey
An extensive accountof good managementpractices in waste control inthe dairy industry
is included in a publication issued by US. EPA [8]. Milk rinsings and whey contribute to the
dairy waste loads and can be recovered. Whey is a by-product of cheese-making and can be
used as a supplement in livestock or poultry feed.
Harper et al. [lo] discuss the xesults of a study undertaken to reduce water and waste dis-
charges at the Kroger DairyCompany, a complex multiproductdairy plant in Indianapolis, In-
diana, throughmanagementcontrolandmodification of equipmentandprocesses.Before
control procedures were introduced, the plant discharged 400,000-800,000 gal of wastewater
per processing day, with a total BOD load of 10,000-15,000 lb. As long as direct supervision
was maintained on a regular basis, water use in the plant was reduced by one-third and the
organic waste load was reducedby one-half. Process and equipment changeswere made in the
plant that reduced waste discharges by 100,000 gaYday and reduced waste strength about20%
at an economic savings projected at $200,000 per year.
111. DAIRYWASTEWATERTREATMENT
Since dairy wastewaters are mainly composed of soluble organic materials, they respond ide-
ally to treatment by biological methods; the conventional methods generally used are (1) acti-
vated sludge, (2) trickling filtration, (3) lagooning, (4) anaerobic digestion, and ( 5 ) irrigation
or land application [l 13.
A. AerobicBiologicalTreatment
Tabulated information on a wide range of activated sludge plants, both laboratory and indus-
trial units, treating dairy wastewater is available elsewhere [8].The treatment efficiency values
vary from about 25%to over 99% with an average removal efficiency of about 85%.With good
operation, BOD removal efficiencies in excess of 90% are easily attainable with activated
sludge systems; however, even an efficient system may not be able to reduce the BOD from
710 Viraraghavan
2000 mg/L in the dairy waste to 20-30 mg/L in the effluent, which may be required by the
regulatory authorities. Westage systems are frequently required to meet such standards [5].
An extended aeration activated sludge systemtreating a dairy wastewater, under proper oper-
ating conditions, removed 99% BOD and 95% SS at an organic loading of 0.14 kg BOD/(kg
mixed liquor suspended solids (MLSS) day), producing an average effluent BOD and sus-
pended solids (SS) of 22 and 55 mg/L, respectively [12]. Guo et al. [l31 evaluated the perfor-
mance of an oxidation ditch treating 140-218 m3/day of dairy wastewater with a BOD in the
range of 380-1900 mg/L (average 950 mg/L) duringthe summer months. The organic loading
-
was 0.08 kg BOD/(kg M U S day) and 0.32 kg BOD/ (m3 day). The average effluent BOD
and SS were 7 and 28 mg/L, respectively, which corresponded to 99% BOD and 98% SS removal.
The wastewater treatment process employed by a condensed milk production plant con-
sisted of a combined extended aeration, trickling filter process treating 160m3/day [14]. The
average BOD and SS of the wastewater were lo00 mg/L and 300 mgL, respectively. When
operating well, an effluent BOD of less than 25 mg/L andSS of less than 100 mg/L were gen-
erally achieved.
The wastewater treatment facilityfor a 7-day week milk processing operation (producing
cheese and butter) consisted of a seven-stage RBC unit followedby aerated lagoons. The waste-
water BOD and SS were 3400 mg/L and 3200 mg/L, respectively, on average [14]. The final
effluent from the aerated lagoon system contained less than 25 mg/L of BOD SS, andfor over-
all removals in excess of 99% for both parameters. Exhaustive performance data on trickling
filters and lagoon systems treating dairy wastewaters are included in a publication of the U.S.
EPA [8].
Goronszy and White [l51 present data on large-scale cyclically operated activated sludge
facilities (batch reactors)treating cheese whey and dairy processing wastewater. Bothfacilities
included a captive selector reactor zone where biomass from the main aeration zone was mixed
with incoming wastewaters according to specific initial loading criteria. Both plants produced
effluents of acceptable quality. Schulte [l61 providesdetails of the design and operations of a
sequencing batch reactor (SBR)treating Meadowland Creamery wastewaterat Conroe, Texas;
the effluent quality consistentlymet the city’s requirementsof BOD andSS less than 200 mg/L
for the discharge of dairy wastewater to its sewer system.
B. AnaerobicBiologicalTreatment
Anaerobic processes have been employed recently for treating dairy wastewaters. A full-scale
anaerobic treatment plant for treating dairy wastewater was first installed in Canada at Granby,
Quebec. This plant, which treats the cheese wasteand several other processing wastes, consists
of two units-a downflow fixed film reactor and an upflow sludge blanket reactor [17-201. The
second Canadian anaerobic digestion system, at Millbank Cheese and Butter Ltd., is treating
cheese whey only [20].
Switzenbaum [21] reported onthe use of an anaerobic expanded-bed process for treating
whey waste; Vandamme and Waes [22] used an anaerobic contact process to treat dairy waste-
water; and Sutton [23] demonstrated the use of a membrane anaerobic reactor system (MARS)
to treat cheese whey permeate. Zaal [24] showed that the dairy waste could be efficiently
treated in an upflow anaerobic sludge blanket reactor.
One of the major limitations in the treatment of organic wastes by fixed-film anaerobic
reactors is the long start-up period that is required before optimum performance is achieved.
The reason for this is the length of time necessary for the development of a stable biofdm.
Start-up time varies from 4 to 8 months [25]. For starting up an anaerobic reactorfor treating
dairy wastewater, different approaches have been followedby different researchers. Varied ex-
Pollution Control in the Dairy Industry 71I
periences with respect to durations of start-up problems encountered during this period have
been reported. Samson et al. [26], who started up the reactorby inoculating the sludge froma
municipal wastewater treatment plant in treating the cheese waste, ran into difficulties during
a 4-month start-up period mainly because of the large fluctuations in the composition of the
plant effluent (pH varying from 2 to 11 and COD from lo00 to 10,OOO mg/L).
Backman et al. [27] started up anaerobic filters by initially seeding the reactors and adding
sodium bicarbonate into the feed influent (dairy wastewater). Both alkalinity and COD con-
centrations were 10oO mg/L. They reported that there were operational failures duringthe first
month that were due to the increased productionof volatile acids (1215 mg/L) and consequently
low pH values (5.6) found in the effluent. Because of these problems, the removal efficiency
fluctuated between 12.5 and 92.0%.
To some extent the problems encountered duringthe start-up operation can be minimized
by carefully monitoring influent and effluent characteristics. The microorganism populations in
the reactor should be stabilized until the steady state is achieved. For instance, Landine et al.
[28] started up a downflow stationary fixed-film reactor treating dairy wastewater with only
20% raw waste. The strength was gradually increased to its full concentration (100%) over a
period of10 weeks, during which period no operational difficulty was reported. Hall and
Adams [29] and Wilson and Murphy[l81 started up their dairy waste reactorsin a manner sim-
ilar to the procedure describedby Landine et al. [28]. They did not report any difficulty during
the start-up period of 240 days.
Various investigators treated different types of dairy wastes such as milk waste, whey
waste, and synthetic milk waste of varying strengths using fixed-film reactors. The COD re-
moval efficiencies of these filters have generally ranged from50% to 98%. These studieswere
conductedwithrespect to differentorganicloading rates and differenthydraulicretention
times. Rittmanet al. [30] reported that the efficiency of the filter dropped drastically from over
80% to less than 30% when the hydraulic retention time was changed to 1 day from 3 days
while treating milk waste (synthetic waste anddairy wastewater) with a strength of 3900 mg/L
COD. De Haast et al. [31] studied the effect ofC/N ratio while treating the diluted cheese whey
waste and concluded that a value muchin excess of 20 would lead toreactor failure,due to poor
buffering. Samson et al. [26] examined the effect of recirculation while treating the dairy
wastewater. Nieuwenhof [32] demonstrated that dairy wastewater could be treated effectively
by means of a two-stage anaerobic process. Cordoba et al. [33] were able to treat whey waste
efficiently in a horizontal flow anaerobic filter.
A laboratory investigation was carried out to evaluate and compare the performances of
three plastic medium upflow anaerobic filters operating at 12.5"C7 21"C, and 30°C treating
dairy wastewaters [34].' b o of the reactors were started at 21°C and the third at 30°C. Steady-
state operation was carried out at three different temperatures: 12.5"C7 21"C, and 30°C. Each
reactor was operated sequentially at different hydraulic retention times (HRTs) of 6, 4, 3,
and 1 day. The difference in start-up performance (COD removal) between anaerobic filters
operating at 21°C and 30°C was not substantial. At an HRT of 4 days, COD removals in the
three anaerobic filters were approximately 92%, 85%, and 78% at 30"C, 21"C, and 12.5"C7
respectively.
IV. LAND APPLICATION

