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Water Research Vol. 14, pp. 491 to 499 0043-1354/80/0501-0499502.

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O Pergamon Press Ltd 1980. Printed in Great Britain

SEDIMENT OXYGEN DEMAND TECHNIQUES:


A REVIEW AND COMPARISON OF LABORATORY
AND IN S I T U SYSTEMS
GEORGE T. BOWMAN and JOSEPH J. DELFINO*
Environmental Sciences Section, Laboratory of Hygiene, University of Wisconsin-Madison,
465 Henry Mall, Madison, Wisconsin 53706, U.S.A.

(Received Au#ust 1979)

Abstract--Sediment oxygen demand (SOD) measurement techniques are reviewed and suggestions
offered for improving their performance, including an experimental approach toward standardizing the
SOD methodology. Five principal analytical systems are used to evaluate SOD. These are conveniently
classified as: (1) batch (laboratory and in situ); (2) continuous flow; (3) manometric; (4) electrolytic and (5)
dehydrogenase activity. Comparison of SOD methods requires establishing certain criteria which should
be met for a given method to be considered acceptable. These criteria are: (1) consistency; (2) reproduci-
bility and (3) efficiency. Laboratory techniques can meet the acceptability criteria more easily than in situ
techniques. A SOD reaction chamber used in our laboratory provided reproducible data for replicate
analyses of stream and lakes sediments and met our acceptability criteria.

INTRODUCTION large amounts of fibrous material that is discharged


from the mills.
Benthic deposits have long been recognized as having One of the most significant parameters in these
a potentially severe impact on the oxygen content of water quality models is SOD. For example, an
natural waters. In certain locations, benthic deposits increase in the SOD by a factor of only 1.5 (under low
may be responsible for about 50% of the total oxygen flow conditions and with Best Practical Treatment
depletion in a given section of a river (Hanes & Technology installed by the mills) will result in a vio-
Irvine, 1966). This depletion is. frequently referred to
lation of the Wisconsin DO standards (Patterson et
as sediment oxygen demand (SOD) although many
al., 1975). Also, during the summer low flow period,
investigators prefer to entitle it benthic oxygen the SOD of benthic sludges limits DO in the St. Louis
demand.
River reservoirs where the stream often approaches
Sediment oxygen demand is a term that includes noncompliance with DO standards (McEIroy & Chiu,
oxygen demand from two separate processes: (1) bio- 1974).
logical respiration of all living organisms in the sedi-
Although SOD is an important parameter, there is
ment and (2) chemical oxidation of reduced sub-
no presently accepted standard method available to
stances in the sediment such as divalent iron and evaluate it. SOD methods vary from state to state and
manganese, and sulfide (Wang, 1979). Pursuant to the
agency to agency; yet, comparisons of results among
1972 Amendments of the Federal Water Pollution disparate techniques are routinely made by investiga-
Control Act (Public Law 92-500), and the subsequent
tors. Reports in the literature frequently compare
implementation of state water quality standards (par-
SOD data without referring to differences in method-
ticularly those for dissolved oxygen), renewed interest
ology. Serious legal and economic consequences can
has been placed on quantifying SOD in natural water
follow from the enforcement of discharge limits based
systems.
on computer models in which one of the most impor-
Predictive computer modeling has gained wide
tant parameters (SOD) contains significant analytical
recognition as a means of evaluating the impact of uncertainty.
point source discharges on water quality parameters,
From 1973 through 1975, we performed laboratory
especially dissolved oxygen (DO). Models have been
SOD measurements for waste load allocation studies
designed for many rivers, including, for example, the
in Wisconsin. An extensive literature review was
Lower Fox River in Wisconsin (Patterson et al., 1975)
undertaken and from the review, it was apparent that
and the St. Louis River in Minnesota (McElroy &
no standardized SOD method was available. How-
Chiu, 1974). These two rivers receive high organic
ever, based on work done in our laboratory and
waste loads from pulp and paper mills. The rivers also
numerous papers available in the literature, we sug-
have extensive benthic sludge deposits which contain
gest that there is sound methodology developed
which can lead to standardized SOD measurements.
* To whom correspondence should be addressed. This paper reviews many of the SOD methods de-
491
492 GEORGE T. BOWMANand JOSEPH J. DELFINO

