United States
Environmental Protection Agency
Office of Water &
Office of Research and
Development
Office of Science and Technology
Health and Ecological Criteria Oiv.
Washington. D.C. 2O460
EPA-S22-R-93-016
September 1993
Sediment Quality Criteria
for the Protection of
Benthic Organisms:
ENDRIN
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CONTENTS
Foreword ii
Acknowledgments iv
Tables , . . . vi
Figures :............... vii
Introduction 1-1
Partitioning ; 2-1
Toxicity of Endrin: Water Exposures 3-1
Toxicity of Endrin (Actual and Predicted): Sediment Exposures 4-1
Criteria Derivation for Endrin 5-1
Criteria Statement 6-1
References 7-1
Appendix A: Summary of Acute Values for Endrin for Freshwater and Saltwater
Species A-l
Appendix B: Summary of Data from Sediment Spiking Experiments with
Endrin B-l
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FOREWORD
Under the Clean Water Act (CWA) the U.S. Environmental Protection Agency (U.S.
EPA) and the States develop programs for protecting the chemical, physical, and biological
integrity of the nation's waters. Section 304(a)(l) directs the Administrator to develop and
publish "criteria" reflecting the latest scientific knowledge on: (1) the kind and extent of effects
on human health and welfare, including effects on plankton, fish, shellfish, and wildlife, which
•may be expected from the presence of pollutants in any body of water, including ground water,
(2) the concentration and dispersal of pollutants, or their byproducts, through biological, physical
and chemical processes, and (3) the effects of pollutants on biological community diversity,
productivity, and stability. Section 304(a)(2) directs the Administrator to develop and publish
information on, among other things, the factors necessary for the protection and propagation of
shellfish, fish, and wildlife for classes and categories of receiving waters.
To meet this objective, U.S. EPA has periodically issued ambient water quality criteria
(WQC) guidance beginning with the publication of "Water Quality Criteria 1972" (NAS/NAE,
1973). All criteria guidance through late 1986 was summarized in an U.S. EPA document
entitled "Quality Criteria for Water, 1986" (U.S. EPA, 1987). Additional WQC documents that
update criteria for selected chemicals and provide new criteria for other pollutants have also been
published. In addition to the development of WQC and to continue to comply with the mandate
of the CWA, U.S. EPA has conducted efforts to develop and publish sediment quality criteria
(SQC) for some of the 65 toxic pollutants or toxic pollutant categories. Section 104 of the CWA
authorizes the administrator to conduct and promote research into the causes, effects, extent,
prevention, reduction and elimination of pollution, and to publish relevant information. Section
104(n)(l) in particular provides for study of the effects of pollution, including sedimentation in
estuaries, on aquatic life, wildlife, and recreation. U.S. EPA's efforts with respect to sediment
criteria are also authorized under CWA Section 304(a).
Toxic contaminants in bottom sediments of the nations's lakes, rivers, wetlands, and
coastal waters create the potential for continued environmental degradation even where water
column contaminant levels meet established WQC. In addition, contaminated sediments can lead
to water quality impacts, even when direct discharges to the receiving water have ceased. EPA
intends SQC be used to assess the extent of sediment contamination, to aid in implementing
measures to limit or prevent additional contamination, and to identify and implement appropriate
remediation activities when needed.
The criteria presented in this document are the U.S. EPA's best recommendation of the
concentrations of a substance that may be present in sediment while still protecting benthic
organisms from the effects of that substance. These criteria are applicable to a variety of
freshwater and marine sediments because they are based on the biologically available
concentration of the substance in sediments. These criteria do not protect against additive,
synergistic or antagonistic effects of contaminants or bioaccumulative effects to aquatic life,
wildlife or human health.
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The criteria derivation methods outlined in this ^document are proposed to provide
protection of benthic organisms from biological impacts from chemicals present in sediments.
Guidelines and guidance are being developed by U.S. EPA to assist in the application of criteria
presented in this document, in the development of sediment quality standards, and in other
water-related programs of this Agency.
These criteria are being issued in support of U.S. EPA'S regulations and policy
initiatives. This document is Agency guidance only. It does not establish or affect legal rights
or obligations. It does not establish a binding norm and is not finally determinative of the issues
addressed. Agency decisions in any particular case will be made by applying the law and
regulations on the basis of the specific facts.
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ACKNOWLEDGEMENTS
Principal Author
David J. Hansen
Coauthors
Walter J. Berry
Dominic M. Di Toro
Paul R. Paquin
Laurie D. De Rosa
Frank E. Stancil,Jr.
Christopher S. Zarba
Technical and Clerical Support
Heinz P. Kofflg
Glen B. Thursby
Maria R. Paruta
Stephanie C. Anderson
Denise M. Champlin
Dinalyn Spears
U.S. EPA, Environmental Research
Laboratory Narragansett, RI
Science Applications International
Corporation, Narragansett, RI
Manhattan College, Bronx, NY
HydroQual, Inc., Mahwah, NT
HydroQual, Inc.,
Mahwah, NJ
HydroQual, Inc.,
Mahwah, NJ
U.S. Environmental Research Laboratory, Athens, GA
U.S. EPA Headquarters, Office of Water, Washington, DC
U.S. Environmental Research
Laboratory, Athens, GA
Science Applications International
Corporation, Narragansett, RI
NCSC Senior Environmental Employment Program
Narragansett, RI
Science Applications International Corporation,
Narragansett, RI
Science Applications International Corporation,
Narragansett, RI
Computer Science Corporation,
Narragansett, RI
IV
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Persons who have made significant contributions to the development of the approach and
supporting science used in the derivation of sediment Briteria for nonionic organic contaminants
are as follows:
Herbert E. Allen
Gerald T. Ankley
Christina E. Cowan
Dominic M. Di Toro
David J. Hansen
Paul R. Paquin
Spyros P. Pavlou
Richard C. Swartz
Nelson A. Thomas
Christopher S. Zarba
University of Delaware, Newark, DE
U.S. EPA, Environmental Research Laboratory,
Duluth, MN
Battelle, Richland, WA
HydroQual, Inc., Mahwah, NJ;
Manhattan College,-Bronx, NY
U.S. EPA, Environmental Research Laboratory,
Narragansett, RI
HydroQual, Inc., Mahwah, NJ
Ebasco Environmental, Bellevue, WA
U.S. EPA, Environmental Research Laboratory,
Newport, OR
U.S. EPA, Environmental Research Laboratory,
Duluth, MN
U.S. EPA Headquarters, Office of Water, Washington, DC
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TABLES
t
Table 2-1. Endrin measured and estimated log10KoW values.
Table 2-2. Summary of log10KoW values for endrin measured by the U.S. EPA,
Environmental Research Laboratory, Athens, GA.
Table 3-1. Chronic sensitivity of freshwater and saltwater organisms to endrin.
Test specific data.
Table 3-2. Summary of freshwater and saltwater acute and chronic values, acute-chronic
ratios and derivation of final acute values, final acute-chronic ratios and final
chronic values for endrin.
Table 3-3. Results of approximate randomization test for the equality of freshwater and
saltwater FAV distributions for endrin and approximate randomization test for the
equality of benthic and combined benthic and water column (WQC) FAV
distributions.
Table 4-1. Summary of tests with endrin-spiked sediment.
Table 4-2. Water-only and sediment LCSOs used to test the applicability of the equilibrium
partitioning theory for endrin.
Table 5-1. Sediment quality criteria for endrin.
Table 5-2. Analysis of variance for derivation of sediment quality criteria confidence limits
for endrin.
Table 5-3. Sediment quality criteria confidence limits for endrin.
Appendix A. - Summary of acute values for endrin for freshwater and saltwater species.
Appendix B. - Summary of data from sediment spiking experiments with endrin. Data from these
experiments were used to calculate KQC values (Figure 2-2) and to compare
mortalities of amphipods with pore water toxic units (Figure 4-1) and predicted
sediment toxic units (Figure 4-2).
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FIGURES
• •. . • '
Figure 1-1. Chemical structure and physical-chemical properties of endrin.
Figure 2-1. Observed versus predicted (equation 2-4) partition coefficients for nonionic
organic chemicals (endrin datum is highlighted).
Figure 2-2. Organic carbon-normalized sorption isotherm for endrin (top) and probability plot
of KQC (bottom) from sediment toxicity tests conducted by Nebeker et. al, (1989),
Schuytema et al. (1989) and Stehly (1992). The line in the top panel represents
the relationship predicted with a log K,,,. of 4.84, that is CI(OC=Koc*Cd.
Figure 3-1. Genus mean acute values, of freshwater species vs. percentage rank of their
sensitivity. Symbols representing benthic species are solid, those representing
water column species are open. Asterisks indicate greater than values. A =
adult; J = juvenile; U = unspecified life stage, habitat unknown; X =
unspecified life stage.
Figure 3-2. Genus mean acute values, of saltwater species vs. percentage rank of their
sensitivity. Symbols representing benthic species are solid, those representing
water column species are open. Asterisks indicate greater than values. A =
Adult, E = embryo, J = juvenile, L = Larvae.
Figure 3-3. Probability distribution of FAV difference statistics to compare water-only data
from freshwater vs. saltwater (upper panel) and benthic vs. WQC freshwater
(middle panel) and benthic vs WQC saltwater (lower panel).
Figure 4-1. Percent mortality of amphipods in sediments spiked with acenaphthene or
phenanthrene (Swartz, 1991), endrin (Nebeker et al., 1989; Schuytema et al.,
1989) or fluoranthene (Swartz et al., 1990), and midge in sediments spiked with
dieldrin (Hoke, 1992) or kepone (Adams et al., 1985) relative to pore water toxic
units. Pore water toxic units are ratios of concentrations of chemicals measured
in individual treatments divided by the water-only LC50 value from water-only
tests. (See Appendix B hi this SQC document, Appendix B hi the acenaphthene,
dieldrin, fluoranthene and phenanthrene SQC documents, and original references
for raw data.)
Figure 4-2. Percent mortality of amphipods in sediments spiked with acenaphthene or
phenanthrene (Swartz, 1991), dieldrin (Hoke and Ankley, 1991), endrin (Nebeker
et al., 1989; Schuytema et al., 1989) or fluoranthene (Swartz et al., 1990; DeWitt
et al., 1992) and midge hi dieldrin spiked sediments (Hoke, 1992) relative to
"predicted sediment toxic units." Predicted sediment toxic units are the ratios of
measured treatment concentrations for each chemical in sediments (/ig/goc)
divided by the predicted LC50 (/tg/goc) in sediments (Koc x Water Only LC50,
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/ig/L) x 1 Kgoe/ljOOOgo,.). (See Appendix B in this document and Appendix B in
the acenaphthene, dieldrin, fluoranthene, and phenarithrene SQC documents for
raw data).
Figure 5-1. Comparison between SQC concentrations and 95% confidence intervals, effect
concentrations from benthic organisms exposed to endrin-spiked sediments and
sediment concentrations predicted to be chronically safe in fresh water sediments.
Concentrations predicted to be chronically safe (Predicted Genus Mean Chronic
Values, PGMCV) are derived from the Genus Mean Acute Values (GMAV),
water-only 96-hour lethality tests, Acute Chronic Ratios (ACR) and KQC values.
PGMCV = (GMAV -T- ACR)Koc. Symbols for PGMCVs are A for arthropods,
O for fishes and D for other invertebrates. Solid symbols are benthic genera;
open symbols water column genera. Arrows indicate greater than values. Error
bars around sediment LC50 values indicate observed range of LC50s.
