SOURCES, CHARACfERISTICS, AND MANAGEMENT OF PRODUCED

WATERS FROM NATURAL GAS PRODUCfION AND STORAGE OPERATIONS

J.P. Fillo, 1 S.M. Koraido, 1 and J .M. Evans2

1 ENSR Consulting and Engineering

Pittsburgh, Pennsylvania
USA
2 Gas Research Institute
Chicago, Illinois
USA

INTRODUCfION
Produced water is the single largest volume source of waste produced by the oil and gas
industry. These waters are generated as a result of crude oil and natural gas production, including
both onshore and offshore sources. Unconventional sources of natural gas, such as coalbed
methane also generate water upon production of the gas. Produced waters are also generated
along with the withdrawal of natural gas from underground storage reservoirs.
Produced waters generally are regulated and managed in accordance with the specific disposal
method used. For example, deep-well disposal of produced waters is regulated under the Safe
Drinking Water Act (SDWA), via the Underground Injection Control (VIC) program, as aass II
injection operations. Waters discharged to surface water require a National Pollutant Discharge
Elimination System (NPDES) permit under the aean Water Act (CWA), to the extent this disposal
method is allowed. Other management methods, including livestock watering and road/landspread-
ing, are utilized, and are typically state regulated and approved on a case-by-case basis.
There has been a significant increase in the quantity and quality of publicly available data
on produced waters since conduct of the U.S. Environmental Protecti.on Agency's (EPA)
Congressionally mandated study of exploration and production (E&P) wastes under the
Resource Conservation and Recovery Act (RCRA). Prior to this point in time, data on the
sources, characteristics, and management of produced waters were sparse (Fillo, et aI., 1987).
Since the EPA study, several major technical and economic studies have been conducted and
research into alternate management practices has increased.
The purpose of this paper is to review results of major studies conducted by the Gas
Research Institute (GRI) and others that address the sources, characteristics, and management
of produced waters from conventional on-shore natural gas operations. Results from GRI's
produced water characterization studies (Wesolowski et aI., 1987, 1988) are reviewed and
compared with those from the EPA study (US EPA, 1987), and studies conducted by the
American Petroleum Institute (ERT, 1987; Gruy, 1991). The major features of each of these
studies are summarized in Table 1. Various aspects of the studies are discussed in the paper, as

Produced Water, Edited by J.P. Ray

and F.R. Engelhart, Plenum Press, New York, 1992 1 51
Table 1. Major features of U.S. EPA, API, and GRI produced water studies

Study Industry Survey! Produced Water Environmental Economic

Volume Estimates Characterization mpacts Impacts
u.S. EPA E&P Waste1 X X X
API Production Waste2 x X X X
API - Gruy RCRA X X
Reauthorization
Economics3
GRI - Gas Production! X X
Storage4
lSource: U.S. EPA (1987)
2Source: ERT (1987)
3Source: Gruy (1991)
4Source: Wesolowski, et a!. (1987, 1988)

appropriate. These studies and others form the initial basis for more comprehensive GRI
investigations of produced waters, which are currently in progress.

SOURCES AND VOLUMES OF PRODUCED WATERS

Produced waters are coproduced during the extraction of natural gas and crude oil from
onshore and offshore production operations. The withdrawal of natural gas from underground
storage reservoirs also generates produced waters. Over 75 percent of the storage fields in the
u.s. are former non-associated gas producing fields (AGA, 1983). Former producing oil and
gas fields and water reselVoirs comprise most of the remainder. Salt domes, condensate fields,
and oil fields are also used to store natural gas.
Produced waters are recovered from several locations. They are typically recovered at or
near the production wellhead, but often times can be recovered via pipeline drips and/or
separators located at gathering stations, processing/conditioning plants, and underground stor-
age facilities. Figure 1 illustrates the major sources of produced waters.
Volumes of water generated from individual extraction or withdrawal wells vary widely.
However, estimates of produced water generation have been developed via the previously cited
American Petroleum Institute (API), EPA, and GRI studies. Nationwide estimates of total
produced water generation, based on wellhead and/or state-specific data compiled in each of
these studies, are presented in Figure 2.
The API conducted a sUlVey ofa cross':section of the E&P industry in 1986 in order to: (1)
develop independent estimates of waste volumes and sources, and (2) analyze current waste
characteristics and management practices, and associated costs. The waste volumes and facility
populations in the survey were representative of 1985 E&P activity and included 16 onshore
production sites, which were mostly oil producing. Four sites in the study were non-associated
gas producing sites. The API survey was accepted and utilized by the EPA as a part of their June
30, 1988 regulatory determination for exploration and production waste.
More recently, Gruy Engineering conducted an economic impact study for the petroleum
extraction industry for the API. Volume data for this study were compiled by Petroleum
Information Corporation (PIC) for 25 of the 32 producing states. Data for the other seven states
(Le., Missouri, New York, Ohio, Pennsylvania, Tennessee, Virginia, West Virginia) were
compiled from various sources including state regulatory agency reports, the 1986 API Produc-
tion Waste Survey, and other sources. Water production from oil wells was reported by PIC in
15 states, as well as water production from gas wells in 13 of these states. It should be noted
that these states account for 95 percent of the total U.S. oil and 92 percent of the total U.S. gas