scribed in the literature and also presents an outline measurement. The DO probe was the predominant method
of our method. used to monitor DO concentrations, although some inves-
tigators used the Winkler titration technique IAPHA.
1975).
REVIEW OF SEDIMENT OXYGEN
DEMAND METHODOLOGY
Continuous f l o w
Analytical systems and techniques used by many investi- Continuous flow systems are open ended systems con-
gators to evaluate SOD may be conveniently classified as: taining a known surface area of sediment and having a
(1) batch; (2) continuous flow; (3) manometric; (4) electro- continuous regulated flow of well-aerated water moving
lytic and (5) dehydrogenase activity. over the sediment. The difference in the DO concentration
measured in the influent and effluent water is used to cal-
Batch culate the SOD.
These systems consist of sealed chambers containing Continuous flow devices are used for long term experi-
sediment of a known surface area and overlying water of a ments that are not possible with sealed batch reactors since
known volume. The water is generally circulated within the the latter are limited to a finite amount of DO. In addition.
chamber and the DO is monitored. The resulting DO de- many investigators suggest that continuous flow systems
crease over time is used to calculate the SOD which is more closely simulate flowing stream conditions.
usually expressed as oxygen demand per unit area of sedi- Most continuous flow measurements are done under
ment. laboratory conditions with the exception of Bradley &
Batch systems can be categorized as either in situ or James (1968) and James (1974). In these two studies, open
laboratory. In situ techniques are direct measurements semi-circular devices were placed in situ, entrapping a
made in the field under ambient conditions. The in situ known surface area of sediment parallel to the direction of
chamber is typically open on the bottom with a vertical flow such that the river flowed uninterrupted over the sedi-
cutting edge and externally attached flanges. The chamber ment. Laboratory devices ranged in size and shape from
is dropped onto the sediment and allowed to penetrate into 201. glass carboys (Oldaker et al., 1968) to 5 in. plexiglass
the sediment. This entraps a known volume of water over a cylinders (Mueller & Su, 1972). Flow detention time in the
known surface area of sediment. The exterior flanges pre- reactors varied from 1 h. (Fillos & Molar, 1972j to 24 h
vent the chamber from excessively penetrating into the (Mueller & Su. 1972).
sediment. The SOD is measured when the chamber is in
place. Manometric
Laboratory techniques require the collection of undis- Manometric techniques are based on the principle that.
turbed sediment cores or dredge samples for later analysis at constant temperature and volume, changes in the
in the laboratory under controlled conditions. amount of gas can be measured by monitoring pressure
Batch chambers have been constructed in many shapes: changes (Umbreit et al.. 1964). When the temperature, fluid
square (Nolan, 1977); rectangular (James, 1974; Butts, 1974; volume, type of gas being exchanged and the density of the
Butts & Evans, 1977); cylindrical (Brewer et al., 1977; fluid in the manometer are known, the amount of gas con-
Davison & Hanes, 1968; James, 1974; Nolan & Johnson, sumed can be calculated.
1978; & Sullivan et al., 1978); and variations of each of SOD measurements are made by placing a known
these configurations. The capacities have ranged from 0.1 1. weight of sediment in a reaction vessel containing DO-
(Pamatmat et al., 1973) to 1251. (Sonzogui et al., 1977). saturated water. The vessel is then attached to a man-
Batch chambers are generally constructed of synthetic ometer and incubated at constant temperature. As oxygen
materials such as: plexiglass (Nolan, 1977; Brewer et al., is utilized during microbial oxidation, carbon dioxide is
1977; Davison & Hanes, 1968); acrylic plastic (Gallagher released. To avoid carbon dioxide pressure interferences.
& Daiber, 1974); fiber glass (Sullivan et al., 1978; Pamat- an alkali trap is used. Any change in the manometer read-
mat, 1971) and perspex (Edwards & Rolley, 1965; Knowles ing is due solely to the amount of oxygen consumed by the
et al., 1962). Some chambers were constructed of metal sediment. The change in pressure ts then used to calculate
(Patterson et al., 1975; Butts, 1974; Butts & Evans, 1977 the SOD.
and 1978) and glass (Hargrave, 1969), The constant volume Warburg-type respirometer
Laboratory SOD measurements have mostly been made (Gardner & Lee. 1965: Baumgartner & Palotas. 1970) and
on undisturbed sediment cores (Bradley & James, 1968; the differential respirometer (Liu. 1973) have both been
Edberg & Hofsten, 1973; Edwards & Rolley, 1965; Gal- used to measure SOD. The differential respirometer com-
lagher & Daiber, 1974; Hargrave, 1969; Hayes & MacAu- pensates for temperature and barometric pressure changes
lay, 1959; Howeler, 1974; James, 1974; Knowles et al., which may occur during the course of an experiment
1962; Lasenby. 1975; Martin & Bella, 1971; Neame, 1975; (Umbreit et al.. 1964). Uncompensated fluctuations in
Nolan, 1977; Nolan & Johnson, 1978; Pamatmat, 197t; barometric pressure will bias results in a constant volume
Pamatmat et al., 1973; Sullivan et al., 1978). However, (Warburg-type) respirometer.
some investigators have made SOD measurements using
dredge samples obtained with an Ekman dredge (Bowman Electrolytic
and Delfino, this paper; Brewer et al., 1977; Lueschow, Electrolytic respirometer techniques employ an
1970-72). Undisturbed sediment cores were obtained with electrolysis-based manometric procedure. The system con-
a variety of coring devices, including the Jenkins corer tinuously replaces the oxygen utilized by the sediment
(Hayes & MacAulay, 1959); Kojak corer (Edberg & Hof- through a manometricatly controlled electrolysis reaction
sten, 1973); K-B corer (Lasenby, 1975); fabricated gravity- A sediment sample can be p l a c ~ in the bottom of the
type corer (Nolan, 1977; Nolan & Johnson, 1978; Pamat- electrolysis cell, with water collected from the sediment
mat, 1971; Sullivan et al., 1978); and SCUBA equipment sampling site added with it, A small air space is left at the
(Neame, 1975). top of the cell. During incubation, as oxygen is biologically
Water circulation in most chambers was maintained or chemically removed from the sample cell. a slight
either by an internal mixing device or an external pump to vacuum is produced. The vacuum causes a fluctuation in
provide uniform distribution of DO. However, Lasenby the electrolyte level and this trig$ers the electrolysts reac-
(1975) and Sonzogni et al. (1977) were among the few inves- tion. Oxygen gas is generated to fill the partial vacuum
tigators who used static systems. until the pressure deficit has been satisfied. The amount of
DO measurements were made either continuously, current drawn by the electrolysis cell can be related.
peridically or at the beginning and end of each SOD through Faraday's Law. to the amount of oxygen pro-
Sediment oxygen demand techniques 493