Land application of dairy wastewater is extensively covered in a publication of the U.S. EPA
[8] and by Marshall and Harper [5]. Environment Canada [35] presented details of the use of
land applicationby four milk processing plants and one cheese plant. Performance data on these
land treatment systems are not available, however.
712 Viraraghuvan
V. CONCLUSIONS
Substantial cost savings canbe realized through good management practices suchas reducing
water use and minimizing raw material and product loss. Such a management strategy will re-
duce capital and operating costs for treatment systems.
Dairy wastewaters contain soluble organic matter and are therefore amenableto biological
treatment. Although aerobic biological treatment systems have been popular in thepast, there
is a growing interest in the design and operation of alternative anaerobic systems, especially
with their capacityto produce biogas. Land treatment of dairy wastewaters, where land is avail-
able, will be advantageous from an economic and environmental perspective.
REFERENCES
1. Hemmings, M. L., The treatment of dairy wastes, Dairy Ind. Int., 45( l l ) , 23-28 (1980).
2. New Zealand Dairy Board, Annual Report for Year Ended 3 1 May 1982, New Zealand Dairy Board,
Wellington, New Zealand, 1982.
3. Environment Canada, Evaluation of Physical-Chemical Technologies for Water Reuse, Byproduct
Recovery and Wastewater Tmatment in the Food Processing Industry, Rep. No. EPS 3-WP-79-3,
Ottawa, Canada, 1979.
4. Harper, W. J., and Blaisdell, J. L., State of the art dairy plant wastes and waste treatment, Second
Natl.Symp.on Food ProcessingWastes,U.S.EnvironmentalProtectionAgency,Washington,
D.C., 1971.
5 . Marshall, K. R., and Harper, W. J., The treatmentof wastes from the dairy industry, inIndustrial
Wastewater Treatment,Vol. 1 (D. Barnes, C. F. Forster, and S. E. Hrudey, eds.), Pitman, London,
1984, pp. 296-376.
6. Choi, E., and Burkhead, C. E., Anaerobic treatment of dairy wastes using fixed-film and without-
media reactors, Doc. 39th Industrial Waste Conference,Purdue Univ., West Lafayette, Ind.,1984,
pp. 223-233.
7. Brown, G. J., Landine, R. C., Steeves, A. L., Bough, W. A., Clark-Thomas, D. L., Burk, E., and
Eckert, R., Anaerobic treatment of dairy wastewater, 58th Annual Conference, Water Pollution
Control Federation, Kansas City, MO., 1985.
8. U.S. EPA, Dairy Food Plant Wastes and Waste 'lhatment Practices, Rep.12060 EGU 03/71, U.S.
Environmental Protection Agency, Washington, D.C., 1971.
9. U.S. EPA, DevelopmentDocumentfor EffluentLimitationsGuidelinesforNewSourcePerfor-
mance Standards for Dairy Products Processing-hint Source Category, U.S. Environmental Pro-
tection Agency, Washington, D.C., 1974.
10. Harper, W. J., Delaney, R. A. M., Igbeka, I. A., Parkin, M. E. Schiffermiller, W. E., Ross, T. E.,
and Williams, R. A., Strategies for Water and Waste Reduction in Dairy Food Plants. Rep. No.
EPA/600/S2-85/076, U.S. Environmental Protection Agency, Cincinnati, Ohio, 1985.
11. Nemerow. N. L.,and Dasgupta, A.,Industrial and Hazardous Waste Treatment,Van Nostrand Re-
inhold, New York, 1991.
12. Guo, F? H.M.,Fowlie, F? J. A., Cairns, V.W.,and Jank, B. E., Performance Evaluation of an
Extended Aeration Activated Sludge b e s s Treating Dairy Wastewaters, Rep. No. EPS 4-WP-
79-8, Environment Canada, Ottawa, Canada, 1979.
13. Guo, F? H. M., Fowlie, F? J. A., Cairns, V.W.,and Jank, B. E., Performance Evaluation of an
Oxidation Ditch Treating Dairy Wastewater, Rep. No. EPS4-WP-79-7, Environment Canada, Ot-
tawa, Canada, 1979.
14. Environment Canada, Biological Treatment of Food Processing Wastewater-Design and Opera-
tions Manual, Rep. No. EPS 3-WP-79-7, Ottawa, Canada, 1979.
15. Goronszy, M. C., and White, J., Activated sludge treatmentof high COD food processing wastes,
1988 Food Processing Waste Conference, Georgia Instituteof Technology, Atlanta, Ga., 1988.
16. Schulte, S. R., SBR technology for dairy wastewater, 1988 Food Processing Waste Conference,
Georgia Inst. Technol., Atlanta, Ga., 1988.
Pollution Control in the Dairy Industry 713
17. Maaskant, W., and Zeevalkink,J. A., First full-scale anaerobic treatment plant for dairy wastewater
in the world, Proc. Eur. Symp. Anaerobic Wastewater Treatment, Noordwijkerhout, Netherlands,
1983, pp. 442-446.
18. Wilson, R. W., and Murphy, K. L., Full-scale anaerobic treatment of dairy effluent, Proc. Seminar
on Anaerobic Fired Film Digestion, Pollution Control Association of Ontario, Toronto, 1986, pp.
201-220.
19. Environment Canada, Anaerobic Treatmentof Dairy Effluent, Rep. No. EPS 3/FP/1, Ottawa, Can-
ada, 1986.
20. Environment Canada, Anaerobic Technology: A Review of Research, Development and Demon-
stration Activity in the Agrifood and Pulp and Paper Industries, Rep. No. EPS 4/AN/1, Ottawa,
Canada, 1988.
21. Switzenbaum, M. S., Anaerobic expandedbed treatment of wastewater Proc. Workshop-Anaero-
bic Filters: An Energy Plusfor Wastewater Treatment,Argonne, Ill., 1980, pp. 115-128.
22. Vandamme, K., and Waes, G . , Purification of dairy wastewater in a two stage treatment plant,
including anaerobic pretreatment,Milchwissenschft, 35( 1 l), 663-666 (1980).
23. Sutton, I? M., Active biomass retention: the key to anaerobic process efficiency,Proc. Seminar on
Anaerobic Fired-Film Digestion, Toronto, Ont.. 1986, pp. 55-64.
24. Zaal, R., Anaerobic treatment of some dairy wastewaters,Proc. Eur. Symp. Anaerobic Wastewater
Treatment, Noordwijkerbout, Netherlands, 1983, pp. 464-465.
25. Henze, M., and Harremoes, l? Anaerobic treatment of wastewaters in fixed film reactors-a liter-
ature review, Water Sci. Technol., 15(8/9), 1-102 (1983).
26. Samson, R., Peters, R., Hade,C.,andvandenBerg, B., Dairywastewatertreatmentusing
industrial-scale fixed-film and upflow sludge bed anaerobic digesters: design and start-up experi-
ence, Proc. 39thIndustrialWasteConference, PurdueUniversity,WestLafayette,Ind., 1984,
pp. 235-241.
27. Backrnan, R. C., Blanc, F. C., and O’Shaughnessy, J. C., The treatment of dairy wastewater by
anaerobic upflow packed bed reactor,Proc. 40th Industrial Waste Conference,Purdue Univ., West
Lafayette, Ind., 1985, pp. 361-372.
28. Landine, R. C., Cocci, A. A., Brown, G . J., Pyke, S. R., and Steeves, A. L., Experiences with
anaerobic treatment using fixed film processes, Proc. Seminar on Anaerobic Fired-FilmDigestion,
Pollution Control Association of Ontario, Toronto, 1986, pp. 141-190.
29. Hall, E. R., and Adams, G. P, Anaerobic treatment of cheese whey, Proc. Seminar on Anaerobic
Fixed-Film Digestion, Pollution Control Association of Ontario, Toronto, 1986, pp. 65-80.
30. Rittman, B. E., Strubler, C. E., and Ruzicka, T., Kinetics of anaerobic filter pretreatment of dairy
wastewater at ambient temperatures, Proc. Natl. Con$ Environmental Engineering, Environmental
Engineering Division, ASCE. New York, 1981, pp. 332-339.
31. De Haast, J., Britz. T. J., Novello, J. C., and Vervwey, E. W., Anaerobic digestion of deproteinated
cheese whey, J. Dairy Res. (GB),52, 457-467 (1985).
32. Nieuwenhof, F. F. J., Anaerobic treatmentof dairy wastewater, Proc. Eur. Symp. Anaerobic Waste-
water Treatment, Noordwijkerhout, Netherlands, 1983, p. 172.
33. Cordoba, I? R., Riera, F. S., and Sineriz, F., Treatment of dairy industry wastewater with an anaer-
obic filter, Biotechnol. Lett., 6(11). 753-758 (1984).
34. Viraraghavan. T., and Kikkeri, S. R., Dairy wastewater treatment using anaerobic filters, Can. Ag-
ric. Eng., 33(2) 143-149 (1991).
35. Environment Canada, Land Application of Food Processing Wastewater, Rep. No. 3-WP-78-5,
EPS
Ottawa, Canada, 1978.
36
Landfill Gas Collection and
Destruction Systems: Evaluating Toxic
Emissions and Potential Health Risk
Karnig Ohannessian, Anna Peteranecz, and Thomas Kear