Figure 5-2. Comparison between SQC concentrations and 95 % confidence intervals, effect
concentrations from benthic organisms exposed to endrin-spiked sediments and
sediment concentrations predicted to be chronically safe in salt water sediments.
Concentrations predicted to be chronically safe (Predicted Genus Mean Chronic
Values, PGMCV) are derived from the Genus Mean Acute Values (GMAV),
water-only 96-hour lethality tests, Acute Chronic Ratios (ACR) and KQC values.
PGMCV = (GMAV H- ACR)Koc. Symbols for PGMCVs are A for arthropods,
O for fishes and D for other invertebrates. Solid symbols are benthic genera;
open symbols water column genera. Arrows indicate greater than values. Error
bars around sediment LC50 values indicate observed range of LCSOs.
Figure 5-3. Probability distribution of concentrations of endrin in sediments from streams,
lakes and estuaries in the United States from 1986 to 1990 from the STORET
(U.S. EPA, 1989b) database compared to the endrin SQC values of 0.42 /wg/g in
freshwater sediments having TOC = 10% and 0.042 jtg/g in freshwater
•sediments having TOC = 1% and compared to SQC values for saltwater
sediments of 0.076 jig/g when TOC =10% and 0.0076 /tg/g when TOC=1%.
The upper dashed line on each figure represents the SQC value when TOC =
10%, the lower dashed line represents the SQC when TOC = 1%.
Vlll
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DISCLAIMER
This report has been reviewed by the Health and Ecological Criteria Division, Office of
Science and Technology, U.S. Environmental Protection Agency, and approved for publication.
Mention of trade names or commercial products does not constitute endorsement or
recommendation for use.
AVAILABP-TTV NOTICE
This document is available to the public through the National Technical Information
Service (NTIS), 5285 Port Royal Road, Springfield, VA 22161. NTIS Accession Number
XXXX-XXXXXX.
IX
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SECTION 1.
INTRODUCTION
1.1 GENERAL INFORMATION
Under the Clean Water Act (CWA) the U.S. Environmental Protection Agency (U.S.
EPA) is responsible for protecting the chemical, physical and biological integrity of the nation's
waters. In keeping with this responsibility, U.S. EPA published ambient water quality criteria
(WQC) in 1980 for 64 of the 65 toxic pollutants or pollutant categories designated as toxic in
the CWA. Additional water quality documents that update criteria for selected consent decree
chemicals and new criteria have been published since 1980. These WQC are numerical
concentration limits that are the U.S. EPA's best estimate of concentrations protective of human
health and the presence and uses of aquatic life. While these water quality criteria play an
important role in assuring a healthy aquatic environment, they alone are not sufficient to ensure
the protection of environmental or human health.
Toxic pollutants in bottom sediments of the nation's lakes, rivers, wetlands, estuaries and
marine coastal waters create the potential for continued environmental degradation even where
water-column concentrations comply with established WQC. In addition, contaminated
sediments can be a significant pollutant source that may cause water quality degradation to
persist, even when other pollutant sources are stopped. The absence of defensible sediment
quality criteria (SQC) makes it difficult to accurately assess the extent of the ecological risks of
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contaminated sediments and to identify, prioritize and implement appropriate clean up activities
t
and source controls. As a result of the need for a procedure to assist regulatory agencies in
making decisions concerning contaminated sediment problems, a U.S. EPA Office of Science
and Technology, .Health and Ecological Criteria Division (OST/HECD) research team was
established to review alternative approaches (Chapman, 1987). All of the approaches, reviewed
had both strengths and weaknesses and no single approach was found to be applicable for SQC
derivation in all situations (U.S. EPA, 1989a). The equilibrium partitioning (EqP) approach was
selected for non-ionic organic chemicals because it presented the greatest promise for generating
defensible national numerical chemical-specific SQC applicable across a broad range of sediment
types. The three principal observations that underlie the EqP method of establishing sediment
quality criteria are:
1. The concentrations of nonionic organic chemicals in sediments, expressed on an
organic carbon basis, and in pore waters correlate to observed biological effects
on sediment dwelling organisms across a range of sediments.
2. Partitioning models can relate sediment concentrations for nonionic organic
chemicals on an organic carbon basis to freely dissolved concentrations in pore
water.
3. The distribution of sensitivities of benthic and water column organisms to
chemicals are similar; thus, the currently established WQC final chronic values
(FCV) can be used to define the acceptable effects concentration of a chemical
freely-dissolved in pore water.
The EqP approach, therefore, assumes that: (1) the partitioning of the chemical between
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sediment organic carbon and interstitial water is at equilibrium; (2) the concentration in either
:
phase can be predicted using appropriate partition coefficients and the measured concentration
in the other phase; (3) organisms receive equivalent exposure from water-only exposures or from
any equilibrated phase: either from pore water via respirationj sediment via ingestion, sediment-
integument exchange, or from a mixture of exposure routes; (4) for nonionic chemicals, effect -
concentrations in sediments on an organic carbon basis can be predicted using the organic carbon
partition coefficient (Koc) and effects concentrations in water; (5) the FCV concentration is an
appropriate effects concentration for freely-dissolved chemical in interstitial water; and (6) the
SQC Otg/goc) derived as the product of the KQC and FCV is protective of benthic organisms.
SQC concentrations presented in this document are expressed as fig chemical/g sediment organic
carbon and not on an interstitial water basis because: (a) pore water is difficult to adequately
sample; and (b) significant amounts of the dissolved chemical may be associated with dissolved
organic carbon; thus, total concentrations in interstitial water may overestimate exposure.
The data that support the EqP approach for deriving SQC for nonionic organic
chemicals are reviewed by Di Toro et al. (1991) and U.S. EPA, (1993a). Data supporting these
. observations for endrin are presented in this document.
SQC generated using the EqP method are suitable for use in providing guidance to
regulatory agencies because they are:
1. numerical values;
2. chemical specific;
3. applicable to most sediments;
4. predictive of biological effects; and
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5. protective of benthic organisms.
i
As is the case with WQC, the SQC reflect the use of available scientific data to: 1) assess the
likelihood of significant environmental effects to benthic organisms from chemicals in sediments;
and 2) to derive regulatory requirements which will protect against these effects.
It should be emphasized that these criteria are intended to protect benthic organisms from
the effects of chemicals associated with sediments. SQC are intended to apply to sediments
permanently inundated with water, intertidal sediment and sedimente inundated periodically for
durations sufficient to permit development of benthic assemblages. They do not apply to
occasionally inundated soils containing terrestrial organisms. These criteria do not address the
question of possible contamination of upper trophic level organisms; or the synergistic, additive
or antagonistic effects of multiple chemicals. SQC addressing these issues may result in values
lower or higher than those presented in this document. The SQC presented in this document
represent the U.S. EPA's best recommendation at this time of the concentration of a chemical
in sediment that will not adversely affect most benthic organisms. SQC values may be adjusted
data or site-specific considerations.
SQC values may also need to be adjusted because of site spescific consideration. In spill
situations, where chemical equilibrium between water and sediments has not yet been reached,
a sediment chemical concentration less than SQC may pose risks to benthic organisms. This is
because for spills, disequilibrium concentrations in interstitial and overlying water may be
proportionally higher relative to sediment concentrations. Research has shown that the source
or "quality" of TOC in the sediment does not effect chemical binding (DeWitt et al., 1992).
However, the physical form of the chemical in the sediment may have an effect. At some sites
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concentrations in excess of the SQC may not pose risks to benthic organisms, because the
compound may be a component of a paniculate, such as coal or soot, or exceed solubility such
as undissolved oil or chemical. In these situations, the national SQC would be overly protective
of benthic organisms and should not be used unless modified using the procedures outlined in
the "Guidelines for Deriving Site-specific Sediment Quality Criteria for the Protection of Benthic
Organisms" (U.S. EPA, 1993b). The SQC may be underprotective where the toxicity of other
chemicals are additive with the SQC chemical or species-of unusual sensitivity occur at the site.
This document presents the theoretical basis and the supporting data relevant to the
derivation of the SQC for endrin. An understanding of the "Guidelines for Deriving Numerical
National Water Quality Criteria for the Protection of Aquatic Organisms and Their Uses"
(Stephan et al., 1985), response to public comment (U.S. EPA, 1985) and "Technical Basis for
Deriving Sediment Quality Criteria for Nonionic Organic Contaminants for the Protection of
Benthic Organisms By Using Equilibrium Partitioning" (U.S. EPA, 1993a) is necessary in order
to understand the following text, tables and calculations. Guidance for the acceptable use of
SQC values is contained in "Guide for the Use and Application of Sediment Quality Criteria for
Nonionic Organic Chemicals" (U.S. EPA, 1993c).
1.2 GENERAL INFORMATION: ENDRIN
Endrin is the common name of a "broad spectrum" organochlorine
insecticide/rodenticide. It was formulated for use as an emulsifiable concentrate, wettable or
dustable powder and granular product. It has been used with a variety of crops, including
cotton, tobacco, sugar cane, rice and ornamentals. One of its major uses in the United States
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was in the control of lepidopteran larvae on cotton. During recent years its use was increasingly
j
restricted until it was banned on October 10, 1984, in part as a result of its observed toxicity
to non-target organisms, bioaccumulation potential and persistence.
Endrin is a cyclic hydrocarbon having a chlorine substituted methanobridge structure
(Figure 1-1). Chemically, it is the endo-endo stereoisomer of dieldrin, and has similar
physico-chemical properties, except that it is more easily degraded in the environment (Wang,
1988). Endrin is a colorless crystalline solid at room temperature, with a melting point of about
235°C and specific gravity of 1.7 at 20°C. Its vapor pressure is 0.026 mPa (25°C), aqueous
solubility approximately 0.024 mg/L at 25°C, and as discussed subsequently, its log
octanol-water partition coefficient (k>g10KoW) is estimated to be 4.90.
Endrin is toxic to non-target aquatic organisms, birds, bees and mammals (Hartley and
Kidd, 1987). The acute toxicity of endrin ranges from 0.08 to 352 jig/L for freshwater and
0.037 to 790 ftg/L for saltwater organisms (Appendix A). There is little difference between the
acute and chronic toxicity of endrin to aquatic species; acute-chronic ratios range from 1.9 to
4.7 for three species (Table 3-3). Endrin bioconcentrates hi aquatic animals from 1,450 to
10,000 times the concentration in water (U.S. EPA, 1980). The water quality criterion for
endrin (U.S. EPA, 1980) is derived using a Final Residue Value calculated using
bioconcentration data and the FDA action level to protect marketability of fish and shellfish;
therefore, the WQC is not "effects based". The Final Chronic Value (FCV) in the endrin WQC
document (U.S. EPA, 1980) is the recommended concentration protective from direct effects of
endrin on aquatic life. This value is modified in this SQC document, and used to derive the
, SQC.
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a et
ei
MOLECULAR FORMULA
MOLECULAR WEIGHT
DENSITY
MELTING POINT
PHYSICAL FORM
VAPOR PRESSURE
C12H8C160
380.93
1.70 g/cc
235°C
Colorless crystal
0.026 mPa (25°C)
CAS NUMBER: 72-20-8
TSL NUMBER: IO 15750
COMMON NAME: Endrin (also endrine and nendrin)
TRADE NAME: Endrex (Shell); Hexadrin
CHEMICAL NAME: l,2,3,4,10,10,hexachloio-lR,4S,4aS,5nS,6,7R,8R,8aR-
octahydro-6,7-epoxy-l,4:5,8-dimethanoaphthalene (IUPAC)
or
Hexachloroepoxy-octahydro-endo-endo-dimethanonaphthalene
FIGURE 1-1. Chemical structure and physical-chemical properties of endrin.