Table 1. Laboratory systems and techniques used by investigators to


determine sediment oxygen demand

Batch: Continuous flow:


Bradley & James (1968) Fair et al. (1941)
Brewer et al. (1977) Fillos & Molof (1972)
Davison & Hanes (1968) McKeown et al. (1968)
Edberg & Hofsten (1973) Mueller & Su (1972)
Edwards & Rolley (1965) Ogunrombi & Dobbins (1970)
Gallagher & Daiber (1974) Oidaker et al. (1968)
Hanes & Irvine (1966)
Hanes & White (1968) Manometric:
Hargrave (1969) Baumgartner & Palotas (1970)
Hargrave (1972) Gardner & Lee (1965)
Hayes & MacAulay (1959) Liu (1973)
Howeler (1974)
James (1974)
Knowles et al. (1962) Electrolytic:
Lasenby (1975) Reynolds et al. (1973)
Martin & Bella (1971)
McKeown et al. (1968) Dehydrogenase:
Neame (1975) Lenhard & DuPlooy (1965)
Nolan (1977) Pamatmat & Bhagwat (1973)
Nolan & Johnson (1978) Pamatmat et al. (1973)
Pamatmat et al. (1973)
Rolley & Owens (1967)
Sullivan et al. (1978)
USEPA (1976)
Wang (1979)