OP&L, Inc.
San Diego, California
1. INTRODUCTION
Concerns in the UnitedStates over limited landfill space have until recently overshadowed the
potential health effects from exposure to landfill gas that is emitted into the air from municipal
solid waste landfills.
The constituents of landfillgas vary. Generally, landfill gas consists of 40-75% methane
(CH,) by volume and25-65% carbon dioxide(CO,) by volume; a safe assumption is 50% CH4
and 50% CO,.In addition, landfill gas contains traces of non-methane organic compounds
(NMOCs),includingaircontaminantsthataretoxic.The U.S. EnvironmentalProtection
Agency (EPA) has based its standards and guidelines for the control of landfill gas on emissions
of NMOCs.
The control of landfillgas would reduce the adverse health effects NMOCs
of that are toxic
or carcinogenic. Another benefitwould be the reduction of methane emissions. Methanesus- is
pected to be a greenhouse gas. Also, landfill gas has been known to migrate under buildings
near landfills, where the methane has caused explosionsand fires.
Individual states often require that landfill
gas control systems not only meet EPA the stan-
dards and guidelines, but also be shownto have insignificant potential health risks. A conve-
nient tool (one that is sometimes required by regulatory agencies fornew or modified sites)for
evaluating health effects is a health risk assessment (HRA).
A health risk assessment is a quantitative analysis of the dispersion of airborne toxins, a
determination of the potential exposure of the public to these contaminants, and the assessment
of the health risks that may result because of this exposure. An excellentofsetHRA guidelines
has been published by the California Air Pollution Control Officers Association (CAPCOA) for
use by facilities as a way of determining the potential risk they poseto the surrounding com-
munity [l]. The EPA also has HRA guidelines that are in many ways less stringent than the
CAPCOA guidelines.
715
716 Ohannessian et al.
The processes, site descriptions, and assumptions found in this chapter have been taken
from work that we have done for numerous landfills. The cases presented are composites of
several sites, and process conditions suchas equipment design parameters, chemicals present,
and the risk and ambientconcentrations of these chemicalshave been changed to ensure client
confidentiality. However, the processes described are representative of the industry. The land-
fills are located in California, a trendsetter in environmental regulations. Therefore, the toxic
emissions evaluations and risk assessments are performed to take into accountthe requirements
of the California Solid Waste Management Board, the California Department of Health Ser-
vices, and local air pollution control districts.
II. LANDFILLGASGENERATION
The rate at which landfill gas is generated depends on a variety of factors that determine the
rate at which the refuse in the landfill breaks down. Thesesite-specificfactors include moisture
content, temperature, waste composition, and acidity. Gas generation occurs over long periods
of time, sometimes lasting up to 50 years.
The EPA has published a landfill gas emissions estimation model that is available on com-
puter disks [2]. The model can predict gas generation rates based on site characteristics. Con-
servative default valuesfor estimating emission rates are provided for cases where site data are
not available. Site information includes the landfilling history, refhe acceptance rate, design
capacity, NMOC concentration, methane generationrate constant (based ona first-order decay
equation), and methane generation potential. Individual air toxics concentrations can also be
used as input. The model calculates emission rates for methane, carbondioxide, and NMOCs,
as well as for individual toxic air components.
Obtaining site-specific NMOC concentration9 and landfill gas generation rates requires
testing that is often expensive.For this reason landfill operators base their initial emission rate
estimates on the conservative default values. Emissionrate estimates are important becausethe
EPA and state standards requirethe installation of costly landfillgas control equipmentfor sites
exceeding established NMOC emission rates. If the default values yield high NMOC emission
rates, the operator can then decide whether actual testing would be warranted.
The California Air Resources Board (CARB) has documented two methods of estimating
average landfill gasgeneration rates over a 70-year period. One method, developed in 1982 by
the South Coast Air Quality Management District (SCAQMD), suggests that methaneis pro-
duced at a rate of 972 tondyear per million tons of in-place refuse [3]. The second method,
recommended for work done tosatisfy the requirements of California’s AirToxics “Hot Spots”
Program (Assembly Bill2588). suggests that methane is producedat a rate of 3000 ft3 per ton
of refuse over a 70-year period [4,5]. CARB assumes that landfill gas consists of 50% by vol-
ume carbon dioxide and50% by volume methane forthe purpose of calculating emission rates;
this assumption partially accounts for the variations in evolution rate observed in the landfill
gas with respectto time [4]. Thus, on average, landfill gas is generated at twice the volumetric
rate at which methane is generated.
Both California methods assume a constant landfill gas generation rate over a 70-year pe-
riod (average human lifespan). This time period doesnot necessarily reflect the actual period
of landfill gas generation.The 70-year periodhas been adoptedby California as a conservative
estimate of exposure based on the average human life span.
The air emissions estimates, coupled with unit cancer risk factors for carcinogenic chem-
icals published in risk assessment guidelines, can be used to conservatively estimate the in-
creased likelihoodthat an individualmay develop cancer over the course of a 70-year exposure
period [l]. In reality, the generation rate of landfill gas will initially be much greater than the
Landfill Gas Collection and Destruction 717
Table 1 Landfill Gas EmissionRateAssumptions