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1.3 OVERVIEW OF DOCUMENT:
f
Section 1 provides a brief review of the EqP methodology, and a summary of the
physical-chemical properties and aquatic toxicity of endrin. Section 2 reviews a variety of
methods and data useful in deriving partition coefficients for endrin and includes the KQC
recommended for use in the derivation of the endrin SQC. Section 3 reviews aquatic toxicity
data contained in the endrin WQC document (U.S. EPA, 1980) and new data that were used to
derive the FCV used in this document to derive the -SQC concentration. In addition, the
comparative sensitivity of benthic and water column species is examined as the justification for
the use of the FCV for endrin in the derivation of the SQC. Section 4 reviews data on the
toxicity of endrin in sediments, the need for organic carbon normalization of endrin sediment
concentrations and the accuracy of the EqP prediction of sediment toxicity using KQC and an
effect concentration in water. Data from Sections 2, 3 and 4 are used in Section 5 as the basis
for the derivation of the SQC for endrin and its uncertainty. The SQC for endrin is then
compared to STORET (U.S. EPA, 1989b) data on endrin's environmental occurrence in
sediments. Section 6 concludes with the criteria statement for endrin. The references used in
this document are listed in Section 7.
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SECTION 2.
PARTITIONING
2.1 DESCRIPTION OF THE EQUILIBRIUM PARTITIONING METHODOLOGY:
Sediment quality criteria (SQC) are the numerical-concentrations of individual chemicals
which are intended to be predictive of biological effects, protective of the presence of benthic
organisms and applicable to the range of natural sediments from lakes, streams, estuaries and
near coastal marine waters. As a consequence, they can be used in much the same way as water
quality criteria (WQC); ie., the concentration of a chemical which is protective of the intended
use such as aquatic life protection. For nonionic organic chemicals, SQC are expressed as /Lig
chemical/g organic carbon and apply to sediments having ^ 0.2 % organic carbon by dry
weight. A brief overview follows of the concepts which underlie the equilibrium partitioning
(EqP) methodology for deriving SQC. The methodology is discussed in detail in the "Technical
Basis for Deriving Sediment Quality Criteria for Nonionic Organic Contaminants for the
Protection of Benthic Organisms by Using Equilibrium Partitioning" (U.S. EPA, 1993a),
hereafter referred to as the SQC Technical Basis Document.
Bioavailability of a chemical at a particular sediment concentration often differs from one
sediment type to another. Therefore, a method is necessary for determining a SQC based on the
bioavailable chemical fraction in a sediment. For nonionic organic chemicals, the
concentration-response relationship for the biological effect of concern can most often be
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correlated with the interstitial water (i.e., pore water) concentration 0*g chemical/liter pore
water) and not to the sediment chemical concentration (/tg chemical/g sediment) (Di Toro et al.,
1991). From a purely practical point of view, this correlation suggests that if it were possible
to measure the pore water chemical concentration, or predict it from the total sediment
concentration and the relevant sediment properties, then that concentration could be used to
quantify the exposure concentration for an organism. Thus, knowledge of the partitioning of
chemicals between the solid and liquid phases in a sediment is a necessary component for
establishing SQC. It is for this reason that the methodology described below is called the
equilibrium partitioning (EqP) method.
It is shown in the SQC Technical Basis Document (U.S. EPA, 1993a) that the final acute
values (FAVs) in the WQC documents are appropriate for benthic species for a wide range of
chemicals. (The data showing this for endrin are presented in Section 3). Thus, SQC can be
established using the final chronic value (FCV) derived using the WQC Guidelines (Stephan et
al., 1985) as the acceptable effect concentration in pore or overlying water (see Section 5), and
the partition coefficient can be used to relate the pore water concentration to the sediment
concentration via the partitioning equation. This acceptable concentration in sediment is the
SQC.
The calculation is as follows: Let FCV (/tg/L) be the acceptable concentration hi water
for the chemical of interest; then compute the SQC using the partition coefficient, (Kp)
(L/KgKdmicni)> between sediment and water:
SQC = KP • FCV (2-1)
This is the fundamental equation used to generate the SQC. Its utility depends upon the
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existence of a methodology for quantifying the partition coefficient, Kp.
Organic carbon appears to be the dominant sorption phase for nonionic organic chemicals
in naturally occurring sediments and thus controls the bioavailability of these compounds in
sediments. Evidence for this can be found in numerous toxicity tests, bioaccumulation studies
and chemical analyses of pore water and sediments (Di Toro et al., 1991). The evidence for
endrin is discussed in this section and in section 4. The organic carbon binding of a chemical
in sediment is a function of that chemical's organic carbon partition coefficient (Koc) and the
weight fraction of organic carbon in the sediment (foe). The relationship is as follows:
(2-2)
It follows that:
SQCoc = KOC • FCV (2-3)
where SQCOC is the sediment quality criterion on a sediment organic carbon basis.
KOC is not usually measured directly (although it can be done, see section 2.3).
Fortunately, KQC is closely related to the octanol-water partition coefficient (KQW) (equation 2-5)
which has been measured for many compounds, and can be measured very accurately. The next
section reviews the available information on the KoWfor endrin.
2.2 DETERMINATION OF KQW FOR ENDRIN:
Several approaches have been used to determine KQW for the derivation of a SQC, as
discussed in the SQC Guidelines. At the U.S. EPA, Environmental Research Laboratory at
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Athens, GA (ERL,A) three methods were selected for measurement and two for estimation of
KQW values. The measurement methods were shake-centrifugation (SC), generator column
(GCol), slow-stir-flask (SSF), and the estimation methods were SPARC (SPARC Performs
Automated Reasoning in Chemistry; Karickhoff et al., 1989) and CLOGP (Chou and Jurs,
1979). Data were also extracted from the literature. The SC method is a standard procedure in
the Organization for Economic Cooperation and Development (OECD) guidelines for testing
chemicals, therefore, it has regulatory precedence.
In the examination of the literature data for endrin, primary references were found listing
measured log10KoW values ranging from 4.40 to 5.19 (Table 2-1). Two primary references were
found for estimated values in the literature, 3.54 and 5.6 (Table 2-1). The range of reported
values for endrin is significantly greater than the range of values for some other compounds.
TABLE 2-1. ENDRIN MEASURED AND ESTIMATED LOG1(VKow VALUES.
METHOD LOG10Kow REFERENCE
Measured 4.40 Rapaport and Eisenreich, 1984
Measured 4.92 Ellington and Stancil, 1988
Measured 5.01 Eadsforth, 1986
Measured '5.19 DeBruijn et al., 1989
Estimated . 3.54 Mabey et al., 1982
Estimated 5.40 SPARC*
Estimated 5.60 Neeley et al., 1974
"SPARC is from SPARC Performs Automated Reasoning in Chemistry., (Karickhoff et al.,
1989).
A KQW value for SPARC is also included in Table 2-1. SPARC is a computer expert
system under development at ERL,A, and the University of Georgia, at Athens. For more
information on SPARC see U.S. EPA (1993a). The SPARC estimated log10KoW value for
2-4
-------
endrin is 5.40. . ..
We had little confidence in the available measured or estimated values for K
-------
TABLE 2-2. SUMMARY OF LOGioKoW' VALUES FOR ENDEIN MEASURED BY THE
U.S. EPA, ENVIRONMENTAL RESEARCH LABORATORY, ATHENS, GA.
SHAKE-
CENTRIFUGATION
(SO
. 4.65
4.91
4.79
4.76
4.84
4.83
4.84
4.83
GENERATOR
COLUMN
fGCott
4.67
5.01
4.73
'4.62
5.09
5.28«
SLOW STIR
FLASK
fSSF)
4,.86
4,.59
4..97
4.95
5.02
4.82
5.04
4.91
5.07
4.93
4.96
4.78
Mean" 4.80b
4.87"
4.92b
•Value considered outlier and omitted from mean computation.
bLog10 of mean of measured values.
2.3 DERIVATION OF KQC FROM ADSORPTION STUDIES:
Two types of experimental measurements of the organic carbon partition coefficient are
available. The first type involves experiments which were designed to measure the partition
coefficient in particle suspensions. The second type of measurement is from sediment toxicity
tests in which sediment endrin, sediment organic carbon (OC) and freely-dissolved endrin in
pore water were used to compute KQC; dissolved organic carbon (DOC) associated endrin was
not included.
2.3.1 KOC FROM PARTICLE SUSPENSION STUDIES:
Laboratory studies to characterize adsorption are generally conducted using particle
2-6
-------
suspensions. The high concentrations of solids and turbulent conditions necessary to keep the
mixture in suspension make data interpretation difficult as a result of a particle interaction effect.
This effect suppresses the partition coefficient relative to that observed for undisturbed sediments
(Di Toro, 1985; Mackay and Powers, 1987).
Based on analysis of an extensive body of experimental data for a wide range of
compound types and experimental conditions, the particle interaction model (Di Toro, 1985)
yields the following relationship for estimating Kp:
(2-4)
1 + mf K / U
where m is the particle concentration in the suspension (kg/L), and % = 1.4, an empirical
constant. In this expression the KQC is given by:
logioKoc = 0.00028 + 0.983 log10KoW (2-5)
Figure 2-1 compares observed partition coefficient data for the reversible component with
calculated values estimated with the particle interaction model (Equation 2-4 and Equation 2-5)
for a wide range of compounds (Di Toro, 1985). The endrin datum (Sharom et-al., 1980) is
highlighted on this plot. The observed log10Kj, of 2.04 reflects significant particle interaction
effects. The observed partition coefficient is about nine times lower than the value expected in
the absence of particle effects ( i.e. logioKp = 2.98 from focKoc = 958 L/kg). KQC was
computed from Equation 2-5).
In the absence of particle effects, KQC is related to KQW via Equation 2-5. For log10KoW
= 4.92 (see section 2.2), this expression results in an estimate of lognjBCoc = 4.84.
2-7
-------
Partition Coefficient
Reversible Component
0)
.*
D)
O
0)
>
i_
-------
2.3.2 KOC FROM SEDIMENT TOXICITY TESTS:
j
Measurements of KQC are available from the sediment toxicity tests using endrin (Nebeker
et al., 1989; Schuytema et al., 1989; Stehly, 1991). These tests were with different freshwater
sediments having a range of organic carbon contents of 0.07 to 11.2 percent (Table 4-1;
Appendix B). Endrin concentrations were measured in the sediment and pore waters providing
the data necessary to calculate the partition coefficient for an undisturbed bedded sediment. In
the case of the data reported by Schuytema et al. (1989), the concentration of endrin in the
overlying water at the end of the 10-day experiment was used. Nebeker et al. (1989)
demonstrated using their methodology, that overlying water and pore water endrin concentrations
were similar.
The upper panel of Figure 2-2 is a plot of the organic carbon-normalized sorption
isotherm for endrin, where the sediment endrin concentration frig/goc) is plotted versus
(dissolved) pore water concentration G*g/L). The data used to make this plot are included in
Appendix B. The line of unity slope corresponding to the legume = 4.84 derived from SSF
is compared to the data. A probability plot of the observed experimental log10Koc values is
shown in the lower panel of Figure 2-2. The log10Koc values are approximately normally
distributed with a mean of log10Koc = 4.67 and a standard error of the mean of 0.036. This
value agrees with the Iog10 KQC = 4.84, which was computed from the SSF determined (Section
2.2) endrin log10KoW of 4.92 using Equation 2-5.