duced. The sediment oxygen demand is then calculated concerning the effects of these factors on SOD. A brief
based on equations given in Reynolds et al, (1973). review of some of these factors is provided here.
Sludge depth. Early work by Fair et al. (1941) indicated
Dehydrogenase activity that sludge depth influenced SOD. Later investigators
In order to determine anaerobic benthic metabolism, de- generally reported that SOD was independent of sludge
hydrogenase activity can be measured in sediments depth, within certain limits (McKeown et al., 1968; Fillos
(Iiamatmat & i3fi~wat, i973). The d~fiydrogenase activity & Molof, 1972; Edwards & Rolley, 1965; Pamatmat et al.,
method is calibrated by direct microcalorimetry and results 1973; Hargrave, 1969; Martin & Bella, 1971; McDonnell
are converted to metabolic heat release. This metabolic & Hall, 1969). '
heat release can then be correlated with oxygen consump- Oxygen concentration. Many investigators have agreed
tion. The SOD (measured by one of the traditional tech- that SOD is independent of DO concentration in the over-
niques), added to the anaerobic metabolism (derived from lying water in the range of approx. 3-Smgl -I DO
dehydrogenase activity measurements), yields the total ben- (Edwards & Rolley, 1965~ Hargrave, 1969; Knowles et al.,
thic metabolism (Pamatmat & BIaagwat, 1973). 1962; Martin & Bella, 1971 ; McKeown et al., 1968; Pamat-
As an aid in summarizing the literature discussed above, mat et aL, 1973).
numerOus investigators and the systems they employed to Sediment resuspension. Essentially all investigators who
measure SOD are listed in Tables 1 and 2. have commented on this factor observed" that SOD
increases as sediments are resuspended (Butts, 1974; Hat-
Factors influencing sediment oxygen demand grave, 1969; Martin & Bella, 1971; Baumgartner &
The various factors that influence oxygen depletion by Palotas, 1970). James (1974) found a linear increase in oxy-
sediments are well documented in the literature. Despite gen consumption with increasing water velocity. With
many studies, however, there is still considerable discussion higher velocities, the rate of increase became exponential.

Table 2. In situ systems and techniques used by investigators to


determine sediment oxygen demand

Batch: Batch:
Bradley & James (1968) Smith et at. (1972)
Butts (1974) Sonzogni et al. (1977)
Butts & Evans (1977) Sullivan et al. (1978)
Butts & Evans (1978) Thomas (1970)
Butts & Sparks (1977) USEPA (1976)
Hunter et al. (1973)
Institute of Paper Chemistry (1976) Continuous flow:
James (1974) Bradley & James (1968)
Lucas & Thomas (1972) James (1974)
Nolan (1977)
Pamatmat & Banse (1969)
Pamatmat & Fenton (1968) Dehydrogenase:
Pamatmat et al. (1973) Pamatmat et al. (1973)
494 GEORGE T. BOWMAN and JOSEPH J. DELFINO

Table 3. Sediment oxygen demand (SOD) in Lower Green Bay: in .situ vs.
laboratory measurements (Patterson et al., 1975)

In situ Laboratory
Sampling SOD Temp. SOD Temp.
locations g 0 2 m 2day-~ C g02m-2day J 'C

Mouth of Fox River 1.90 12 0.48 20


Near Red Bank 1.65 12 0.16 20

Table 4. In situ vs. laboratory sediment oxygen demand measurements (Edberg


& Hofsten, 1973)

In situ Laboratory
Sampling SOD Temp. SOD Temp.
locations g 02 m - 2 day - ~ ~C g O2 m - 2 day- a "C

Baltic Sea*
Edeboviken 1 3.0 13 0.71 10
Edeboviken 2 0.92 15 0.40 10
Lakes
Erken 0.43 4 0.32-0.36 10
Norruiken 11" 1.8 5 1.1 10
Norruiken 2t' 2.4 7 1.5 10
Ramsen 2.3 17 0.21-1.08 10
Ekoln 2.6 18 0.58 12 13
Streams
Venaviken 1.44 2 0.26-1.2 5
Jaders Bruk 1.4 2 0.42-0.63 5
Sjomosjon 0.31 0 0.31-0.61 10

* Sediments contained fibrous matter from sulphite and pulp mills.


1"Eutrophic lake with newly deposited algae.