Emission rate
Assumption (Ib landfill gadyear)
A. 3000 ft3 of methane

per
ton per 70 years
of refuse (CARB) 6.7 X lo6
B. 972 tons of methane per million tons of refuse
per
year
(CARB) 7.3 x IO6
C. 370 ft3/min
million
tons
per of refuse (BAAQMD) 15.2 X lo6
estimated rate, but eventually it will taper off. Landfill gas generation reaches its peak rate
during or just after landfill closure. Therefore, a decade after landfill closure,would
one expect
to see gas generation rates that are lower than those estimated by either of these California
techniques [3,5]. For this reason, calculated health risks using these estimation techniques may
not be representative of actual exposure [5]. These methodsare conservative enough, however,
to satisfy the requirements of regulatory agencies.
Another emission estimation technique that has been used by the Bay Area Air Quality
Management District (BAAQMD) assumes that 370 ft3/min of landfill gas is evolved per mil-
lion tons of refuse for 10 years [6].This is a much higher estimated rate of production over a
much shorter amount of time than is used in the CARB methods. Table 1 compares the landfill
gas generation rates from each of the California methods per million tons of refuse onefor
year.
Aside from the presented emission rate assumptions, actual measured landfill gas gener-
ation rates can be used for calculation of cancer risks, and chronic (long-term exposure) and
acute (short-term exposure) hazard indices, over a 70-year exposure period. Note that these
methods can be employed in a health risk assessment to calculate average acute hazard indices,
as opposed to the peak acute hazard indices thatwould result during the peak landfillgas gen-
eration period within the first few years after landfill closure.
111. LANDFILL GAS COLLECTION SYSTEMS

Landfill gas collection systems comprise verticalor horizontal gas extraction wellsor trenches
that are connected to header pipes, and gas moving equipment such as blowers or compressors.
This type of system is called an active collection system, because the gas is extracted from the
landfill by creating a pressure gradient. Thereare also passive collection systems that channel
the generated landfill gas to control devices without pumping. The EPA suggests that active
vertical collection systems can best meet its emission standards and guidelines [7].
Vertical extraction wells are normally placed in areas of a landfill that are no longer ac-
cepting waste. The wells are spaced according to the vacuum generated such that gas is col-
lected from every part of the landfill.An effective collection system shouldbe able to handle
the maximum predicted landfill gas generation rate. The wellhead is connected to the header
pipes,whichsometimesareburiedunderthetopsoilcover.Eachwellheadassemblyis
equipped with valvesso that the flow through each well can be regulated and gas samples can
be taken. The operator must guard againsttoo large a pressure gradient that would cause large
amounts of air to penetrate into the landfill.An excess of air in the landfill has been linked to
underground fires.
Wells are often made of polyvinyl chloride (PVC) or high-density polyethylene (HDPE)
pipe about4 in. in diameter.The EPA requires that wells descend to a minimum75% of of the
landfill depth [7].The bottom two-thirds of the pipe is perforated with slots. The pipe is sur-
rounded by a 2-ft bore, which is backfilled with gravelup to 1 ft above the perforations, then
with bentonite, concrete, and top cover soil [7].
Blowers or compressors conveythe gas through the header piping. The gas is directed to
a knockout drumto remove water, and sometimes atoscrubber to remove particulates. The gas
then flows to the control equipment. Compressors causethe moisture to condense more easily
because of the higher gas pressures, but they are more costly than blowers.
Collection efficiencies generally range from 40 to 6095, with some systems having effi-
ciencies as high as 90% [3]. Covering closed landfills with plastic lining material and com-
pacted soil (e.g., clay) results in greater gas collection rates. Also, a liner system installed
during landfilling to seal the bottom would control gas migration. In the toxics emission eval-
uation presented in Section V it is assumed that the efficiency of the landfill gas collection
system to be installed at the hypothetical landfills inquestion would be 60%.
Because of the difficulties in estimating the actual landfill gas generation rates and other
factors that influence the emission rate of landfill gas (e.g., temperature, type of refuse, fluc-
tuations in groundwater depth), the actual efficiencyof any landfill gas collection system may
differ from the design efficiency of the system. If the design efficiency is not reached in the
landfill gas collection system, the health risks associated with the landfill will be higher than
those calculated, because a smaller amount of gas will reach the control devices.
IV. LANDFILL GAS TREATMENT SYSTEMS

A.Energy-RecoveringTreatment Systems
Landfill gas is usually burned. There are cases where the gas is purified by removing the car-
bon dioxide, NMOCs, and water and is then sold as a product gas with a heating valueof about
lo00 Btu/ft3. Carbon dioxide is removedwith gels, activated carbon, molecular sieves, or
membranes [8]. In recent years this process has become too expensive, and most landfills now
simply bum the collected gas.
Four common devices used for combustion of collected landfill gas are flares, internal
combustion (IC) engines, gas turbines, and boilers. IC engines, turbines, and boilers are used
to recoverenergyfrom the combustionprocess.However,whentheseenergy-recovering
devices are used as the primary destruction devices, flares are also employed as a backup
for periods during downtime or maintenance. If there is a market for the energy generated,
then energy-recovering devices may be economically more attractive and viable alternatives
than flares.
B. Flares
Flares are increasingly becomingthe only control devices installed, because they have higher
destruction efficiencies, can operate at wider gas flow ranges, and are easier to operate and
maintain than other devices. The current trend is toward enclosed flares (EPA recommends
either open or enclosed flares [7]).
Enclosed flares have burners at ground level that are enclosed by a shell that acts as a
stack. This simplifies the gas sampling and source testing procedure.The flares are equipped
with flame arresters, temperaturesensors,and other controlinstrumentation. The pilot
flame burns either natural gas or propane. Exhaust gas temperatures range from 1200 to
1700"F, with a typical value of 1400°F. The destruction efficiency is required by regulatory
agencies to be greater than 98% for NMOCs; destruction efficiencies regularly reach levels
above 99%.
Higher temperatures resultin higher destructionefficiencies but also result in higher emis-
sion rates of nitrogen oxides (NO,) and carbon monoxide (CO). In California, the NO, emis-
sion limit is 0.06 lb per million Btu heat input, and CO emission limit is 0.30 lb per million
Table 2 Enthalpies of Combustion Product Gases