2.4 SUMMARY OF DERIVATION OF Koc FOR ENDRIN:
The KQC selected to calculate the SQC for endrin is based on the regression of log10Koc
2-9
-------
10000 E-T-TTT
ENDRIN
O 1000
cc
'o
' OB
^
3§
55
to
0.1
Mill I I I I IIIII
I 11111 l l l l l 11 lu" i i i i 11
LEGEND
T -
Nebeker et al., 1989
Schuytemo et al., 1989 =
Stehly, 1991
I l I I I III) I I I I I III! L
HIM
I I i Hill 1
lilt
001 0,1 1 10 100 1000
PORE WATER CONCENTRATION (ug/L)
6.0
6JS
4J5
& 4JO
3JS
3.0
t I Illltlt I I I I Mill
mill 11 i
i 11 IIIIH i i i 11 nil
i i
i- i nun i i i mini i
0.1
10 20 60 80 CO
PROBABILITY
99
Figure 2-2.
Organic caibon-normalized sorption isotherm for endiin (top) and probability plot
of KQC (bottom) from sediment toxicity tests conducted by Nebeker et. al, (1989),
Schuytema et al. (1989) and Stehly (1991). The line in the top panel represents
the relationship predicted with a log K^ of 4.84, that is C,iOC=Koc*Cd.
2-10
-------
to log10KoW (Equation 2-5), using the endrin logy^ow of 4.90 recently measured by ERL,A.
i
This approach rather than the use of the K^ from the toxicity tests was adopted because the
regression equation is based on the most robust data set available that spans a broad range of
chemicals and particle types, thus encompassing a wide range of KQW and foe- The regression
equation yields a log10Koc of 4.84. This value is in agreement with the logics of 4.67
measured in the sediment toxicity tests.
2-11
-------
-------
SECTION 3
TOXICITY OF ENDRIN: WATER EXPOSURES
3.1 TOXICITY OF ENDRIN IN WATER: DERIVATION OF ENDRIN WATER QUAIITY.
CRITERIA . .
The equilibrium partitioning (EqP) method for derivation of sediment quality criteria
(SQC) uses the endrin water quality criterion (WQC) Final Chronic Value (FCV) and partition
coefficients (K^.) to estimate the maximum concentrations of nonionic organic chemicals in
. sediments, expressed on an organic carbon basis, that will not cause adverse effects to benthic
(epibentbic and infaunal) organisms. For this document, life stages of species ckssed as benthic
are either species that live in the sediment (infauna) or on the sediment surface (epibentbic) and
obtain their food from either the sediment or water column (U.S. EPA, 1989c). In this section
(1) the FCV from the endrin WQC document (U.S. EPA, 1980) is revised using new aquatic
toxicity test data, and (2) the use of this FCV is justified as the effects concentration for SQC
derivation.
3.2 ACUTE TOXICITY - WATER EXPOSURES:
One hundred and one standard acute toxicity tests with endrin have been conducted on
45 freshwater species from 35 genera (Figure 3-1; Appendix A). Overall genus mean acute
values (GMAVs) range from 0.15 to > 165 /*g/L. Fishes, amphipods, ostracods, glass shrimp,
0
mayflies, stoneflies, caddisflies, damselflies and dipterans were most sensitive; overall GMAVs
for the most sensitive generation of these taxa range from 0.15 to 4.7 /tg/L. Thirty-nine tests
on the benthic life-stages of 25 species from 21 genera are contained in this database (Figure
3-1
-------
3-1; Appendix A). Benthic organisms were among both the most sensitive, and most resistant
,•
freshwater species to endrin. Of the epibenthic species, amphipods, grass shrimp, mayflies,
stonefiies, caddisflies, damselflies and dipterans are most sensitive; GMAVs range from 0.25
to 5.9 jtg/L. Infaunal species tested included endrin sensitive ampMpods, stonefiies, mayflies,
dipterans and an ostracod (LC50s range from 0.54 to 4.6 /tg/L) the endrin-tolerant mayfly,
Hexagenia bilineata (LC50=63 jig/L) and the oligochaete, Lumbriculus variegatus. (LC50> 165
Atg/L). The Final Acute Value (FAV) derived from the overall GMAVs (Stephan et al. 1985)
for freshwater organisms is 0.19 /tg/L (Table 3-2).
Thirty-seven acute toxicity tests have been conducted on 21 saltwater species from 19
genera (Appendix A). Overall GMAVs range from 0.037 to 790 /*g/L. Fishes and a penaeid
shrimp were most sensitive; however, only 7 of 21 species tested were invertebrates. Within
this database there are results from 26 tests on benthic life-stages of 14 species from 12 genera
(Figure 3-2; Appendix A). Benthic organisms are among both the most sensitive and most
resistant saltwater genera to endrin. The most sensitive benthic jjpecies is the commercially
important pink shrimp, Penaeus duorarum. with a flow-through 96-hour LC50 of 0.037 /*g/L
based on measured concentrations. Other benthic species for which there are data appear less
sensitive; GMAVs range from 0.094 to 12 jig/L. The FAV for saltwater species is 0.033 jtg/L
(Table 3-2).
3.3 CHRONIC TOXICITY - WATER EXPOSURES:
Life-cycle toxicity tests have been conducted with the freshwater fiagfish (Jordanella
floridael and fathead minnow (Pimephales promelas'). and the saltwater sheepshead minnow
3-2
-------
1000
100
1
HI
_l
tu
z
1U
5
CO
LU
10
0.1
A Arthropods
D Other invertebrates
O Fishes
Lumbriculus '(A) \
Hexagenia (J)\
Copepod(X)\j
Daphnia (L)4
Simocephalus (X),
Orconectes (J)
Tipula (J)
Baetus (J)
Jordanella (J)
Tanytarsus (L)
Pteronarcys (A) '
Gasterosteus (U)
lctalurus(J)
Oncorhynchus (J) '
Pimephales (J)
AtherixfJ) .
^A Ephemerella (X)
Gammarus (A)
Rana (L)
r Ischnura (J)
Cypridopsis (A)
, *Palaemonetes (A)
Poecilia (X)
Carassius (J)
Micropterus (J)
gyprinus (J)
\ A^Jl^,
^_ Brachycentrus (X)
_ Acroneuria (L)
. Classenia(A)
Lepomis (J)
'Perca (J)
r Gambusia (J)
Pteronarcella (L)
^Salvelinus (J)
J_
J.
J_
J_
20 40 60 80
PERCENTAGE RANK OF FRESHWATER GENERA
100
Figure 3-1. Genus mean acute values, of freshwater species vs. percentage rank of their
sensitivity. Symbols representing benthic species are solid, those representing
water column species are open. Asterisks indicate greater than values. A =
adult; J = juvenile; U = unspecified life stage, habitat unknown; X =
unspecified life stage. 3-3
-------
1000
100
10
'i
ui
I
z
I
UJ
CJ
0.1
0.01
Figure 3-2.
A Arthropods
0 Other Invertebrates
O Fishes
Crassostrea IE,L)
Gasterosteus (J)
Poedlla (A)
Anguilla(J)
Cymatogaster(J)
Cyprinodon (J,A)
Sphaeroides(A)
Crangon (A)
Palaemon (A)
Palaemonetes (A)
Fundulus (A)
Morone (J)
Micrometrvs (A)
nha(assoma(A.)
fMenidia(J)
'Oncorhynchus (J)
" Penaeus (A)
_L
20 40 60 80
PERCENTAGE RANK OF SALTWATER GE-NERA
100
Genus mean acute values, of saltwater species vs. percentage rank of their
sensitivity. Symbols representing benthic species an; solid, those representing
water column species are open. Asterisks indicate greater than values. E =
embryo, J = juvenile.
3-4
-------
(Cyprinodon variegatus) and grass shrimp (Palaemonetes pugio) (Table 3-1; 3-2). Each of these
; •
species, except for P. promelas. have one or more benthic life stages.
Two life-cycle toxicity tests have been conducted with J. floridae. The concentration-
response relationships were almost identical among the tests. Hermanutz (1978) observed ah
8% reduction in growth (length) and a 79% reduction in number of eggs spawned per female
in 0.3 jig/L endrin relative to response of control fish; progeny were unaffected (Table 3-2).
Neither parental or progeny (Ft) generation J. floridae were significantly affected when exposed
to endrin concentrations from 0.051 to 0.22 jtg/L. In the second life-cycle test, Hermanutz et
al. (1985) observed a 51 % decrease in reproduction in parental fish exposed to 0.29 /*g/L endrin
and reductions of 73% in survival, 18% in (growth) length and 92% in numbers of eggs per
female in 0.39 jtg/L. No significant effects were detected in parental or progeny generation
fiagfish in 0.21 /tg/L.
The effect of endrin on P. promelas in a life-cycle test was only marginally enhanced
when exposure was via water and diet vs. water-only exposures (Jarvinen and Tyo, 1978).
Parental fish in 0.25 ng/L in water-only exposures exhibited about 60% mortality relative to
controls. Mortality of Ft progeny was 70% in 0.14 jig/L, the lowest concentration tested, and
85 % in 0.25 /*g/L. Tissue concentrations increased marginally in fish exposed to the water and
diet treatment relative to fish in water-only exposures. Effects were observed at all
concentrations tested.
One saltwater invertebrate species, P. pugio. has been exposed to endrin in a partial life-
cycle toxicity test (Tyler-Schroeder, 1979). Mortality of parental generation shrimp generally
increased as endrin concentrations increased from 0.11 to 0.79 jig/L. Onset of spawning was
3-5
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delayed, duration of spawning was lengthened and the number of female P. pugio spawning was
less in all exposure concentrations from 0.03 to 0.79 jtg/L. These effects on reproduction may
.not be important because embryo production and hatching success were apparently not affected.
Larval mortality and time to metamorphosis increased and growth of juvenile progeny decreased
in endrin concentrations ^0.11 jtg/L.
C_. variegatus exposed to endrin in a life-cycle toxicity test (Hansen et al., 1977) were
affected at endrin concentrations similar to those affecting the two freshwater fishes described
above. £. variegatus embryos exposed to 0.31 and 0.72 pg/L. hatched early; all fry exposed to
0.72 /*g/L, and about half those exposed to 0.31 /
-------
calculating the sediment quality criterion for protection of benthic species. The FCV for
T '^ ';&«; s$
:
freshwater organisms of 0.061 /ig/L is the quotient of the FAV of 0.19 /*g/L and the FACR of
3.1. Similarly, the FCV for saltwater organisms of 0.011 /tg/L is the quotient of the FAV of
0.033 /*g/L and the FACR of 3.1.
3.4 APPLICABILITY OF THE WATER QUALITY CRITERION AS THE EFFECTS
CONCENTRATION FOR DERIVATION OF THE ENDRIN SEDIMENT
QUALITY CRITERION:
The use of the FCV (the chronic effects-based WQC concentration) as the effects
concentration for calculation of the EqP-based SQC assumes that benthic (infaunal and
epibenthic) species, taken as a group, have sensitivities similar to all species tested to derive the
WQC concentration. Data supporting the reasonableness of this assumption over all chemicals
for which there are published or draft WQC documents are presented in Di Toro et al. (1991),
and the SQC Technical Basis Document (U.S. EPA, 1993a). The conclusion of similarity of
sensitivity is supported by comparisons between (1) acute values for the most sensitive benthic
and acute values for the most sensitive water column species for all chemicals; (2) acute values
for all benthic species and acute values for all species in the WQC documents across all
chemicals after standardizing the LC50 values; (3) FAVs calculated for benthic species alone and
FAVs calculated for all species in the WQC documents; and (4) individual chemical comparisons
of benthic species vs. all species. Only in this last comparison are endrin-specific comparisons
in sensitivity of benthic and all (benthic and water-column) species conducted. The following
paragraphs examine the data on the similarity of sensitivity of benthic and all species for endrin.