152
 I - - - - - - - - - - - - - - - I
GATHERING STATION

L _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ .J

I - - - - - - - - - - - - - - - I
PROCESSING/CONDITIONING PLANT

L _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ .J

,-- - - - - - - - - - - - - - I
UNDERGROUND STORAGE FACILITY

L _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ .J

PRODUCTION OR WELLHEAD PIPELINE INLET OUTLET

WITHDRAWAL WELL SEPARATOR DRIP SEPARATOR SEPARATOR

Figure 1. Major sources of produced waters.

production. Water/oil and water/gas ratios for states where water production was not reported
were estimated from data for neighboring states in the API survey.
Volume estimates for gas production and underground storage operations were based on
the average produced water to gas ratios for 16 production sites and 7 underground storage
facilities, respectively, in the GRI study. The average ratios were extrapolated using total U.S.
production and withdrawal rates for 1985 (AGA, 1986, 1987), respectively.
Estimates of produced water generation vary significantly between studies, but are of a
similar order of magnitude. Based on the results of the API studies, between 14 and 21 billion
barrels per year of produced water are generated from onshore oil and gas production. The
difference between the two API studies can be attributed mostly to the differences in oil
production for the two study years. Gas production appears to generate less produced water than
oil production. Based on 1985 statistics, produced water from gas operations (GRl study)
accounts for less than 10 percent of the total generated from oil and gas production (API/EPA
studies). Based on the Gruy study, less than 2% of the volume of produced waters is generated
from gas production operations. Gas storage operations generate approximately 51 million
barrels per year, which is between 3 and 25 percent of the volume of produced waters generated
from gas production operations.

PRODUCED WATER CHARACfERISTICS

Produced waters can be characterized generally as saline water. They contain other
inorganic and organic constituents, largely dependent upon the nature of the producing/storage
formation from which they are withdrawn and the operations associated with a given facility.
The composition of produced water between different sources and formations can vary by orders
of magnitude on a constituent-specific basis. However, produced water composition is qualita-
tively similar from oil production, gas production, and gas storage operations.
Comprehensive characterization data were generated for produced waters as a result of the
exploration and production waste studies conducted by EPA (1987), API (ERT, 1987), and GRl
(Wesolowski, et a1., 1987, 1988). Produced water from primarily crude oil production (Le., 4 of 16

153
 25,--------------------------------------------,

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n:: 15
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:::0
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API/EPA GRUY-GAS GRI-STG
GRUY-OIL GRI-PROD
STUDY

Figure 2. Produced water volume estimates reported in API's, EPA's and GRI's studies.

total sites were non-associated natural gas fields) were characterized in both the API and EPA
studies. Produced water from non-associated natural gas production and gas storage reservoirs were
characterized in the GRI studies. Although, a small population of samples was collected relative to
the number of producing oil and gas fields and underground storage fields, samples were carefully
selected to represent a wide cross-section of geographic locations and/or geologic conditions.
The slate of analytical parameters included conventional water quality parameters, minor
and trace metals, volatile and semivolatile organic compounds, and RCRA criteria. The studies
utilized EPA-approved protocols to ensure that quality data were developed and the results of
the studies were comparable. In addition, the GRI study performed organics analyses using both
conventional (Le., EPA Methods 624 and 625) and isotope dilution (Le., EPA Methods 1624
and 1625) gas chromatography/mass spectroscopy (Ge/MS) methods. In this manner, GRI's
results for all samples could be related to results from EPA's study (Le., using isotope-dilution
GC/MS methods) and results for gas production samples could be related to results from API's
study (i.e., using conventional GC/MS methods). The analytical aspects of the GRI study are
discussed in Shepherd et aI., (1992).
Salt Constituents
The predominant constituents in produced water were dissolved salts (see Figure 3). Total
dissolved solids concentrations ranged from less than 100 ppm to over 300,000 ppm. While the
large majority of these salts consists of sodium chloride, the ionic composition of these waters
varied considerably. Major cations included sodium, calcium, magnesium, and potassium listed
in gneerally decreasing concentrations. Anions, other than chloride, included sulfate and
bicarbonates.
Minor and Trace Metals
Dissolved minor and trace metals were present at substantially lower concentrations than
the salt constituents (see Figure 4). Barium, boron, iron, manganese, potassium, strontium,
arsenic, silicon, zinc, and lithium were detected most frequently. The maximum values for
barium and strontium in the GRI production samples represent single samples taken from
production fields with naturally high levels of each element.
Cadmium, cobalt, copper, lead, mercury, and nickel were detected least frequently. Priority
pollutant metals were generally detected less frequently and at lower levels (Le., generally less
than ppm quantities) in storage samples.