The effect was apparently due to increased sediment resus- result in increased rates of bacterial respiration, yielding
pension, leading to increased surface area. higher SOD rates. McDonnell & Hall (1969), for example.
Photosynthetic activity. Most investigators recognized reported that biological processes increase two-fold for
the potential effect that photosynthesis a n d respiration each 10°C rise in temperature.
have on SOD. For example, Lucas & Thomas (1972)
reported that benthic algae can offset SOD during daylight Comparisons of sediment oxygen demand methodologies
when light penetration is great. They also n o t ~ that part Frequently, researchers refer to SOD values in the litera-
of the measured SOD resulted from respiration of viable ture without adequately considering methodologicaldiffer-
algae. ences. Yet, these differences among the various methods
Invertebrate activity. Edwards & RoI!cy (1965), McDon- may be significant. Some investigators have compared
nell & Hall (1969) and Teal & Kanwlaher (1961) found that laboratory and in situ measurements and reported con-
invertebrate respiration significantly inerea___~-_~_SOD. Butts siderable differences between the two approaches.
& Sparks (1977) reported that about 50*,4 of the SOD at For example, Patterson er al. (1975) found up to a
one station in the Keokuk Pool of the Miuil~ippi River lO-fold difference between laboratory and in situ measure-
could be attributed to fingernail clams. Sullivan ez al. ments, uncorrected for temperature (Fable 3) while Edherg
(1978) indicated that snails in some portions of the Wiscon-
sin River contributed 10 to 25% of the total SOD. Table 5. In situ vs laboratory sediment oxygen demand
Salinity. Hanes & White (1968) observed a slight increase measurements (USEPA, 1976)
in SOD with increased salinity while Baumgartner &
Palotas (1970) noted no apparent increase. In situ SOD Laboratory SOD
pH. McKeown et al. (1968) found a significant change in g 02 m - 2 day - ~ g 02 m - 2 day-
SOD upon adjusting the pH of sludge to a neutral pH. No
other investigators have apparently reported similar find- 4.8 11.0
ings. 6.2 9.8
Chemical oxygen demand. It is difficult to examine SOD * 4.1
without also considering the interaction between chemical " 9.8
oxygen demand (COD) and biological respiration. Smith et 5.4 7.7
al. I1972), Hargrave (1972), Martin & i~lla (1971), Teal & 5.6 9.8
Kanwisher (1961), Neame (1975), Sottzogni et al. (1977), 1.9 11.0
Brewer et al. (1977g Pamatmat (1971) and Wang (1979) 4.7 12.2
used bacterial inhibitors to measure non-biolo#cal (chemi- 4.3 9.2
cal) oxygen demand while total oxygen demand was 3.1 11.0
measured in uninhibited systems. The biological oxygen
demand component was calculated by ~ . * The SOD rates could not be estimated because dis-
Temperature. The effect of temperature on SOD has been solved oxygen levels in the overlying water were depressed
well documented in the literature. Increases in temperature f3.4 and 2.8 nag I- t respectively).
Sediment oxygen demand techniques 495

Table 6. Comparison of sediment oxygen demand measurements using four different


techniques (James, 1974)

Respiration Respiration Mud-core


tunnel chamber respirometer
(in situ continuous (in situ (Laboratory Mass
flow)* batch)* batch)* balance
gO2m-2day-l-t gO2m-2day-I t gO2m-2day-I t gO2m-2day-li-

5.28 3.84 3.6 4.56


38.16 27.12 22.08 44.16
10.08 -- 5.28 8.16
-- 3.6 -- 0.72
-- 9.6 9.36 8.4
-- 8.4 5.28 7.68
-- 3.12 1.68 --

* These terms indicate equivalent categories as used in this paper.


t Originally reported as g O2 m- 2 h- 1 but converted to a daily basis for consistency
with data from other studies.