-mol)]
EnthalpyChemical
19,138
14,832
12,092
12,805
Btu. Many regulatory agencies also have established emission limitsfor PM,,, or particulates
with diameters less than or equal to 10 pm.
The combustion of landfill gas in flares requires a supply of forced excess air to assure
complete oxidation. The following is a quick and rough procedure for estimating the air re-
quirements. The air requirement information can be used to size the flare.
Assume that 1400 standard cubic feet per minute (scfm)of landfill gas is to be burned at
1700°F.The inlet gas is at 70°F and consistsof 50% CH, and 50% CO2. The gas has a heating
value of 460 BNft3 [assume a molar volume of 379 ft3/(lb-mol)]. The combustion reactionfor
1 mol of gas is
0.5 C& +
0.5 C02 + +
X(02 3.76 N2) "*
C02 + H20 +
(X - 1)02 +
(X) (3.76)N2
where X - 1 is the excess amount of air required.
The heat released is
(460Btulft?) [379 f 9 / (lb-mol)] (1 Ib-mol) = 174,340Btu (2)
The enthalpies of the product gases at 1700°F are shown in Table 2. The heat balance (as-
suming that 20% of the heat is lost by radiation) is
0.8 (174,340)= 19,138 + 14,832 + (X - 1) (12,805)+ (X) (3.76) (12,092) (3)
The solution gives
X = 2.03, X -(4)1 = 1.03
Therefore, 100% excess air is neededin the flare. The balancedchemical equation
becomes
0.5 C& + 0.5 C02 + (2)(02+ 3.76 NZ)"*
C02 + H 2 0 + 0 2 + (2)(3.76)N2
The exhaust flow rate is
(1400scfm) [l + 1 + 1 + (2)(3.76)] = 14,728 scfm (6)
The excess air also serves to maintain the exhaust gasesat the desired temperature. With-
out the excess gas, the temperature rise would be
1700 - 70
= 0.0205"F/Btu
19,138 + 14,832 + 3.76(12,092)
and the exhaust gas temperature rise would be
(0.0205)
(0.8)(174,340) = 2860°F (8)
V. LANDFILL GASEMISSIONS
A. Emissions of Non-Methane Organic Compounds
At the hypothetical subjectsite presented in this chapter, landfill gas is collected and is routed
to an enclosed flare. The flare oxidizes any toxic compounds present into less harmful com-
pounds(ideally,carbondioxideandwater).Becauselandfillgas after combustionhas a
significantly lower health risk than unburned gas, the choice of the landfill gas collection sys-
tem efficiency has a large effect on the final estimate of the health risks in the vicinity of the
landfill.
Emission factors of individual chemicals inthe toxics evaluationare based on source tests
for landfill gas from actual landfills. Flares are assumed to have a destruction efficiency of
99.8%for the toxic constituents based upon the same source tests. This destruction efficiency
is higher than the 98% NMOC destruction efficiency required by the EPA. There is no de-
struction of the NMOCs being emitted fromthe landfill surface. It is also assumed that metals
present in the landfill gas are not reduced by the flares. It is believed that combustionof landfill
gases may actually add metals into the exhaust [lo].
Three different kindsof data are available to quantify the presence of toxic constituents in
landfill gas:
1 . Emission factors from local regulatory agencies based on submitted reports

2. Source test results of inlet landfill gas and exhaust gases
3. AirSolid Waste Assessment Test (Air-SWAT) reports for compounds assessed at landfills
in California
The data from these sources are shown in Table 3.

Dioxins and furans will notbe formed in the flares. Recent research indicatesthat dioxins
and furans are destroyed at flame temperatures exceeding 1380°F [9].
Occasionally, data from the regulatory agencies indicate that several metalsthat should not
be present in the landfill gas are present in the exhaust gases. Examples are cadmium, man-
ganese, nickel, and zinc. It is believed that these metals result from corrosion. Such effects
have been documented in other equipment such as IC engines located on landfills andare be-
lieved to be caused by high levels of chlorine, in the form of chlorinated hydrocarbons, in the
landfill gas. Combustion of these halocarbons resultsin decomposition into hydrogenchloride
and carbon dioxide withinthe IC engines. The acid then attacks engine componentsand creates
a source of metal release and contamination of the exhaust stream [lo].
Most of the compounds that were detected in the data from the regulatory agencies, the
source test data, and the Air-SWAT data had different concentrations in each data set. One
reason for the variations is that landfill gas, even gas from different regions of the same land-
fill, will vary greatly in composition.
B. Emission Rates of Exhaust Gases

Since the actual landfill gas flow rate varies over time, the California method of 3000 ft3 of
methane produced per ton of refuse per 70 years is used to estimate the gas flow rate. This
model accountsfor human exposure to the toxic pollutants over a lifetime, which corresponds
with the assumptions made in the health risk assessment methods.
Assuming a landfill capacity of 20 million yd3 and a refuse density of 1200 lb/yd3, the
result is 12 million tons in place at landfill closure. This amount yields an average landfillgas
flow rate of 2000 scfm.
Table 3 Non-Methane Organic Compounds in Landfill Gas"