154
 -
35O,-~~~~~~~~~~~~~~~~~-'

TOTAL DISSOLVED SOUDS c==J

' TDS (min)
<t 300
Ul
::J ~
l TDS (avg)
f- 250 f----~-~------
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D- TDS (max)
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;- 150 f------~--
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o
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EPA GRI-STG
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STUDY

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~,-~~~~~~~~~~~~~~~~~-,

CHLORIDE
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o CI- (avg)
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58

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z
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f- 30
<t
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f-
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API GRI-PROD
EPA GRI-STG
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Figure 3. Comparison oflotal dissolved solids, chloride, and sodium concentrations in produced waters from
API's, EPA's, and GRI's gas production and gas storage studies.

155
 ~
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I!'
I
--
c:::::::J
Bo (m;,)

Bo (""'l)

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- -~

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~ Sr (max)
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Figure 4. Comparison of barium and strontium concentrations in produced water from API's, EPA's, and
GRI's gas production and gas storage studies.

Volatile Organic Compounds

The most prevalent volatile organics detected in production and storage samples were
benzene, toluene, and ethylbenzene (see Figure 5). Their presence is a direct result of the nature
of hydrocarbons present in crude oil and natural gas liquids that can accompany natural gas in
producing formations; they were detected in roughly 75 to 80% of the production samples and
all of the storage samples. Produced waters from gas production operations generally contained
higher levels of benzene, toluene, and ethylbenzene than produced waters from either oil
production or gas storage. This is not surprising because several of the gas production sites
produced natural gas liquids along with the gas. Other volatile organics, particularly solvents
(Le., 2-butanone, chlorinated solvents), were detected infrequently in the produced water
samples. The presence of certain solvents in the produced water (e.g., acetone, methylene
chloride) could be related to contamination from the analytical laboratory.
Semivolatile Organic Compounds
The most prevalent semivolatile organics detected in the produced water samples were ClO
to C 30 straight-chain alkanes (see Figure 6).l..evels of semivolatile organics generally decreased
as compound molecular weight increased, and the studies that included data from oil production

'56
sites generally had higher mean, median, and maximum values. Storage sites had appreciably
lower levels than either oil or gas production sites. Other semivolatile organics that were detected
most frequently included phenols, carboxylic acids, and naphthalene. High molecular weight
PAHs were detected infrequently and at levels lower than naphthalene.

PRODUCED WATER MANAGEMENT

There are several alternatives for effective management of produced waters. These are
illustrated in Figure 7, and are summarized as follows:
deepwell disposal,
surface discharge, and
recycl e/reuse.
The specific methods used are a function of the geographic/geologic location, the specific
regulations that govern management, and the cost of produced water disposal.

Deepwell Disposal
Based on the results of the aforementioned E&P waste studies, deepwell injection of
produced waters is the most frequently practiced management alternative. This is the case
because most of the gas production in the U.S. occurs in areas where underground injection is
geologically feasible and cost effective.
An injection well operation can be captive to a producing site, or produced waters can be
collected and hauled to a central disposal facility. For example, produced water was disposed
at off-site injection wells for 17 of the 24 sites sampled in the GRI study. Four other sites utilized
on-site injection wells for produced water disposal.