For endrin, benthic species account for 21 out of 35 genera tested in freshwater, and 12
3-9
-------
out of 19 genera tested in saltwater (Figures 3-1, 3-2). An initial test of the difference between
r
the freshwater and saltwater FAVs for all species (water column and benthic) exposed to endrin
was performed using the Approximate Randomization method (Noreen, 1989). The Approximate
Randomization method tests the significance level of a test statistic when compared to a
distribution of statistics generated from many random subsamples. The test statistic in this case
is the difference between the freshwater FAV, computed from the freshwater (combined water
column and benthic) species LC50 values, and the saltwater FAV, computed from the saltwater
(combined water column and benthic) species LC50 values (Table 3-3). In the Approximate
Randomization method, the freshwater LC50 values and the saltwater LC50 values are combined
into one data set. The data set is shuffled, then separated back so that randomly generated
"freshwater" and "saltwater" FAVs can be computed. The LC50 values are separated back
i
such that the number of LC50 values used to calculate the sample FAVs are the same as the
number used to calculate the original FAVs. These two FAVs are subtracted and the difference
used as the sample statistic. This is done many times so that the sample statistics make up a
distribution that is representative of the population of FAV differences (Figure 3-3). The test
statistic is compared to this distribution to determine it's level of significance. The null
hypothesis is that the LC50 values that comprise the saltwater and freshwater data bases are not
different. If this is true, the difference between the actual freshwater and saltwater FAVs should
be common to the majority of randomly generated FAV differences. For endrin, the test-statistic
falls at the 99 percentile of the generated FAV differences. Since the probability is greater than
95%, the hypothesis of no significant difference in sensitivity for freshwater and saltwater
species is rejected (Table 3-3).
3-10
-------
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PROBABILITY
DISTRIBUTION OF FAV DIFFERENCE STATISTICS
Figure 3-3. Probability distribution of FAV difference statistics to compare water-only data
from freshwater vs. saltwater (upper panel) and benthic vs. WQC (lower panel)
data.
3-11
-------
TABLE 3-3. RESULTS OF APPROXIMATE RANDOMIZATION TEST FOR
THE EQUALITY OF THE FRESHWATER AND SALTWATER FAV
DISTRIBUTIONS FOR ENDRIN AND APPROXIMATE
RANDOMIZATION TEST FOR THE EQUALITY OF BENTHIC AND
COMBINED BENTHIC AND WATER COLUMN (WQC) FAV
DISTRIBUTIONS.
Comparison
Habitat or Water Type* AR Statistic* Probability6
Fresh
vsSalt
Fresh (35)
Salt (19)
.156
99
Fresh:
Benthic
vs Water
Column +
Benthic (WQC)
Salt:
Benthic
vs Water
Column +
Benthic (WQC)
Benthic (21) WQC (35)
-.045
Benthic (12) WQC (19)
.010
66
"Values in parentheses are the number of LC50 values used in the comparison.
bAR statistic = FAV difference between original compared groups.
°Pr(AR statistic theoretical ^ AR statistic observed) given that the samples
came from the same population.
Since freshwater and saltwater species do not show similar sensitivity, separate tests were
conducted for freshwater and saltwater benthic species. For the species from each water type,
a test of difference in sensitivity for benthic and all (benthic and water column species combined,
hereafter referred to as "WQC") organisms using the Approximate Randomization method was
j
performed. The test statistic in this case is the difference between the WQC FAV, computed
from the WQC LC50 values, and the benthic FAV, computed from the benthic organism LC50
3-12
-------
values. This is slightly different than the previous test for saltwater and freshwater species. The
•f .-. • •> 4
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.difference is that saltwater and freshwater species represent two separate groups. In this test the
benthic organisms are a subset of the WQC organisms set. In the Approximate Randomization
method for this test, the number of data points coinciding with the number of benthic organisms
are selected from the WQC data set. A "benthic" FAV is computed. The original WQC FAV
and the "benthic" FAV are then used to compute the difference statistic. This is done many
times and the distribution that results is representative of the population of FAV difference
statistics. The test statistic is compared to this distribution to determine its level of significance.
The probability distribution of, the computed FAV differences are shown in the bottom two
panels of Figure 3-3. The test statistic for this analysis falls at the 7 percentile for freshwater
organisms and the 66 percentile for saltwater organisms. Therefore the hypothesis of no
difference in sensitivity is accepted (Table 3-3). This analysis suggests that the FCV for endrin
based on data from all tested species is an appropriate effects concentration for benthic
organisms.
3-13
-------
-------
SECTION 4
TOXICITY OF ENDRIN (ACTUAL AND PREDICTED): SEDIMENT EXPOSURES
4.1 TOXICITY OF ENDRIN IN SEDIMENTS:
The toxicity of endrin spiked into sediments has been tested with two saltwater species
(a polychaete and the sand shrimp) and four freshwater species (two tubificid worms and two
amphipods) (Table 4-1). The most common endpoint measured was mortality, however, impacts
on sublethal endpoints such as growth, sediment avoidance and sediment reworking rate have
been reported. All concentrations of endrin in sediments or interstitial water where effects were
observed are greater than SQC or FCV concentrations reported in this document. Details about
exposure methodology are provided because, unlike aquatic toxicity tests, sediment testing
methodologies have not been standardized. Generalizations across species or sediments are
limited because of the limited number of experiments.
The only saltwater experiments that tested endrin-spiked sediments were conducted by
McLeese et al. (1982) and McLeese and Metcalfe (1980). These began with clean sediments
that were added to endrin-coated beakers just prior to the addition of test organisms. This is in
marked contrast to tests with freshwater sediments that were spiked with endrin days or weeks
prior to test initiation. As a result, the endrin concentrations in the sediment and overlying
4-1
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water varied greatly over the course of these saltwater experiments and exposure conditions are
uncertain. In addition, transfer of test organisms to freshly prepared beakers every 48 hours
further complicates interpretation of results of McLeese et al. (1982) because exposure
conditions are uncertain.
McLeese et al. (1982) tested the effects of endrin on the polychaete worm, Nereis virens..
in sediment with 2 % TOC (17 % sand and 83 % silt and clay) in 12 day toxicity tests. Only two
of five worms died in 28 /tg/g dry wt. sediment, the highest concentration tested. McLeese and
Metcalfe (1980) tested the effects of endrin in sand with a TOC content of 0.28% on the sand
shrimp, Crangon septemspinosa. The 4 day LC50 was 0.047 ug/g dry wt. sediment, and 16.8
ug/goc- Concentrations of endrin in water overlying the sediment were sufficient to explain the
observed mortalities of sand shrimp in sediments.
The effects of endrin-spiked sediments from Lake Michigan on oligochaete worms has
been studied by Keilty et al. (1988a,b) and Keilty and Stehly (1989). For all tests, sediments
were dried, passed through a 0.25 mm sieve, reconstituted with lake water, spiked with endrin
dissolved in acetone, and stirred for 24 hours. The water (containing the carrier) was aspirated
off, new overlying water added, and sediments were placed into individual beakers for 72 hours
before the worms were added.
Keilty et al. (1988a) examined the effects of endrin-spiked sediment on sediment
avoidance and mortality of two species of oligochaete worms in replicate 4 day exposures (Table
4-1). Four day LC50 values for five tests with Stylodrilus heringianus averaged 2,220 /ig
endrin/g dry wt. sediment; range 1,050 to 5,400 /*g/g. Four day LC50 values for three tests
with Limnodrilus hoffmeisteri averaged 3,390 pg/g dry wt. sediment; range 2,050 to 5,600
4-5
-------
/zg/g. Four day LC50 values from these tests averaged 194,000 ^g/g^ for L.. hoffmeisteri and
t
127,000 fig/goe for S.. heringianus. Data using this test method suggest within laboratory
variabilities of factors of 3 to 5 in LC50 values for the same sediment. Sediment avoidance was
seen at much lower concentrations. Over all tests burrowing was markedly reduced at ^ 11.5
•jiig/g and possibly at £» 0.54 pg/g. Concentrations where 50% of the worms failed to burrow
into sediments (EC50) were 59.0 /tg/g (3,371 jig/goc) for L,. hoffmeisteri and 15.3 and 19 jtg/g
dry wt. (874 and 1,086 pg/goc) sediment for two tests using S. heringianus. Keilty et al.
(1988b) observed 18% mortality of S. heringianus in 11.5 /tg/g after a 54 day exposures and
26% mortality in 42.0 /tg/g. Sediment reworking rate was reported to be significantly reduced
or increased in sediments containing 5: 0.0031 jig/g. Dry weights of worms in J>.2.33 >g/g
were reduced after 54 days. Keilty and Stehly (1989) observed no effect of a single, nominal
concentration of 50 /zg/g dry wt. sediment on protein utilization by SL heringianus over the 69
day exposure period. However dry weights of worms were significantly reduced.
Nebeker et al. (1989) and Schuytema et al. (1989) in a series of experiments important
to the development of sediment quality criteria, exposed the amphipod Hyalella azteca to two
of the same endrin-spiked sediments; one with a TOC of 11 % and the other 3 %. Nebeker et
al. (1989) mixed these two sediments to obtain a third sediment with a TOC of 6.1%.
Sediments were shaken for 7 days in endrin-coated flasks, and subsequently for 62 days in clean
flasks. The 10 day LCSO's for amphipods in the three sediments tested by Nebeker et al. (1989)
did not differ when endrin concentration was on a wet or dry weight basis. The LC50 values
decreased with increase in organic carbon when the concentration was on an organic carbon
basis (Table 4-1). The authors conclude that endrin data do not support equilibrium partitioning
4-6
-------
theory. LC50's normalized to dry weight (4.4 to 6.0 /tg/g) or wet weight (0.9 to 1.0 /tg/g)
- '•"*,' '- 5$,
differed by less than a factor of 1.5 over a 3.7 fold range of TOC. In contrast, the organic
carbon normalized LCSOs ranged from 53.6 to 147 uglg^., a factor of 2.7 (Table 4-1).
Schuytema et al. (1989) stored an aliquot of sediments dosed by Nebeker et al. (1989)
for an average of 9 months and then froze one-half for 2 weeks; the other half was stored at 4°C
for 2 weeks. Endrin's toxicity to H. azteca did not differ in refrigerated and frozen sediments
from Mercer Lake, OR. and differed minimally (LC50=5.1 vs 7.7 /*g/g dry wt. sediment) in
sediments from Soap Pond. In contrast to the findings of Nebeker et al. (1989), Schuytema et
al. (1989) using the same sediments observed higher LC50 values in four tests with Mercer Lake
sediments (9.8, 10.3, 19.6 and 21.7 /tg/g dry wt. sediment), which had a TOC of 11%, than
LC50 values from two tests using Soap Creek sediments (5.1 and 7.7 /tg/g dry wt. sediment)
where TOC was 3%.
The need for organic carbon normalization of the concentrations of nonionic organic
chemicals in sediments is presented in the SQC Technical Basis Document (U.S. EPA, 1993a).
The need for organic carbon normalization for endrin is supported by the results of spiked-
sediment toxicity tests described above. When examined individually, experiments in which H.
azteca were exposed to the same sediments by both Nebeker et al. (1989) and Schuytema et al.