RegulatorySubstance
Acetaldehyde ND D -
Benzene -
Carbon ND
Chlorobenzene ND -
Chloroform ND -
1,l-Dichloroethane -
1,1-Dichloroethylene -
1 -
Ethylene ND -
Formaldehyde -
Hydrogen -
Hydrogen ND -
Hydrogen D -
Methyl
Methylene
Perchloroethylene
PAHs)
hydrocarbons
aromatic
Polycyclic - -
Styrene -
Toluene -
Trichloroethylene
Vinyl -
Xylene D -
Zinc D -
Acrolein ND ND -
Chromium(VI) ND ND -
Lead ND ND -
Mercury -
Selenium ND -
Phenol ND - -
Vinylidene chloride D ND -
'D denotes compounds that were detected. ND denotes compounds with concentrations at or below the detection
limit. Blank entries (-) denote compounds that were not tested.
For design purposes it mustbe assumed that theflare can handle allof the landfill gas that
is generated. If the flare operates at 1400°F and 100% excess air is used, then the exhaust flow
rate is 75,260 cfm. Assuming an exhaust velocity of25 Wsec, the flare will have a diameter of
8 ft. For air dispersion modeling purposes, the flare is assumed to be 40 ft tall.
If the heating value of the gas is assumed tobe 520 BNft3, then the flare will be rated at
62 million Btu/hr. California NO, and CO emission limitsof 0.06 and 0.30 lb per million Btu
heat input, respectively, are used. An industry-wide emission limit of 40 lb/106 ft3 for total
suspended solids, of which 50% is PM,,, is also used.
To estimate emissions of toxic chemicals, it is assumed that60% of the total landfill gas
generated is collected and directed to theflare, and 40% is emitted from the landfill surface.
Toxics emissionrates from the flare are calculatedby multiplying the landfill gas inletrate by
the chemical concentration and the destruction efficiency. For emissions from the landfill sur-
face, the destruction efficiency is not applied. These emissionrates are used in the evaluation
of health effects.
VI. MODELINGMETHODOLOGY
A. AirDispersionModeling
For air dispersion modeling purposes, the enclosed flare is treated as a point source (stack), and
the landfill surface is treated as an area source. Commonly usedair dispersion models are the
EPA’s IndustrialSourceComplex, Short Term(ISCST)andSCREENmodels[11,12].
SCREEN, which is referred to as a “screening” model, is easy to run. ISCST is a refined
model that is much more difficult to run, requires many more site-specific parameters, and
yields more representative values than SCREEN.
The modeling is done using an emission rate of 1 @sec, facilitating scaling of the predicted
relative concentrationsto compound-specific concentrations.The equation that is used forseal-
ing of relative groundlevel concentrations, obtainedfromdispersionmodeling runs, to
compound-specific concentrations based on actual emission rates is [l11
(xu/Qu)Qo = X, (9)
where X J Q , is the relative or unit concentration, (pg/m3)/(g/sec);Q, is the compound-specific
actual emission rate, g/sec; and X , is the compound-specific actualconcentration, pg/m3.
UnlikeISCST,SCREENdoesnottakeactualmeteorological conditions intoaccount.
SCREEN calculates the maximum hourly concentration using worst-case meteorological con-
ditions. Actual concentrations would be much lower than these hypothetical concentrations.
B. PointSources
Flare emissions are modeled with the SCREEN model at a 1 @sec emission rate. SCREEN
does have a flare emission release type that requests specific emission parametersas input, but
this release type applies to open flares. For exhausts from enclosed flares (flame at ground
level), it is more appropriate to input the point source (stack) parameters. SCREEN calculates
the maximum relative concentrations of pollutants from the flare.
Using Equation(9), the emission rates for each chemicalin the flare exhaust are multiplied
by the relative concentration to yield the maximum predicted ambientconcentrations for each
substance.
C.AreaSources
Area sourcesare the best representation for fugitive releases froma landfill surface. One char-
acteristic of an area source (with sides of length L) is that estimated concentrations are inac-
curate withindistances of lessthan L to the areasourceitself. In addition, the EPA
recommends using area sources withside lengths of between 50 and 150 m. Therefore, if 100
m by 100 m area sources were used, 100 of these area sources would be needed to cover a
square landfill surface 1 km2. vpically ISCST, which can model multiple sources in one run,
would be used for such an application. However,the resources and time required by 100 sources
are extensive.
An estimate of the health risk associated with the fugitives can be calculated using the
SCREEN model as follows.
Find the nearest distance to the property boundary fromthe landfill surface. This point is
the nearest receptor site. SCREEN is not direction-specific in its air dispersion modeling, so
the nearest off-site receptor will usually be the point of maximum impact. If the model is run
using the regulatory defaultoptions, it will automatically findthe worst-case hypothetical me-
teorological conditions (wind speed, stability, and mixing height) for air dispersion. Although
these conditions may actually never occur at a particular site, this procedure gives the worst-
case ground level air concentrations. In the hypothetical subject site presented here, assume
that the point of maximum impact is 200 m from the midpoint of an area source with a side
length of 100 m located on the edge of the landfill.
Determine the maximum number of 100 m by 100 m area sources acrossthe surface of the
landfill that lie along a straight line tothe receptor point. Thesearea sources lie along the plume
line of the dispersed gases.In the subject landfill area of1 km2, there would be a maximum of
10 such area sources.
It is assumed that all of the emissions from the area sources are impacting the chosen re-
ceptor point throughout the entire year. This is a conservative assumption that increases the
calculated maximum ambientconcentration but drastically reduces the number of sources that
are modeled. The maximum numberof area sources that can impact this receptor witha single
wind direction throughout the year is the maximum number of area sourcesthat can be aligned
in a straight line with the impact point.SCREEN assumes onewind direction. Sources thatare
not lined up inthe single wind direction cannot affect the impact point. Forthis reason, not all
the 100 square area sources need to be modeled. In this case (modeling 10 area sources) there
is a substantial reduction fromthe number of sources thatwould have been modeled (100 area
sources) using a refined algorithm such ISCST
as that accounts for real meteorological conditions.
The number of sources modeled can befurther reduced to one, since the modeling param-
eters are the same for the identical areas. The concentrations at 10 discrete distances 100 m
apart are calculated, beginning at the nearest distance from an area source and ending at the
farthest distance. In the subject landfill, the nearest distanceis 200 m, and thefarthest distance
is 1100 m. These distances from one area source correspondto the distances from the midpoints
of the given number of aligned squares(10) to the single point of impact locatedat the nearest
distance downwind from the first area source. Therefore,this method is equivalent to separately
modeling 10 area sources, each with a single distance.
D. Calculation of Ground Level Concentrations

The predicted concentrations at each distanceare then summed to yield the cumulative impact
from all of the fugitive emissions fromthat particular landfill. Since each area source is mod-
eled as emitting 1@sec, the cumulative concentration is divided by the number of sources to
yield the relative concentration. This is the unit concentration based ona 1 @sec emissionrate
from the fugitive sources. Equation (9) is used with chemical emission rates from the landfill
surface to calculate substance-specific concentrations.
All of the emissions calculatedfor the total landfill surfaceare assumed to be emitted from
the modeled area sources. Again, this is a conservative assumption that supposes that allof the
emissions impact a single point. These emissions rates are multiplied by the relative concen-
tration to yield calculated maximum concentrations.
A less conservative approach would be to assume that the emission rate from each area
source is 1/N of the total emissions from the landfill surface, whereN is the total number ofarea
sources that lie on the landfill.
SCREEN calculates maximumhourlyconcentrations.Factors are available to convert
these values to annual average concentrations. Annual averageconcentrations are used for the
health risk assessment calculations regarding long-term health effects. Maximum hourly con-
centrations are used for short-term health effects.
VII.DEVELOPINGHEALTH RISK EVALUATIONS

There are eight primary steps necessary to quantify the health risks associated with landfiil
gas emissions:
1. Determination of the landfill gas generation rate