Surface Discharge
There are several options for effecting surface discharge. In certain locations, it is possible to
treat produced waters and dispose them to surface water. This typically requires an NPDES permit
for the affected facility or water can be hauled to a central facility for treatment and ultimate disposal.
Produced water can be discharged to the ocean, to inland surface waters, or to a municipal
treatment facility, in accordance with applicable federal and/or state regulations. Effluent
limitations guidelines for offshore oil and gas development have been reproposed (Federal
Register, 1991) and produced water discharges to the outer continental shelf are regulated
(Federal Register, 1986). Discharge of produced waters to the ocean or tidal wetlands is
becoming increasingly more restrictive, as the State of Louisiana recently issued a ruling that
mandates the deepwell injection of produced waters currently being discharged to coastal
wetlands (Environmental Reporter, 1991). Discharge of produced waters to surface waters is
often considered on a case-by-case basis, but can be strictly prohibited unless treatment for
removal of salt constituents is conducted (e.g., New York, West Virginia, Virginia, New
Mexico). One storage site, which was a depleted oil/gas producing field in the GRI study,
discharged produced water to a Publicly Owned Treatment Works (POTW).
Land and/or road application can be allowed in certain states if composition criteria are
met for the produced water. Examples of such states include Wyoming, Pennsylvania, and
Virginia, and this typically is allowed only for low-TDS waters or for waters within a given
range ofTDS values (e.g., between 5,000 and 50,000 ppm in Wyoming). One site from the GRI
study utilized road application for the disposal of produced water. In most cases, land application
is considered on a case-by-case basis and must be conducted in accordance with a specific state's
water quality regulations. Protection of ground water typically controls the extent to which land
spreading can be practiced.

157
 -
30
BENZENE c:=:=:J
Ben (min)
25 ~
Ben (OV9)
~
1z 20
Ben (max)
Q
f-
<! 15 -~--

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f-
W
~ 10
0
u

0
API-624 EPA-1624 GRI-1624 GRI_62~-1624 (STG)
STUDY

-
40
TOLUENE c:=:=:J
Tal (min)
35
~
30 --- . Tal (OV9)
~
'"
-.S 25 - - - - - - - - - - - -----
Tal (max)
z
Q
f-
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n::
f-
zw
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." ___ 0 - ___
-----
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0
u
10

0
API-624 GRI-1624 GRI-1624 (STG)
EPA-1624 GRI-624
STUDY

-
22
ETHYlBENZENE c:=:=:J
20 EB (min)
18 ~-~~
~
EB (OV9)
~ 16
'"
-.S 14 EB (max)
z
Q
f-
12

n:: 10
f-
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w
zu 8
0
u 6 --------~~

4 -

2 ------------ -- ---- ---- ----

0
API GRI-1624 GRI-STG
EPA GRI-624
STUDY

Figure S. Comparision of benzene, toluene, and ethylbenzene concentrations in produced waters from API's,
EPA's, and GRI's gas production (EPA Method 1624 and 624) and gas storage studies.

158
 -
600 - - - - - - - - - - - - - - - - - - - - - - - ,
n-DECANE c=:::J
g-' 500
C10 (min)
~
::I ClO (avg)

~ 400
if) ClO (max)
f-
e>:

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is
f-
ri 200
!z
w
~
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100- --- ----

OL-----.-,----~V%~, I
API GRI-PROD
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STUDY

-
----------- n-HExAnECANE! I L =:J I
, C16 (min)
I
~
C16 (ovg)
I
[ 16 (max)

o
API GRI-PROD
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STUDY

-
25 --------------------------------,
n-EICOSANE c=:::J
C20 (min)
g-' 20
4

::I C20 (avg)

:r'"
Ul 15
C 20 (max)
f-

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~

is
f-
10

'"w
f-
Z

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o
u

0'-------"1"'
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EPA GRI-STG
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Figure fl. Comparison orn-decane, n-bexadecane, and n-eicosane concentrations in produced water from
API's, EPA's, and GRI's gas production and gas storage studies.

159
 r----------------~
.... DEEPWELL DISPOSAL

CLASS 1/ DISPOSAL

PRODUCED
WATER
.. . TREATMENT
(ON-SITE/OFF,-SITE)
. . SURFACE DISCHARGE
NPDES
POTW
LAND/ROAD APPLICATION

RECYCLE/REUSE
---------------- p p LIVESTOCK WATERING
BYPRODUCT RECOVERY
ENHANCED RECOVERY

Figure 7. Schematic or major produced water management alternatives.

Recycle/Reuse
There are several options to effect produced water recycle/reuse. One alternative that is
practiced in oil production operations is the use of produced water for enhanced recovery.
Produced water removed from a producing formation is recovered, treated, and reinjected into
the producing formation to extend the producing life of a field. This method of recycle/reuse is
not feasible for gas production operations.
In a manner similar to land application, certain states allow the use of produced water for
livestock watering. Specific composition criteria must be achieved to enable use of this
management alternative, which is practiced predominantly in the western U.S.
Treatment of produced water can be conducted to recover salt byproducts and generate an
essentially salt-free water stream. This concept has been demonstrated and uses chemical
treatment combined with evaporative crystallization (Hart, 1986, 1990). Chemical treatment
prior to crystallization provides for the removal of oil, ferric chloride, barium sulfate, and other
heavy metals. The remaining aqueous solution is processed via evaporative crystallization to
produce sodium chloride crystals and a salable calcium chloride solution. This concept poten-
tially could be applied to produce a low-IDS water for surface discharge or possibly for process
consumption.