(1989) provide contradictory data concerning the need for organic carbon normalization (Tables
4-1). Nebeker et al. (1989) observed no change in toxicity and Schuytema et al. (1989) a
decrease in toxicity on a dry weight basis. However, mean LC50 values calculated for
individual experiments from both studies were similar when concentrations were normalized by
organic carbon content. The LC50 was 109 /tg/goc (5 tests) for sediments from Mercer Lake
4-7
-------
having a TOG of 11 % and 186 jig/g^ (3 tests) for sediments from Soap Creek Pond having 3 %
;
organic carbon. The lack of consistent evidence supporting organic carbon normalization in the
individual tests (Nebeker et al., 1989), is in contrast with evidence supporting normalization
overall tests with the same sediments spiked with endrin, is most likely because organic carbon
concentrations differed by less than a factor of four and variability inherent in these tests limited
the capacity for discrimination. Sediments tested by Stehly (1992) further provide strong
evidence which also supports the need for normalization for endrin (Table 4-1). The organic
carbon concentrations for these sediments ranged from 0.07 to 1.75% (a factor of 25). On a
dry weight basis, 4-day LC50 values for Diporeia sp. ranged from 0.012 to 0.224 /tg/g (a factor
of 18.7). The organic carbon normalized LCSOs were within a factor of 2.4; range 12.8 to 31.3
/ig/goc-
Although it is important to demonstrate that organic carbon normalization is necessary
if SQC are to be derived using the EqP approach, it is fundamentally more important to
demonstrate that 'Koc and water only effects concentrations can be used to predict the effects
concentration for endrin and other nonionic organic chemicals on an organic carbon basis for
a range of sediments. Evidence supporting this prediction for endrin and other nonionic organic
chemicals follows in Section 4.3.
4.2 CORRELATION BETWEEN ORGANISM RESPONSE AND PORE WATER
CONCENTRATION:
One corollary of the EqP theory is that pore water LCSO's for a given organism should
be constant across sediments of varying organic carbon content (U.S. EPA, 1993a). Appropriate
;
pore water LC50 values are available from two studies using endrin (Table 4-1). Nebeker et
4-8
-------
al. (1989) found 10 day LC50 values for endrin based on pore water concentrations ranged 1.8
.• '* i; >,
to 2.1 /tg/L for EL azteca exposed to three sediments. Overlying water LC50 values from these
static tests and those conducted using the same sediments by Schuytema et al. (1989) were
similar; 1.1 to 3.9 /tg/L. Stehly (1992) found that 10 day pore water LC50 values for Diporeia
sp. ranged from 0.63 to 2.2 jig/L (a factor of 3.5); this is considerably less than the range in
*
dry wt. LCSO's, 0.012 to 0.224 /tg/g (a factor of 18.7), for three sediments from Lake
Michigan having 0.07 to 1.75% organic carbon.
A more detailed evaluation of the degree to which the response of benthic organisms can
be predicted from toxic units of substances hi pore water can be made utilizing results from
toxicity tests with sediments spiked with other substances, including acenaphthene and
phenanthrene (Swartz, 1991), endrin (Nebeker et al., 1989; Schuytema et al., 1989), dieldrin
(Hoke 1992), fluoranthene (Swartz et al., 1990, DeWitt et al., 1992), orkepone (Adams et al.,
1985) (Figure 4-1; Appendix B). The data included in this analysis come from tests conducted
at EPA laboratories or from tests which utilized designs at least as rigorous as those conducted
at the EPA laboratories. Tests with acenaphthene and phenanthrene used two saltwater
amphipods (J^jocheirus plumulosus and Eohaustorius estuarius). Tests with fluoranthene used
a saltwater amphipod (Rhepoxynius abronius') and marine sediments. Freshwater sediments
spiked with endrin were tested using the amphipod (H. azteca): the midge Chironomus tentans
was tested using kepone. Figure 4-1 presents the percentage mortalities of the benthic species
tested in individual treatments for each chemical versus "pore water toxic units" (PWTUs) for
all sediments tested. PWTUs are the concentration of the chemical in pore water G*g/L) divided
by the water only LC50 (jt/L). Theoretically, 50% mortality should occur at one interstitial
4-9
-------
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4-10
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water toxic unit. At concentrations below one PWTU there should be less than 50% mortality,
i
.and at concentrations above one PWTU there should be greater than 50% mortality. Figure 4-1
shows that at concentrations below one PWTU mortality was generally low, and increased
sharply at approximately one PWTU. Therefore, this comparison supports the concept that
interstitial water concentrations can be used to predict the response of an organism to a chemical
that is not sediment-specific. This concept was not used to derive sediment quality criteria
because of the complexation of non-ionic organic chemicals with pore water DOC (Section 2)
and the difficulties of adequately sampling pore waters.
4.3 TESTS OF THE EQUILIBRIUM PARTITIONING PREDICTION OF SEDIMENT
TOXICITY:
SQC derived using the EqP approach utilize partition coefficients and FCVs from WQC
documents to derive the SQC concentration for protection of benthic organisms. The partition
coefficient (KoC) is used to normalize exposure concentrations to those which are biologically
available across sediment types. The data required to test the organic carbon normalization for
endrin in sediments are available for one benthic species. Data from tests with water column
species were not included in this analysis. Testing of this component of SQC derivation requires
three elements: (1) a water-only effect concentration, such as a 10-day LC50 value in /*g/L; (2)
an identical sediment effect concentration on an organic carbon basis, such as a 10-day LC50
value in /*g/goc; and (3) a partition coefficient for the chemical, KQC in L/Kgoc. This section
presents evidence that the observed effect concentration in sediments (2) can be predicted
utilizing the water effect concentration (1) and the partition coefficient (3).
Predicted ten-day LC50 values from endrin-spiked sediment tests with H. azteca (Nebeker
4-11
-------
et al.,1989; Schuytema et al., 1989) were calculated (Table 4-2) using the Log,oKoC value of
:
4.84 from Section 2 of this document and the sediment LCSO's (Nebeker et al. 1989) from tests
conducted jointly by these authors. Overall, ratios of actual to predicted LCSOs for endrin
averaged 0.44 (range 0.18 to 0.90) in nine tests with three sediments.
. . A more detailed evaluation of the accuracy and precision of the EqP prediction of the
response of benthic organisms can be made using the results of toxicity tests with amphipods
exposed to sediments spiked with acenaphthene, phenanthrene, dieldrin, endrin, or fluoranthene.
The data included in this analysis come from tests conducted at EPA laboratories or from tests
which utilized designs at least as rigorous as those conducted at the !BPA laboratories. Data from
the kepone experiments are not included because a measured KQW for kepone obtained using the
slow stir flask method is not available. Swartz (1991) exposed the saltwater amphipods E.
estuarius and L. plumulosus to acenaphthene in three marine sediments having organic carbon
contents ranging from 0.82 to 4.2% and to phenanthrene in three marine sediments having
organic carbon contents ranging from 0.82 to 3.6%. Swartz et al. (1990) exposed the saltwater
amphipod IL abronius to fluoranthene in three marine sediments having 0.18, 0.31 and 0.48%
organic carbon. Hoke and Ankley (1991) exposed the amphipod Hyalella azteca to three
dieldrin-spiked freshwater sediments having 1.7, 3.0 and 8.5 % organic carbon and Hoke (1992)
exposed the midge C. tentans to two freshwater dieldrin-spiked sediments having 2.0 and 1.5
% organic carbon. Nebeker et al. (1989) and Schuytema et al. (1989) exposed H. azteca to
three endrin-spiked sediments having 3.0, 6.1 and 11.2% organic carbon. Figure 4-2 presents
the percentage mortalities of amphipods in individual treatments of each chemical versus
"predicted sediment toxic units" (PSTU) for each sediment treatment. PSTUs are the
4-12
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concentration of the chemical in sediments G*g/goc) divided by the predicted LC50 (/tg/goc) i°
sediments {the product of KQC and the 10-day water only LC50). In this normalization, 50%
mortality should occur at one PSTU. At concentrations below one PSTU mortality was
generally low, and increased sharply at one PSTU. The means of the LCSOs for these tests
calculated on a PSTU basis were 1.90 for acenaphthene, 1.16 for dieldrin, 0.44 for endrin, 0.80
for fluoranthene and 1.22 for phenanthrene. The mean value for the five chemicals is 0.99.
This illustrates that the EqP method can account for the effects of different sediment properties
and properly predict the effects concentration in sediments using effects concentration from water
only exposures.
4-15
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-------
SECTIONS
CRITERIA DERIVATION FOR ENDREST
5.1 CRITERIA DERIVATION:
The water quality criteria (WQC) Final Chronic Value (FCV), without an averaging
period or return frequency (See section 3), is used calculate the sediment quality criteria (SQC)
because it is probable that the concentration of contaminants in sediments are relatively stable
over time, thus exposure to sedentary benthic species should be chronic and relatively constant.
This is in contrast to the situation in the water column, where a rapid change in exposure and
exposures of limited durations can occur due to fluctuations in effluent concentrations, dilutions
in receiving waters or the free-swimming or planktonic nature of water column organisms. For
some particular uses of the SQC it may be appropriate to use the areal extent and vertical
stratification of contamination of a sediment at a site in much the same way that averaging
periods or mixing zones are used with WQC.
The FCV is the value that should protect 95% of the tested species included in the
calculation of the WQC from chronic effects of the substance. The FCV is the quotient of the
Final Acute Value (FAV), and the final Acute Chronic Ratio (ACR) for the substance. The
FAV is an estimate of the acute LC50 or EC50 concentration of the substance corresponding to
5-1
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a cumulative probability of 0.05 from eight or more families for the genera for which acceptable
:
acute tests have been conducted on the substance. The ACR is the mean ratio of acute to
chronic toxicity for three or more species exposed to the substance that meets minimum database
requirements. For more information on the calculation of ACRs, FAVs, and FCVs see the
•National Water Quality Criteria Guidelines (Stephan et al., 1985). The FCV used in this
document differs from the FCV in the endrin WQC document (U.S. EPA, 1980) because it
incorporates recent data not included in that document, and omits some data which does not meet
the data requirements established in the WQC Guidelines (Stephan et al., 1985).
The equilibrium partitioning (EqP) method for calculating SQC is based on the following
procedure. If FCV Gig/L) is the chronic concentration from the WQC for the chemical of
interest, then the SQC ftig/g sediment), is computed using the partition coefficient, KP (L/g
sediment), between sediment and pore water:
SQC = KP FCV (5-1)
Since organic carbon is the predominant sorption phase for nonionic organic chemicals
in naturally occurring sediments, (salinity, grainsize and other sediment parameters have
inconsequential roles in- sorption, see sections 2..1 and 4.3) the organic carbon partition
coefficient, (Koc) can be substituted for KP. Therefore, on a sediment organic carbon basis, the
SQCoc (Mg/goc), is:
SQCoc = Koc FCV (5-2)
Since (Koc) is presumably independent of sediment type for non-ionic organic chemicals, so also
is SQCoc. Table 5-1 contains the calculation of the endrin SQC.
The organic carbon normalized SQC is applicable to sediments with an organic carbon
5-2
-------
fraction of f^c S: 0.2%. For sediments with f^ < 0.2%, organic carbon normalization and
} -•" ,:-;.;, ' *'"- - ,i*
SQC may not apply.
TABLE 5-1. SEDIMENT QUALITY CRITERIA FOR ENDRIN.