& Hofsten (1973) reported up to a 5-fold difference, again Finally, the procedure must be efficient to permit the
uncorrected for temperature (Table 4). The USEPA (1976) measurement of many samples over a relatively short
published data showing up to 6-fold differences between period of time. Depending on the number of effluents dis-
laboratory and in situ measurements (Table 5). James charged to a river, and the length of the river under investi-
(1974) noted similar differences when comparing results gation, many SOD measurements may be needed to satisfy
among four types of SOD systems (Table 6). The mass the data needs for modeling and other interpretive appli-
balance technique listed in Table 6 is based on hourly cations. If the three criteria are met, a given method should
changes in oxygen concentration at two stations located be suitable for measuring SOD.
upstream and downstream of a test reach. Although some The laboratory vs in situ issue has long been discussed in
of the data given in Table 6 show relatively good agree- the literature. Both SOD measurement approaches have
ment among two or more techniques, methodological dif- certain advantages and disadvantages. In situ techniques
ferences were identified as the biggest source of variations are desirable since they are employed under approximately
in the data. ambient conditions. Yet, they present distinct disadvantages.
Pamatmat (1971) and Nolan (1977) were among the few Investigators must tolerate a variety of natural conditions.
investigators who have been able to successfully replicate Local weather conditions determine when, and for how
SOD using both in situ and laboratory measurements long, in situ measurements can be performed. For example,
(Tables 7 and 8, respectively). Pamatmat (1971) replicated rapid and substantial changes in the hydrological condi-
in situ and shipboard laboratory SOD measurements to tions of a river might interrupt in situ studies.
within about 10% while Nolan (1977) found reasonably In the northern United States, measurements are usually
good agreement among his replicate experiments. These made during the ice-free months. Surveys made during the
results are considered to be good, despite occasional dis- ice cover period can be difficult; particularly in terms of
agreement, and were obtained by careful analysis and con- installing SOD devices and most importantly, in keeping
trol of the experimental variables that can affect SOD the probes and other equipment functioning properly in
measurements in situ and in the laboratory. below-freezing conditions. Variables that can affect SOD
Using many of the results reported in the literature, in and which are uncontrollable include: temperature, turbu-
addition to our own experiences, we find that three criteria lence, light and current velocity. Thus, there are many fac-
must be met for a SOD method to be considered accept- tors which must be controlled during measurement in
able. These are: (1) consistency; (2) reproducibility and (3) order to collect accurate and reproducible SOD data and
efficiency. An investigator must closely adhere to a pre- these are not easily accomplished in situ. Furthermore,
scribed method to insure that the sediment is handled and logistical and field labor costs can limit the total number of
analyzed consistently from one experiment to another. The SOD measurements made under a given research budget.
method must also be as reproducible as a biologically Initially, laboratory techniques might appear to be less
dependent assay technique will allow (we consider good desirable since they do not precisely reproduce natural
reproducibility among replicates to be within + 20%). conditions. Also, it may be more difficult to interpret and
compare the results of laboratory SOD systems with those
Table 7. In situ vs. shipboard laboratory sediment oxygen developed from field studies. Laboratory variables, though,
demand measurements (Pamatmat, 1971) can be controlled more easily, thereby allowing improved
precision among replicates. For example, temperature,
In situ Shipboard laboratory
Bell jars cores
Set No. mi O 2 m - 2 h - t ml O 2 m - 2 h - t Table 8. In situ vs. laboratory sediment oxygen demand
measurements (Nolan, 1977)
9.6 ~ =9.0* 7.7 ; =8.6
In situ Laboratory
1 9.6 iSD =0.98 8.4 SD =0.74 g 02 m- 2 day- i g 02 m- 2 day- t
7.9 9.5
5.6 ~ = 6.2 6.6 ~ =6.9 0.45 0.73
2 6.7 SD=0.55 5.1 SD=1.45 1.90 1.80

6.2 8.4 1.12 1.34


7.6 0.95 2.55
1.18 1.95
* X ~ mean.
496 GEORGE T. BOWMANand JOSEPH J. DELFINO

Table 9. Volume/surface ratios of laboratory sediment oxygen demand devices

Volume Surface area V/S Ratio


I. m2 1 m- z Investigators

0.1-0.15 0.0102 9.8 1 4 . 7 Pamatmat et al. (1973)


2.1 0.0295 71 Brewer et al. (1977)
1.93 0.0215 94 Hanes & Irvine (1966)
3.05 0.0231 132 This paper
25.1 0.093 270 Nolan (1977)
6.91 0.0181 380 McDonnell & Hall (1969)
9.8 0.0231 424 Lueschow (1970-1972)