FUTURE DIRECTIONS
Produced waters are generated in appreciable volumes from the extraction of oil and gas
and the withdrawal of gas from underground storage reservoirs. While the majority of this water
has been managed through use of deepwell injection, other methods can and have been used to
effect proper management. Because the regulations governing management of produced waters
from both conventional and unconventional sources are becoming increasingly stringent, it is
essential to accurately understand the sources, characteristics, and management of produced
water.
The studies discussed in this paper are being augmented to develop a more thorough
understanding of produced water and feasible alternatives for its management. A more in-depth
evaluation of produced water sources, characteristics, and management is in progress. The
objective is to supplement existing data with more recent data, including produced waters from

160
coalbed methane production and natural gas industry operating statistics, to develop more
complete regional and national profiles for produced waters. In addition, GRI research focused
to produced water treatment and disposal is presented in another paper in this volume (Naldes
et aI., 1992).

REFERENCES
AGA, 1983, "Survey of Underground Gas Storage Facilities in the United States and Canada." Operating
Section Report, American Gas Association, Statistics Task Group, Arlington, VA
AGA, 1986, "Gas Facts 1985, A Statistical Record of the Gas Utility Industry, American Gas Association,"
Department of Statistics, Arlington, VA
AGA, 1987, "Gas Facts 1986, A Statistical Record of the Gas Utility Industry, American Gas Association,"
Department of Statistics, Arlington, VA
ERT, 1987, "Oil and Gas Industry Exploration and Production Wastes." Prepared for the American Petroleum
Institute. July.
Environmental Reporter, 1991, Volume 21,1989, Bureau of National Affairs, Inc., Washington, D.C. March 8
Federal Register, 1986, Volume 51,24897, July 9.
Federal Register, 1991, Volume 56,10664, March 13.
FilIo, J.P., Hamaker, T.A., Koraido, S.M., Stefanacci, R.G., Tallon, J.T., and Wesolowski, D., 1987.
"Production Waters Associated with the Production, Processing, Transmission, and Storage of Natural
Gas" A Literature Survey: GRI Report No. GRI-87/0126. July.
Gruy Engineering Corporation, 1991, "Estimates ofRCRA Reauthorization Economic Impacts on the
Petroleum Extraction Industry." Prepared for the American Petroleum Institute. July 20.
Hart, L., 1986, "Crystallization of Sodium Chloride from Gas Well Brine." Presented at the Forty-sixth Annual
Appalachian Gas Measurement Shoot Course, Coraopolis, PA August 12-15.
Hart, L., 1990, Hart Chemical Company. Personal Communication with M. Conedero, ENSR Consulting and
Engineering, Pittsburgh, PA August 28.
Nakles, D., Ortiz, I., and Frank, J., 1992, An analysis of management strategies for produced waters from
natural gas production. in: "Produced Water: Technological/Environmental Issues and Solutions," J.P.
Ray and F.R. Engelhardt, eds., Plenum Publishing Corp., New York, New York, USA.
Shepherd, M.C., Shore, F.L., Mertens, S.M., and Gibson, J.S., 1992, Characterization of Produced Waters from
Natural Gas Production and Storage Operations. in: "Produced Water: TechnologicallEnvironmental
Issues and Solutions," J.P. Ray and F.R. Engelhardt, eds., Plenum Publishing Corp., New York, New
York, USA
USEPA, 1987, "Report to Congress-Management of Wastes from the Exploration, Development, and
Production of Crude Oil, Natural Gas, and Geothermal Energy." NTIS Report EPA-530-SW-88-003.
December.
Wesolowski, D., Broughton, A., Hansotte, C.A., Koraido, S.M., and Fillo, J.P., 1987, "Characterization of
Produced Waters from Natural Gas Production Operations." GRI Report No. GRI-87!0335.1. December.
Wesolowski, D., Broughton, D., Hansotte, C.A., Koraido, S.M., and Fillo, J.P., 1988, "Characterization of
Produced Waters from Natural Gas Storage Reservoir Operations." GRI Report No. GRI-88!OO80.1. June

161