Type of LogKow LogKoc FCV
Water Body (L/kg) (L/kg) fcg/L) (ftg/goc)
Freshwater 4.92 4.84 • 0.061 4.2'
Saltwater 4.92 4.84 0.011 0.76"
Soc
= (104-84 L/kgocXlO-3 kgoc/gocKO.061 ug endrin/L) = 4.2 /tg endrin/g0
= (104-84 L/kgo^-aO-3 kgoc/gocWO.Oll fig endrin^) = 0.76 jig endrin/goc
Since organic carbon is the factor controlling the bioavailability of nonionic organic
compounds in sediments, SQC have been developed on an organic carbon basis, not on a dry
weight basis. When the chemical concentrations in sediments are reported as dry weight
concentration and organic carbon data are available, it is best to convert the sediment
concentration to /tg chemical/gram organic carbon. These concentrations can then be directly
compared to the SQC value. This facilitates comparisons between the SQC and field
concentrations relative to identification of hot spots and the degree to which sediment
concentrations do or do not exceed SQC values. The conversion from dry weight to organic
carbon normalized concentration can be done using the following formula:
jtg Chemical/goc = Mg Chemical/gDRYWT -f- (% TOC -*• 100)
= /tig Chemical/gDRYWT • 100 •*• % TOC
5-3
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For example, a freshwater sediment with a concentration of 0.1 /*g chemical/gDRY wr and
r
0.5% TOG has an organic caiix>n-norrnalized concentration of 20 /*g/goc (0-1 A*g/gnRYwr * 100
-t- 0.5 = 20 /tg/goc) which exceeds the SQC of 4.2 jtg/goc- Another freshwater sediment with
the same concentration of endrin (0.1 /*g/gDRYwr) but a TOC concentration of 5.0% would have
an organic carbon normalized concentration of 2.0 ftg/goc (0.1 /xg/goRYwr • 100 -5- 5.0 = 2.0
Mg/goc). which is below the SQC for endrin.
In situations where TOC values for particular sediments are not available, a range of
\
TOC values may be used in a "worst case" or "best case" analysis. In this case, the organic
carbon-normalized SQC values (SQCoc) may be "converted" to dry weight-normalized SQC
values (SQCDRYWT.)- This "conversion" must be done for each level of TOC of interest:
SQCDRYWT = SQCoc Otg/goc) • (% TOC -J- 100)
where SQCDRy\vT is the dry weight normalized SQC value. For example, the SQC value for
freshwater sediments with 1 % organic carbon is 0.042 /tg/g:
SQCDRYWr. = 4.2 Atg/goc • 1% TOC 4- 100 = 0.042 ftg/gnRYwr
This method is used in the analysis of the STORET data in section 5.4.
5.2 UNCERTAINTY ANALYSIS:
Some of the uncertainty of the endrin SQC can be estimated from the degree to which the
EqP model, which is the basis for the criteria, can rationalize the available sediment toxicity
data. The EqP model asserts that (1) the bioavailability of non-ionic organic chemicals across
sediments is equal on an organic carbon basis, and (2) that the effects concentration in sediment
Gig/goc) can be estimated from the product of the effects concentrations from water only
exposures (/ig/L) and the partition coefficient KQC (L/kg). The uncertainty associated with the
5-4
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SQC can be obtained from a quantitative estimate of the degree to which the available data
•• '''. '-; ** '•'.
support these assertions.
The data used in the uncertainty analysis are from the water only and sediment toxicity tests
that have been conducted to fulfill the minimum database requirements for the development of
SQC (See Section 4.3 and the Technical Basis Document; U.S. EPA, 1993a). These freshwater
and saltwater tests span a range of chemicals and organisms; they include exposures using water
only and a number of sediments; and they are replicated within each chemical - organisms -
exposure media treatment. These data are analyzed using an analysis of variance (ANOVA) to
estimate the uncertainty (i.e. the variance) associated with each of these sources of variation: that
associated with varying the exposure media; and that associated with experimental error. If the
EqP model were perfect, then there would be only experimental error. Therefore, the
uncertainty associated with the use of EqP is the variance associated with varying exposure
media.
The data used in the uncertainty analysis are illustrated in Figure 4-2. The data for endrin
are summarized in Appendix B. LCSOs for sediment and water-only tests were computed from
these data. The EqP model can be used to normalize the data in order to put it on a common
basis. The LC50s from water-only exposures (LC50W; pg/L) are related to the organic carbon-
normalized LCSOs from sediment exposures (LC50SiOC; /*g/goc) v& the partitioning equation:
LC50S>OC = KocLC50w (5-3)
The EqP model asserts that the toxicity of sediments expressed on an organic carbon basis equals
5-5
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the toxicity in water tests multiplied by the KQC. Therefore, both LC50S(OC and Koc*LC50w
t
are estimates of the true LC50oc for each chemical-organism pair. In this analysis, the
uncertainty of KQC is not treated separately. Any error associated with KQC will be reflected in
the uncertainty attributed to varying the exposure media.
In order to perform an analysis of variance, a model of the random variations is required.
•
•
As discussed above, experiments that seek to validate equation 5-3 are subject to various sources
of random variations. A number of chemicals and organisms have been tested. Each chemical -
organism pair is tested in water only exposures and using different sediments. Let a represent
the random variation due to this source. Also, each experiment is replicated. Let G represent
the random variation due to this source. If the model were perfect, there would be no random
variations other than that due to experimental error which is reflected in the replications. Hence
or represents the uncertainty due to the approximations inherent in the model and G represents
the experimental error. Let (O2 and (oc) corresponding to a water only sediment
exposure; & are the population ln(LC50) for chemical - organism pair i. The error structure is
assumed to be lognormal which corresponds to assuming that the errors are proportional to the
means, e.g. 20%, rather than absolute quantities, e.g. l>g/goc- The statistical problem
is to estimate ^ , (ffj2, and (
-------
estimates (U.S. EPA, 1993a). The results are shown in Table 5-2.
TABLE 5-2: ANALYSIS OF VARIANCE FOR DERIVATION OF SEDIMENT
QUALITY CRITERIA CONFIDENCE LIMITS FOR ENDRIN.
Source of Uncertainty Parameter Value
0*g/goc)
Exposure media
-------
TABLE 5-3. SEDIMENT QUALITY CRITERIA
CONFIDENCE LIMITS FOR ENDRIN.
Sediment Quality Criteria
95 % Confidence Limits (/
Type of SQCoc
Water Body /*g/goc Lower Upper
Freshwater 4.2 2.0 9.1
Saltwater 0.73 0.35 1.6
The organic carbon normalized SQC is applicable to sediments with an organic carbon
fraction of fix: 3: 0.2%. For sediments with f^ < 0.2%, organic carbon normalization does
not apply and the sediment quality criteria do not apply.
5.3 COMPARISON OF ENDRIN SQC AND UNCERTAINTY CONCENTRATIONS TO
SEDIMENT CONCENTRATIONS THAT ARE TOXIC OR PREDICTED TO BE
CHRONICALLY ACCEPTABLE.
Insight into the magnitude of protection afforded to benthic species by SQC
concentrations and 95% confidence intervals can be inferred using effect concentrations from
toxicity tests with benthic species exposed to sediments spiked with endrin and sediment
concentrations predicted to be chronically safe to organisms tested in water-only exposures
(Figures 5-1 and 5-2). This is because effect concentrations in sediments can be predicted from
water-only toxicity data and KOC values (See Section 4). Chronically acceptable concentrations
are extrapolated from Genus Mean Acute Values (GMAV) from water-only, 96-hour lethality
5-8
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1000000
100000
o
o
w
§
O
o
DC
X
O
IU
5
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z
UJ
o
o
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o
01
rr
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10000
1000
100
10
Figure 5-1.
Water-only tests: (96HR LC50 + ACR) Koc
A Arthropods
D Other Invertebrates
O Fishes
ACR. 3.10 4
Sediment Tests: 10d LC50
*k Diooreia sp. - 18.
range 3 tests. 12.8-31.1
® H. azteca- 126 ng/gjjc
range 9 tests « 53.6 - 257
HH L hoffmeisteri - 194000 gg/q^ (4d>
range 3 tests - 117000 - 320000
^ S. heringianus - 127000 Hg/g^. (4d)
range 4 tests - 60000 - 309000
oo
upper: 9.1 jig/goc
lower: 2.0 jig/goc
20
40
60
80
100
PFRCENTAGE RANK OF FRESHWATER GENERA
Comparison between SQC concentrations and 95% confidence intervals, effect
concentrations from benthic organisms exposed to endrin-spiked sediments and
sediment concentrations predicted to be chronically safe in fresh water sediments.
Concentrations predicted to be chronically safe (Predicted Genus Mean Chronic
Values, PGMCV) are derived from the Genus Mean Acute Values (GMAV),
water-only 96-hour lethality tests, Acute Chronic Ratios (ACR) and KOC values'
PGMCV = (GMAV * ACR)Koc. Symbols for PGMCVs are A for arthropods,
O for fishes and D for other invertebrates. Solid symbols are benthic genera;
open symbols water column genera. Arrows indicate greater than values. Error
bars around sediment LC50 values indicate observed range of LCSOs.
5-9
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100000
*0
^ 10000
UJ
§ 1000
o
o
DC
0 100
z
UJ
E
CO
z 10
UJ
C3
PREDICTED i
o
•
f Water-only tests: (96HR LCSO-s-ACR) KOc
A Arthropods
] D Other Invertebrates
O Fishes •
~ Log10 KQC -4.84
: ACR-3.10
•
r
-
; A
f o
: A
•o.A* .
r ,o»
• o °
Q Q upper, i .0 M-y/Qoc
'I'll III! 1
20 40 60 80
PERCENTAGE RANK OF SALTWATER GENERA
100
Figure 5-2. Comparison between SQC concentrations and 95% confidence intervals, effect
concentrations from benthic organisms exposed to endrin-spiked sediments and
sediment concentrations predicted to be chronically safe in salt water sediments.
Concentrations predicted to be chronically safe (Predicted Genus Mean Chronic
Values, PGMCV) are derived from the Genus Mean Acute Values (GMAV),
water-only 96-hour lethality tests, Acute Chronic Ratios (ACR) and KQC values.
PGMCV = (GMAV + ACR)Koc. Symbols for PGMCVs are A for arthropods,
O for fishes and D for other invertebrates. Solid symbols are benthic genera;
open symbols water column genera. Arrows indicate greater than values. Error
bars around sediment LC50 values indicate observed range of LC50s.
5-10
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tests using acute-chronic ratios (ACR). Therefore, it may be reasonable to combine these two
predictive procedures to estimate, for endrin, chronically acceptable sediment concentrations
(Predicted Genus Mean Chronic Value (PGMCV)) from GMAVs (Appendix A), ACRs (Table
3-2) and the KOC (Table 5-1): .
PGMCV = (GMAV + ACR)*Koc (5-7)
Each predicted GMCV for tested fishes, arthropods or other invertebrates tested in water
is plotted against the percentage rank of its sensitivity. Results from toxicity tests with benthic
organisms exposed to sediments spiked with endrin (Table 4-1) are placed in the predicted
GMCV rank appropriate to the test-specific effect concentration. (For example, the 10-day
LC50 for H. azteca. 126 Mg/goc) is placed between the PGMCV of 105 /tg/goc for the mayfly,
Ephemerella. and the PGMCV of jig/goc for the dipteran, Jjpjila.) Therefore, sediment test
LC50 or other effect concentrations are intermingled in this figure with concentrations predicted
to be chronically safe. Care should be taken by the reader in interpreting these data with
dissimilar endpoints. The following discussion of SQC, organism sensitivities and predicted
GMC Vs is not intended to provide accurate predictions of the responses of taxa or communities
of benthic organisms relative to specific concentrations of endrin in sediments in the field. It
is, however, intended to guide scientists and managers through the complexity of available data
relative to potential risks to benthic taxa posed by sediments contaminated with endrin.