light, degree of agitation, and DO concentration are more studies indicated that the water circulating through the
easily controlled in the laboratory than in situ. reactor mixed completely within 2 rain.
All SOD measurements were made in a dark incubator
room held at 20 _+ I°C. Sediment was placed in the reactor
LABORATORY SEDIMENT OXYGEN to a depth of 5 cm. Dilution water was slowly pumped into
DEMAND MEASUREMENTS the reactor with a peristaltic pump, with care taken to
minimize disturbance of the sediment. All air was flushed
Experiments have been performed in o u r labora- from the pump tubing and the plexigtass lid carefully
tory using a batch device capable of determining sedi- placed on the reactor to prevent entrapment of air, The rid
ment oxygen d e m a n d in less t h a n 24 h. The device was secured with wing nuts and the reactor stabilized for
1 h. The peristaltic pump, the DO probe and the r e o r d e r
was designed to give an o p t i m u m volume to surface were startedtogether. The DO measurements were recorded
ratio to maximize consistency, reproducibility a n d continuously for 24 h or until the DO fell below 2 mgi-1.
efficiency. Volume to surface ratios (V/S) of batch The method used to calculate the SOD followed that
reactors reported in the literature (Tables 9 a n d I0) described by Hanes & White (19681 A DO depiction curve
was constructed with the cumulative DO depletion, plotted
were used to select what appeared to be an o p t i m u m
as the abscissa and time plotted as the ordinate. The slope,
value. W e found t h a t a V/S ratio of 1321 m -2 allowed calculated as a least square fit from the linear mid-portion
sufficient oxygen c o n s u m p t i o n to occur within 2 4 h of the DO depletion curve, represented the SOD in units of
a n d enabled the determination of S O D values in the gO2 m -2 h -1 All calculations were based on the assump-
range of 1 to 10g O2 m - 2 day - I . tion that SOD rates vary linearly with time within the DO
range of 2 to 8 mg 1- ~.
Materials and Method
R e s u l t s and Discussion
The batch reactor was constructed of plexiglass and had
a volume of 3.051., a nominal ~ i m c n t surface area of Initial studies showed that the batch reactor system
0.0231 m 2 and a V/S ratio o f i 3 2 lin -~. Additional design provided reproducible data. Replicate S O D measure-
features are shown i n Fig. I.
ments taken on sediments collected from Lower
The s e d ~ t sampks analyzed with the reactor were
collected with an Ekman dredge. The overlying medium G r e e n Bay, an e m b a y m e n t of Lake Michigan located
was distilled water to which were added nutrient salts as in northeastern Wisconsin, produced a m e a n S O D of
specified in the-bqochemical oxyg~a---de~hd procedure 0.0063 g m - 2 h - i (Fig. 2), a n d a relative standard de-
(APHA, 1975). Water circulation :through the batch reactor viation (RSD) of 9.5%. This precision correslmnded to
was maintained with a peris~tic pump, operated at a rate
of approx: 110 to 120 ml rain- i, which allowed continuous that observed by P a m a t m a t (1971) w h o reported
contact with the D O and temperature sensors (Fig. 1). Dye RSDs ranging from 8.6 to 21% for replicate S O D

Table 10. Volume/surface ratios of in situ sediment oxygen demand devices

Volume Surface area V/S Ratio


1. m2 I m- 2 Investigators

12 0.25 48 Lucas & Thomas (1972)


13 0.25 52 Thomas (1970)
76.4 0.166 60 Sullivan et al. (1978)
12 0.186 64 USEPA (1976)
5.723 0.0572 100 Pamatmat & Fenton (1968)
125 1 125 Sonzogni et al. (1977)
30.27 0.217 139 Butts (1974)
30.27 0.217 139 Butts & Evans (1977)
30.27 0.217 139 Butts & Sparks (1977)
30.27 0.217 t39 Butts & Evans (1978)
10.95 0.0730 150 Smith et al. (1972)
4.82 0.0316 152 Butts & Evans (1978)
33.2 0.166 200 Sullivan et al. (1978)
15.54 0.0707 220 Edherg & Hofsten (1973)
109.76 0.3716 295 Patterson et al. 1975)
Sediment oxygen demand techniques 497

ImCOaOtRI

Dissolved
Protective

in out

Peris~lUc
~mp

Tightening
Jwing nuts

plate bolt
11,,7 ~ water
Plexiglass
•~ - . ~ sediment cylinder
• i " J ~
Siliconej
quarium / Plexiglass-
Sealer plate REACTION CHAMBER DIMENSIONS
volume of water: 3.05 liters
diameter: 17.1cm
nominal surface "]. 0 0231 m 2
area o f s e d i m e n t J "

Fig. 1. SOD reaction chamber used in laboratory experiments.

measurements. Nolan & Johnson (1978) reported calibration drift in the DO l~robe occurred. This led
poorer precision (RSD = 35%) for a series of 24 sets to increased imprecision among replicate experiments.
of replicate SOD measurements. We also performed Our batch reactor (Fig. 1) reduced probe error by
duplicate SOD measurements of sediment collected optimizing the V/S ratio. This led to more precise and
below the Nine Springs Sewage Treatment Plant in efficient laboratory SOD measurements.
Madison, Wisconsin and likewise found good agree- Based on numerous experiments, a 24 h equilibra-
ment between duplicates (Fig. 3). tion and measurement period is quite adequate to
An earlier version of our batch reactor had too measure SOD precisely and efficiently. This period
large of a V/S ratio (V/S = 424) (Luesehow, unpub- decreases the possibility of error due to an initial
lished data). Sediments with low SOD required many chemical oxygen demand which might be exerted by
days incubation to achieve DO depletions adequate chemically reduced ions in sediments.
to calculate SOD. Oyer this time frame, error due to Only dredge samples have been analyzed, to date,