2. Determination of the efficiency of the landfill gas collection system
3. Determination of the compounds that are present in the landfill gas
4. Development of a dispersion modeling scenario and emission rates
5 . Completion of dispersionmodeling
6. Scaling of the dispersion model results for specific compounds
7. Application of unit risk values
8. Summation of the risks for the maximum exposed individual
The EPA and individual regulatory agencies have developed extensive guidance for the
quantification of health impacts, from ambient concentrations of a wide rangeof air toxics [l].
California methodologiesare based on dose-response curves developed by the EPA, the Cali-
fornia Air Resources Board, and the California Department of Health Services. Three surro-
gates for potential health risk are used: cancer risk, chronic hazard indices, and acute hazard
indices.
Cancer risk is calculated by multiplying the annual averageconcentration of a compound
by a compound-specific unit risk factor. Unit risk factors are available from regulatory agen-
cies. Cancerrisk is a conservative estimate of the likelihood that an individual whois exposed
to the emissions in question for 70 continuous years will contract cancer as a result of this
exposure.
Chronic hazard indices are a measure of the likelihood that an individual who is exposed
to the emissions in question for 70 continuous years will contract a noncancer health effectin
one of several target organdsystems as a result of inhalation of emissions. Other pathwaysof
exposure include ingestion of contaminated soil, water, food, and mother’s milk. These non-
cancer healtheffects may occur because of the toxicityof the chemicals. Chronic hazard indices
are calculated by dividing the annual average concentration of a compound by a compound-
specific acceptable chronic level of exposure. That is, a chronic hazard index is the ratio of
calculated long-term exposure to acceptable long-term exposure.
Acute hazard indices are a measure of the likelihood of an individual suffering adverse
health effects asa result of an acute exposure via emissions inhalation. Acute hazard indices are
calculated by dividing the maximumhourlyaverage concentration of a compound by a
compound-specific acceptable acute level of exposure. That is, an acute hazard index is the
ratio of calculated short-term exposure to acceptable short-term exposure.
Once all of the surrogates for the health risk are calculated, like surrogates are summed
over all of the compounds present at the point of maximum concentration. The point of max-
imum concentration is the peak off-site concentration for the fugitives and the peak receptor
from the flare.This calculation yields the maximum health risk associated with each emitting
source. It is assumed thatthe sources are placed in a manner that would cause their respective
peak concentration points tooverlap, a conservative assumptionthat is physically impossible.
The total healthrisks from the flare are added to the health risks associated with the fugitives.
This summation is a result of the assumption thatthe peak receptors from each source overlap.
VIII. RESULTS
The resulting assessment displaysa total cancer risk from all of the sources of less than 10 in
a million, the value that is generally consideredsignificant. This value represents the potential
risk of 1 excess cancercase per 100,OOO individuals. However, the exposure must take placefor
70 continuous years in order for the excess cancer burden to be representative. Values repre-
senting chronic and acute hazard indices are found to be less than 1.O, the value that is gen-
erally considered to be significant. A value under 1.O for either of these indices represents an
acceptable level of exposure for an individual.
Emissions of the EPA criteria pollutants, NO,, CO, and PM,,, are found to be lower than
the rates acceptable by the regulatory agencies.
Although 60% of the gas is assumed to be collected and diverted to the flare, the risk
associated with flare emissions is orders of magnitude lower thanthe risk from landfill surface
emissions.This is a resultof the destruction of the toxicchemicals in the flare during
combustion. Therefore, higher landfill gas collection efficiencies result in lower associated
health risks.
1. CAPCOA, Air Toxics “Hot Spots” Program, Risk Assessment Guidelines,California Air Pollution
Control Officers Association. January 1991.
2. EPA, Landfill Air Emissions Estimation Model Version I .I . User’sManual, PB9 -11677 18, prepared
by Radian Corp., Research Triangle Park, N.C., April 1991.
3. CAPCOA, Suggested Control Measure for Landfill Gas Emissions, California Air Pollution Control
Officers Association, August 1990.
4. CARB, AB 2588 Landfill Gas Emission Rate Estimation Technique (letter toAir Pollution Control
Officers of various Districts), April 1990.
5. CARB, The Landfill Testing Program: Data Analysis and Evaluation Guidelines,California Air Re-
sources Board, August 1990.
6. BAAQMD, Suggested Generation Rate and Unit Risk Factors for Landfill Gas Emissions (letter
from Laura Harnish of CH2MHillto Steve Hill of the Bay Area Air Quality Management District),
January 1990.
7. EPA, Air Emissionsfrom Municipal Solid Waste Landfills-Background Information for Proposed
Standards and Emission Guidelines, EPA-450/3-90-01l(a), Research Triangle Park, N.C., 1991.
8. Christensen, T. H., Cossu, R., and Stegmann,R. (eds.), Sanitary Landfilling:Process, Technology
and Environmental Impact, Academic, San Diego, Calif., 1989.
9. Wong, T. S., Dioxin formation and destruction in combustion processes, 77th Annual Meeting of
the Air Pollution Control Association, June 1984.
10. Dernbach, H., Corrosion of gas engines at landfill gas utilization plants caused by chlorohydrocar-
bons, Recycling International, 1989.
11. Wagner, C., Industrial Source Complex Dispersion ModelUser’s Guide, 2nd ed. rev., Vol. 1, EPA-
450/4-88-002a, U.S. EPA, Washington, D.C., 1987.
12. Brode, R., Screening Proceduresfor Estimating the Air Quality Impact of Stationary Sources, EPA-
45014-88410, U.S. EPA, Washington, D.C., 1988.
Index
Activated sludge treatment, 500-504 Cementitious materials, 442, 445, 447

Aerobic digestion, 509, 709-710 CERCLA, 119, 644
AHP (analytic hierarchy process), 42 Chelates, metal silicate, 444
Air dispersion modeling, 722 Chlorination, 536
Alternate point of compliance (APC), Chlorine, 475, 536
119-142 Chromate, 535, 554
Amalgam, 561 reduction, 538, 540
Ammonia stripping, 508 Cleanup level, 87
Anaerobic digestion, 509, 710-711 Clean Water Act, 535
Aquifer parameters, 581 Confining zone, 354
Arsenic contamination, 454 Cost analysis, 20-21, 28-44, 397
Ash, 476-478 Creosote, 89, 94
Cyanide, 535-537, 554
Baseline risk assesment, 87 Cyanogen chloride, 536
Bayesian approach, 576-577
Biodegradation, 276, 405 Dairy
BOD (biochemical oxygen demand),491- wastes, 705
493,497,499-506,509 wastewater treatment,709-7 11
Decision theory, 30-44
Calcium oxide, 559 Denitrification, 507
Cancer, 724 Department of Defense, 17
Carbonation, 315-318, 321, 322, 327-328 Destruction efficiency, 720
Carbon dioxide, 715 Deterministic management model, 572-573
Casing, 311-320, 322, 329, 330 Deterministic simulation, 105-1 18
Caustic soda, 559, 561-563 Dewatering, 322, 329, 510
Cavern closure, 35 1-352 Diaphragm cell, 561
Cement-based techniques, 272-273 Dioxins, 384
727
728 Index
Dispersion, 461, 464 Hydrocarbons

DO (dissolved oxygen), 490 petroleum, 405
polycyclic aromatic (cPAHs), 88-94
Electrode Hydrochloric acid, 474
calomel, 544 Hydrogen peroxide, 390
glass, 558
reference, 558 Incineration, 510
saturated silver, 545 Injection
Electrolytic oxidation, 537 interval, 354
Electrowinning, 312, 318-19, 324, 326, zone, 354
328,330 Intrinsic properties, 19
Environmental Protection Agency, 17,20
Equilibrium temperature, 515 Kinetics, 385
Exposure pathways, 724 Land application, 711
Extraction prccedures, 446, 453, 464 Landfarming, 405
Landfill gas, 71
FBC (fluidized bed combustion), collection systems, 717
467-470
emissions, 720
FC (freeze concentration), 513 generation, 716
Feasibility analysis, 660 treatment systems, 718
Feed pumps, 545, 548 Leachability, 276, 290-291
Filters, trickling, 497-500 Lead, 31 1-330
Flares, 718 Legal requirements, 639
Flow rates, 389, 552 Life cycle, 20
Fluosilicic acid, 318-319, 324-325 Light intensity, 385
Fly ash, 271 Lime, 559-561
Freeze-thaw, 290
Material balances, 656-658
GIS (geographic information systems), 32 Membrane
Gross national product, 26 cell, 561-562
Groundwater, 569,577 systems, 516
Mercury cell, 561
Halogens, 474 Methane, 715
Hazardous materials, 18, 21-22 Military facilities, 637-642
Hazardous waste residuals, 331 Mishap probability ( M E ) , 19
Hazard severity, 19 MLSS (mixed liquor suspended solids),
Heat treatment, 510 501-504
Heavy metals, 271 Mobility index, 124
arc furnace dust, 441 Monte Carlo simulation, 105-118
auto shredder residue, 441 MSDS (material safety data sheets), 22
groups, 446, 450 Multimedia exposure assessment model
sludges, 441 (Multimed), 88, 101-118
soil, 441 Multistage systems, 520
wastewater, 535
HRA (health risk assessment), 715, National priorities list, 31, 40
723-725 Navy substitution algorithm, 21
HSWA (Hazardous and Solid Waste Neutralization, 557-566
Amendments), 644 Nitric acid, 317-318, 322
Hydraulic load, 499 Nitrificatioddenitrification,507
Indf?X 729
Nitrogen, 491-492,506-508 Ripening, 516