The freshwater SQC for endrin (4.2 Mg/goc) is less than 34 of the 35 predicted GMCVs
and all of the LC50 values from spiked sediment toxicity tests. The PGMCV for the fish Perca
(3 pg/goc) is less than the SQC. PGMCVs for 26 of 35 freshwater genera are greater than the
upper 95% confidence interval of the SQC (9.1 /*g/goc)- PGMCVs for nine genera, including
5-11
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six water column fish and three benthic arthropod genera are below the SQC upper 95%
i
confidence interval. This illustrates why the slope of the species sensitivity distribution is
important. It also suggests that if the extrapolation from water only acute lethality tests to
chronically acceptable sediment concentrations is accurate, these or similarly sensitive genera
may be chronically impacted by sediment concentrations marginailly less than the SQC and
possibly less than the 95 % upper confidence interval. For endrin, the predicted GMCVs range
over three orders of magnitude from the most sensitive to the most tolerant genus. A sediment
concentration 10 times the SQC would include the GMCVs of 11 of the 21 benthic genera tested
including stoneflies, caddis flies, isopods and fish. Tolerant benthic genera such as the annelid
Lumbrieulus might be expected to not be chronically impacted in sediments with endrin
concentrations 1000X the SQC. Data from lethality tests with two freshwater amphipods, and
two freshwater annelids, exposed to endrin spiked into sediments substantiate this range of
sensitivity; the LC50s from these tests range from 3 to 80,000 times the SQC of 4.0 jig/gbc.
The saltwater SQC for endrin (0.76 A*g/goc) is less than any of the PGMCVs for saltwater
genera. The PGMCV for the penaeid shrimp Penaeus (0.83 /tg/goc) a°d the fishes
Oncorhynchus (1.07 jig/goc) and Menidia .(1-12 /*g/goc) are lower than the upper 95%
confidence interval for the SQC (1.6 i^g/goc)- F°r endrin, PGMCVs from the most sensitive
to the most tolerant saltwater genus range over four orders of magnitude. A sediment
concentration 20 times the SQC would include the GMCVs of one-half of the 12 benthic genera
tested including one arthropod and five fish genera. Other genera of benthic arthropods and
polychaetes, are less sensitive and might not be expected to be chronically impacted in sediments
with endrin concentrations 300X the SQC.
5-12
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5.4 COMPARISON OF ENDRIN SQC TO STORET AND NATIONAL STATUS AND
TRENDS DATA FOR SEDIMENT ENDRIN:
A STORET (U.S. EPA, 19895) data retrieval was performed to obtain a preliminary
assessment of the concentrations of dieldrin in the sediments of the nation's water bodies. Log
probability plots of dieldrin concentrations on a dry weight basis in sediments are shown in
•v
Figure 5-3. Endrin is found at significant concentrations in sediments from rivers, lakes and
near coastal water bodies in the United States. This is due to its widespread use and quantity
applied during the 1970s and 1980s. It was banned on October 10, 1984. Median
concentrations are generally at or near detection limits in most water bodies for data from before
and after 1986. There is significant variability in endrin concentrations in sediments throughout
the country. Lake samples in EPA Region 9 appear to have relatively high endrin levels
(median = 0.030 /tg/g) prior to 1986. The upper 10% of the concentrations were
disproportionally found in streams, rivers and lakes in EPA Region 7 and streams, rivers, lakes
and estuaries in Region 9 prior to 1986. In some streams and rivers in Region 7 concentrations
remained high after 1986.
The SQC for endrin can be compared to .existing concentrations of endrin in sediments
of natural water systems in the United States as contained in the STORET database (U.S. EPA,
1989b). These data are generally reported on a dry weight basis, rather than an organic carbon
normalized basis. Therefore, SQC values corresponding to sediment organic carbon levels of
1 to 10% are be compared to endrin's distribution in sediments as examples only. For fresh
water sediments, SQC values are 0.042 /tg/g dry weight in sediments having 1 % organic carbon
and 0.42 jig/g dry weight in sediments having 10% organic carbon; for marine sediments SQC
are 0.0076 /tg/g dry weight and 0.076 /tg/g dry weight, respectively. Figure 5-3 presents the
5-13
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Is
B3
CO »
10
10
TOTAL SAMPLES: 2677
MEASURED SAMPLES: 87
50
80 90
99
99.9
10'
10
10
10
10
10
10
'1
"2
-4
"6
LAKE
TOTAL SAMPLES: 478
MEASURED SAMPLES: 12
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1
fllltll 1
Illllllll
O.lV VV 1
10 20
50
80 90
99
99.9
10
10 20 50 80 90
PROBABILITY
99
99.9
Figure 5-3. Probability distribution of concentrations of endrin in sediments from streams,
lakes and estuaries in the United States from 1986 to 1990 from the STORET
(U.S. EPA, 19895) database compared to the endrin SQC values of 0.42 pg/g in
freshwater sediments having TOC = 10% and 0.042 /tg/g in freshwater
sediments having TOC = 1% and compared to SQC values for saltwater
sediments of 0.076 jtg/g when TOC =10% and 0.0076 jtg/g when TOC=1%.
The upper dashed line on each figure represents the SQC value when TOC =
10%, the lower dashed line represents the SQC when TOC = 1%.
5-14
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comparisons of these SQC to probability distributions of observed sediment endrin levels for
streams and lakes (fresh water systems, shown on upper panels) and estuaries (marine systems,
lower panel). For streams (n = 2,699) both the SQC of 0.042 pg/g dry weight for 1 % organic
carbon sediments and the SQC of 0.42 pg/g dry weight criteria for 10% organic carbon
freshwater sediments are exceeded by less than 1 % of the data. For lakes (n = 478) the SQC
for 1 % organic carbon sediments is exceeded by about 2% of the data and the SQC of 0.42 pg/g
dry weight criteria for 10% organic carbon freshwater sediments is exceeded by less than 1 %
of the data. For estuaries (n = 150) the SQC of 0.0076 /tg/g dry weight for 1 % organic carbon
salt water sediments are exceeded by about 8% of the data, and the SQC of 0.076 pg/g dry
weight criteria for 10% organic carbon freshwater sediments are not exceeded by any of the
data. The above description of endrin distributions in Figure 5-3 is misleading because it
includes data from most samples in which the endrin concentration was below the detection
limit. These data are indicated on the plot as "less than" symbols (<), and plotted at the
reported detection limits. Because these values represent upper bounds and not measured values
the percentage of samples in which the SQC values are actually exceeded may be less than the
percentage reported.
Regional specific differences in endrin concentrations may affect the above conclusions
concerning expected criteria exceedences. This analysis also does not consider other factors
such as the type of samples collected; (i.e., whether samples were from surficial grab samples
or vertical core profiles), the relative frequencies of sampling in different study areas and
whether or not the same study areas were sampled during different time periods. It is presented
as an aid in assessing the range of reported endrin sediment concentrations and the extent to
5-15
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which they may exceed the SQC.
5.5 UMTTAHONS TO THE APPLICABILITY OF SEDIMENT QUALITY CRITERIA:
Rarely, if ever, are contaminants found alone in naturally occurring sediments.
»
Obviously, the fact that the concentration of a particular contaminant does not exceed the SQC
does not mean that other chemicals, for which there are no SQC available, are not present in
concentrations sufficient to cause harmful effects. Furthermore, even if SQC were available for
all of the contaminants in a particular sediment, there might be additive or synergistic effects
that the criteria do not address. In this sense the SQC represent "test case" criteria.
It is theoretically possible that antagonistic reactions between chemicals could reduce the
toxicity of a given chemical such that it might not cause unacceptable effects on benthic
organisms at concentrations above the SQC when it occurs with the antagonistic chemical.
However, antagonism has rarely been demonstrated. What should be much more common are
instances where toxic effects occur at concentrations below the SQC because of the additivity
of toxicity of many common contaminants (Alabaster and Lloyd, 1982), e.g. heavy metals and
PAHs, and instances where other toxic compounds for which no SQC exist occur along with
SQC chemicals.
Care must be used in application of EqP-based SQC in disequilibrium conditions. In
"i
some instances site-specific SQC may be required to address this condition. EqP-based SQC
assume that nonionic organic chemicals are in equilibrium with the sediment and IW and are
associated with sediment primarily through adsorption into sediment organic carbon. In order
for these assumptions to be valid, the chemical must be dissolved hi IW and partitioned into
5-16
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sediment organic carbon. The chemical must, therefore, be associated with the sediment for a
sufficient length of time for equilibrium to be reached. In sediments where particles of
undissolved endrin occur, disequilibrium exists and criteria are over protective. In liquid
chemical spill situations disequilibrium concentrations in interstitial and overlying water may be
proportionately higher relative to sediment concentrations. In this case criteria may be
underprotective.
In very dynamic areas, with highly erosional or depositional bedded sediments,
equilibrium may not be attained with contaminants. However, even high KQW nonionic organic
compounds come to equilibrium in clean sediment in a period of days, weeks or months.
Equilibrium tunes are shorter for mixtures of two sediments each previously at equilibrium.
This is particularly relevant in tidal situations where large volumes of sediments are eroded and
deposited, yet near equilibrium conditions may predominate over large areas. Except for spills
and paniculate chemical, near equilibrium is the rule and disequilibrium is uncommon. In
instances where it is suspected that EqP does not apply for a particular sediment because of
disequilibrium discussed above, site-specific methodologies may be applied (U.S. EPA, 1993b).
5-17
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SECTION 6
CRITERIA STATEMENT
The procedures described in the "Technical Basis for Deriving Sediment Quality Criteria
for Nonionic Organic Contaminants for the Protection of Benthic Organisms by Using
Equilibrium Partitioning" (U.S. EPA, 1993a) indicate that benthic organisms should be
acceptably protected in freshwater sediments containing <_ 4.2 pg endrin/g organic carbon and
saltwater sediments containing .<_ 0.76 /*g endrin/g organic carbon, except possibly where a
locally important species is very sensitive or sediment organic carbon is < 0.2%.
Confidence limits of 2.0 to 9.1 /tg/goc for freshwater sediments and 0.35 to 1.6 pg/goc
for saltwater sediments are provided as an estimate of the uncertainty associated with the degree
to which the observed concentration in sediment (jug/goc), which may be toxic, can be predicted
using the organic carbon partition coefficient (Koc) and the water-only effects concentration.
Confidence limits do not incorporate uncertainty associated with water quality criteria. An
understanding of the theoretical basis of the equilibrium partitioning methodology, uncertainty,
the partitioning and toxicity of endrin, and sound judgement are required in the regulatory use
of SQC and their confidence limits.
These concentrations represent the U.S. EPA's best judgement at this time of the levels
of endrin in sediments that would be protective of benthic species. It is the philosophy of the
Agency and the EPA Science Advisory Board that the use of sediment quality criteria (SQCs)
as stand-alone, pass-fail criteria is not recommended for all applications and should frequently
6-1
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trigger additional studies at sites under investigation. The upper confidence limit should be
;
interpreted as a concentration above which impacts on benthic species should be expected.
Conversely, the lower confidence limit should be interpreted as a concentration below which
impacts on benthic species should be unlikely.
6-2
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SECTION?
REFERENCES
Adams W.J., R.A. Kimerle and R.C. Mosher. 1985. Aquatic safety assessment of chemicals
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7-7
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