06 GREEN BAY SEDIMENT


z REPLICATE SAMPLES (20"± I'C)
9 : :No.I Slope= 0.0069m Oz/m2/hr
I--
I,t.I 0.~ I - - - = No2 Slope= 0.0069m 02/mZ/hr
_1 ~'""&No.3 Slope= 0.0079m 02/rna/hr
Q.
uJ
a 04
Z~

~ 0.3
0
~ o2
.J
~ 0.1
~.o.~°"~
u
I ~ I i 'I I i i i
0 5 15 20 25 30 35 40 45
TIME (HOURS)

Fig. 2. SOD measured on sediment collected from Lower Green Bay in northeastern Wisconsin.
498 G[!{}RGf! T. BOWMAN a n d JOSIiPH J. D[!LHN()

SLUDGE DEPOSITS DOWNSTREAM from


0.6 NINE SPRINGS SEWAGE TREATMENT PLANT
Z
O DUPLICATE SAMPLES (20"-*I'C)
I-- ~ ' - " ~ NO. I Slope = 0.02 gln 021m21hr
Ld 05 ='- -=No.2 Slope=O.O2gmO21m21hc
_1
0.

WZ~ 04
~E
x~ o~
,,,E [
..~.."

g °-'I
I I I I
o 1, ~ 8 b ,2 ,:, ,o ,8 2'o
TIME (HOURS)
Fig. 3. SOD measured on sediment collected below the Nine Springs Sewage Treatment Plant.
Madison, Wisconsin.

in our reactor system. However, based on recent Report of Investigation 76. Illinois State Water Survey,
information in the literature and greatly increased Urbana. IL.. 32 p.
Butts T. A. & Evans R. L. (1977) The art and science of
sediment coring capabilities, we believe additional measuring sediment oxygen demand in the field. Pre-
experimentation is needed, using our basic reactor sented at AMSA-MSD Water Quality Conference.
design but modified to a c c o m m o d a t e undisturbed Chicago, I L April 20°22. 19 p.
sediment core samples. Butts T. A. & Evans R. L. [1978] Sediment oxygen demand
studies of selected northeastern Illinois streams. Circular
129. Illinois State Water Survey, Urbana. II1,, 117 p.
CONCLUSIONS Butts T. A. & Sparks R. E. (1977) Sediment oxygen
demand-fingernail clam relationship in the Mismssippi
A review of the sediment oxygen d e m a n d literature River. Keokuk Pool. Presented at 1977 Joint Meeting,
a n d initial experiments in our laboratory have shown Ill. State Academy of Science. Missouri Acadmny of
that: (1)consistency, reproducibility and efficiency Science. Univ. of Missouri-St. Louis. St. Louis. Missouri.
are suitable criteria for judging the acceptability of April 29--30, 13 p.
Davison R. I. & Hanes N. B. 11968) Effect of d~pfla on
S O D measurement techniques; (2) laboratory S O D oxygen uptake of a benthal system. Prec. 23rd Industrial
measurements generally meet the acceptability criteria Waste Conf.. Purdue Univ.. Engr. Ext. Series 132.
better than in situ techniques and (3) replicate S O D Lafayette. IN. 311-324.
measurements using a laboratory device that can ac- Edberg N. & Hofsten B V. (1973) Oxygen uptake of bot-
c o m m o d a t e undisturbed sediment cores represent a tom sediments studied in situ and in the laboratory.
Water Res. 7. 1285-1294.
realistic a p p r o a c h toward standardizing S O D Edwards R. W. & Rolley H. L. J. (1965) Oxygen consump-
measurements. tion of river muds. J. Ecol. 53. 1-19.
Fair G. M.. Moore E. W. & Thomas H. A. Jr. (1941) The
Acknowledgements-Support for this work was provided, natural purification of river muds and pollutional sedi-
in part, by the Wisconsin Department of Natural ments. Sewage Wks J. 13, 270-307: 756-778.
Resources and the Laboratory of Hygiene. L. A. Lueschow Fillos J. & Molof A. H. (1972) Effects of benthal deposits
of the Wisconsin DNR provided valuable assistance in the on oxygen and nutrienl economy of flowing waters. J.
initial development of the SOD apparatus. Wat. Pollut. Control Fed. 44, 644-662.
Gallagher J. L. & Daiber F. C. (1974) Oxygen consumption
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w.R. 14/5---G,

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