NMOCs, 715 Risk, 36-44,94
NO,, 473 RIS (risk information system), 43
N,O, 474 Rotating biological contractors, 504-505
Optimization, 569 Salt deposits, 332

Organics, 405 SARA (Superfund Amendments Reauthori-
concentration, 385 zation Act), 644-645
load, 499 Semiconductors, 381
organic leachate model (OLM), 88, Simulation, 32
120- 142 Site inspection, 655-656
polymer techniques, 272, 275 Sludges
ORP (oxidation-reduction potential), disposal, 511
546-547 heavy metals, 441
Oxygen concentration, 385 pulp mill, 473
residuals management, 360
Particle size distribution, 461 wastewater, 508
PCBs, 384 Soil, 311-314, 319-322, 324-330, 405
Permissible exposure limits (PEL), 18 petroleum contaminated, 280
Pesticides, 384 Solar illumination, 396
pH, 387,557-559 Solidification, 346, 349, 442
Phenols, 88, 94, 384, 395 Solution-mined repository, 332
Phosphorus, 491-492, 506-508 Solution-mining, 333
Photoexcitation, 380 Solvents, 384
PM,,, 719 Sorbent
Pollution prevention, 17, 591 techniques, 272, 275
Pollution Prevention Act of 1990, 644 utilization, 479
Polysilicate, 441, 447 Source reduction, 647
Potency factors, 89-92 Specific surface area, 388
Precipitation SS (suspended solids), 490, 492
metal hydroxide, 541, 554 Stabilization ponds, 505
metal sulfide, 542 Stochastic, 569, 574
Priority measurement, 19 Stochastic unit influence coefficient, 574
Problem avoidance, 34, 38, 42 Strategic Petroleum Reserve, 333, 340
Process changes, 648 STS technology, 4 4 1
Process performance data, 549 Substitution methods, 17
Pug mill, 447 Superfund, 94, 311, 330
Surface reactions, 382-383
Quinhydrone, 544 SVI (sludge volume index), 504
RAC (risk assessment code), 18-19 Synthetic general rinse effluent, 552
System performance, 555
RASS (resource allocation support
system), 43 Titanium dioxide, 381-383, 386
RCRA (Resource Conservation and Recov- Toxicity
ery Act), 644-645 aquatic, 593
tank, 453, 456 and cancer, 724
Records of decision (RODS), 119 effects, 22
Recycling, 638-639, 641, 650 effluent, 593
Relative ground level concentrations, 722 hazards, 22
Residuals management, 360 TQM (total quality management), 591
730 Index
Training, 641-642 Treatment units, transportable, 447, 452

Treatability studies, 445 TSS, 491, 493, 506
Treatment
activated sludge, 500-504 Unit response functions, 571-572
aerobic, 509, 709-710 Uranium, 641
anaerobic, 509, 7 10-7 1 1
caustic, 559, 561-563
chemical, 442 Vertical and horizontal spreading (VHS),
dairy wastes, 709-71 1 88, 120- 142
efficiency, 553 Viscosity, 5.15
heat, 510 Vitrification, 272, 275, 276
landfill, 7 18 VOC (volatile organic compound), 20
levels, 454, 456
metals, 444, 541-542, 554 Wartime operations, 641
on-site, 453, 454 Wash column, 518
oxidative, 537 Waste
preliminary, 493 minimization, 591
priority, 493-494, 498 reduction, 646-647
secondary, 494,497, 506 streams, 658
studies, 445 WIPP (waste isolation pilot plant), 340,
tertiary, 494, 506 35 1

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EDITED BY

Marcel Dekker, Inc. New YorkaBaselaHongKong

This book is printed on acid-free paper.

Copyright 0 1994 by Marcel Dekker, Inc. All Rights Reserved.

Marcel Dekker. Inc.

Current printing (last digit):

PRINTED IN THE UNITED STATES OF AMERICA

Selection of Least Hazardous Material Alternatives 17

Multiple Approaches to Environmental Decisions 25

Introduction to Engineering Evaluation for Contaminated Sites 47

Innovative Approaches to Cleanup Level Development 87

Designing to Prevent Pollution 145

Biochemical, Genetic, and Ecological Approaches to Solving Problems During

8 Commandments of Waste Management 193

9 A Proactive Approach to Environmental Management: Meeting

l2 Solidification and Stabilization Techniquesfor Waste Control 271

l3 Soil Remediation with Environmentally Processed Asphalt @PATM) 297

14 Lead Decontamination of Superfund Sites 311

15 A Secure Geologic Repository for Hazardous Waste Residuals 331

16 Photocatalytic Degradation of Hazardous Wastes 363

17 Photocatalytic Oxidation of Organic Contaminants 377

18 Biodegradation of Organic Pollutants in Soil 405

19 Siallon: The Microencapsulationof Hydrocarbons Withina Silica Cell 425

20 Remediation of Heavy Metal Contaminated Solids Using Polysilicates 441

21 Fluidized Bed Combustion for Waste Minimization: Emissions andAsh

23 FreezeConcentration: Its Application in HazardousWastewaterTreatment 513

24 OrganoclaySorbents for Selective Removalof OrganicsfromWater

25 Removal of Chromate,Cyanide,and Heavy MetalsfromWastewater 535

28 Application of Total QualityManagement(TQM)Principles to Pollution

29 PC Software for OptimizingGroundwaterContaminantPlumeCapture

32 Waste Reduction Strategies for Small Businesses 643

33 Contaminated Soils in Highway Construction 663

34 Management of Waste Compressed Gases 685

35 Pollution Control in the Dairy Industry 705

36 Landfill Gas Collection and Destruction Systems: Evaluating Toxic Emissions

AlaaH.Aly Utah State University,Logan,Utah

Paul D. Kuhlmeier Consulting Environmental Engineer,Boise,Idaho

*Current affiliation: Lamar University,

John Hanna and Osawaru A. Orumwense

II. SOURCE OF WASTES

I mlnlng, quanylng. dredglng. exploratlon -Slurries

B. Mining and ProcessingLiquidWastes

Table 1 Characterization of FoundryDust

111. METHODS OF CONTROL AND TREATMENT OF BULK SOLID WASTES

A. Copper Mine Wastes

C.Phosphate Rock Wastes

Table 2 mid Results of HSAD West Oxidation of Phosphorus Sludge [32]

1 Solution 50.20 64.60 53.39" 99.97

F. 'Brass and Bronze Foundries Dust

B. Substitution Methods as an Element of Pollution Prevention

II. HAZARDOUS MATERIAL SUBSTITUTION ACTION

Table 1 Risk Assessment Code Rating Schemea

model, an individual property or a number of properties of a given chemical can be evaluated

111. LIFECYCLE AND MANAGEMENT CONSIDERATIONS

Table 2 Life Cycle HazardousMaterialsCostsandCost

B. Management Decisions and Actionsfor Selection of Least

B. Understanding the Basis for the “Points”

Circumstancesof Exposure. In addition to the specifics of probable work areas, questions on

V. CONCLUSIONS AS TO UTILITY OF THE METHODOLOGY

1. THE IMPORTANCE OF DECISION MAKING

As an example, compliance requirementsfor wastewater treatment facilities have changed

W. HOW CERTAIN IS ENVIRONMENTAL SCIENCE?