&EPA
0%
United States 0 Rice o f Science and Technology
Environmental Protection Agency Health and Ecological Criteria Div.
Office of Water & Washington, DC 20460
Office or Research and Development,
5 -ti -me
EPA xxx/x-ut-ux
November 1991
WATER
Proposed Sediment Quality
Criteria for the Protection
of Benthic Organisms:
PHENANTHRENE
CO
I HEADQUARTERS LI8RARY
- PROTECTION AGENCY
WASHINGTON, O.C. 20460
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CONTENTS
PAGE
Foreword
Acknowledgments
Tables
Figures
n
iii
v
vi
Introduction 1-1
Partitioning 2-1
Toxicity of Phenanthrene: Water Exposures 3-1
Toxicity of Phenanthrene (Actual and Predicted): Sediment Exposures 4-1
Criteria Derivation for Phenanthrene . 5-1
Criteria Statement • 6-1
References 7-1
Appendix A: Summary of Acute Values for Phenanthrene for Freshwater and Saltwater
Species - A-l
Appendix B: Evaluation of Octanol-Water Partition Coefficient for Phenanthrene . B-l
Appendix C: Summary of Data from Sediment Spiking Experiments with
Phenanthrene C-l
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FOREWORD
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. 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. Section 304(a)(l) directs the
Administrator to develop and publish "criteria" reflecting the latest scientific knowledge on the
kind and extent of effects on plankton, fish, shellfish, and wildlife which may be expected from
the presence of pollutants in any body of water, including ground water, the concentration and
dispersal of pollutants, or their byproducts, through biological, physical and chemical processes;
and the effects of pollutants on biological community diversity, productivity, and stability!
Section 304(a)(2) directs the administrator to develop and publish information on the factors
necessary for the protection and propagation of shellfish, fish, and wildlife for classes and
categories of receiving waters.
To meet this objective, in 1980 EPA published ambient water quality criteria
(WQQ for 64 of the 65 toxic pollutants or pollutant categories designated as toxic under
Section 307(a)(l) of the CWA. Additional water quality documents that update criteria for
selected consent decree chemicals and new criteria have also been published since 1980. In
addition to the development of water quality criteria and to continue to comply with the
of the CWA, EPA has conducted efforts to develop and publish sediment quality criteria for
some of the 65 toxic pollutants or toxic pollutant categories.
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 comply with established water quality criteria. In addition,
contaminated sediments can lead to water quality degradation, even when pollutant sources are
stopped. It is intended that sediment quality criteria 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. Environmental Protection
Agency's best recommendation of the concentrations of a substance in «**«™*nt that will not
unacceptably affect benthic organisms. These criteria are applicable to a variety of freshwater
and marine sediments because they are based on the biologically available concentration of the
substance hi sediments. These criteria do not protect against additive, synergistic or
antagonistic effects of contaminants or bibaccumulative effects to aqua*y? life or fr"«»a" health.
The criteria and derivation methods outlined in ***** documgnt are proposed to
provide protection of benthic organisms from biological impacts from chemicals associated with
sediments. Recommendations on the use of these criteria will follow completion of the public
response process. In the interim, until final Sediment Quality Criteria are promulgated, these
criteria should only be used to support site specific assessments for «**ti«n««** that are consistent
with assumptions of equilibrium partitioning theory on which these Sediment Quality Criteria
are developed.
Guidelines and guidance have been developed by 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.
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ACKNOWLEDGEMENTS
Principal Author
David J. Hansen
Coauthors
Walter J. Berry.
Dominic M. Di Toro
Paul Paquin
Laurie Davanzo
Frank E. Stancil, Jr.
Heinz P. Koilig
Technical and Clerical Support
Glen Thursby
Dinalyn Spears
Charito Panita
Betty Anne Calise
U.S. EPA, Environmental Research Laboratory,
Narragansett, RI
Science Applications International Corporation,
Narragansett, RI
Manhattan College, Bronx, NY;
HydroQual, Inc., Mahwah, NJ
HydroQual, Inc.,
Mahwah, NJ
HydroQual, Inc.,
Mahwah, NJ
U.S. Environmental Research Laboratory,
Athens, GA
U.S. Environmental Research Laboratory,
Athens, GA
Persons who have made significant contributions to the development of the approach and
supporting science used in the derivation of sediment criteria for non-ionic organic contaminants
are as follows:
Herbert E. Allen
Gerald Ankley
Christina E. Cowan
Dominic M. Di Toro
David J. Hansen
Paul R. Paquin
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
111
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Spyros P. Pavlou
Richard C. Swartz
Nelson A. Thomas
Christopher S. Zarba
Ebasco Environmental, Bellevue, WA
U.S. EPA, Environmental Reserach Laboratory,
Newport,OR
U.S. EPA, Environmental Research Laboratory,
Duluth, MN
U.S. EPA Headquarters, Office of Water, Washington, DC
IV
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TABLES
Table 2-1. Summary of measured and estimated KQW values for phenamhrene by the U.S.
EPA, Environmental Research Laboratory, Athens, GA.
Table 3-1. Acute sensitivity of freshwater and saltwater benthic species to phenamhrene.
Table 3-2. Chronic sensitivity of freshwater and saltwater organisms to phenanthrene.
Test specific data.
Table 3-3. Summary of acute and chronic values, acute-chronic ratios and freshwater and
saltwater final acute values, final acute-chronic ratios, and final chronic values
for phenanthrene.
Table 3-4. Kolmogorov-Smirnov test for the equality of freshwater and saltwater LCSO
distributions for phenanthrene. Kolmogorov-Smirnov test for the equality of
benthic and water column LC50 distributions.
Table 4-1. Summary of tests with phenanthrene-spiked sediment.
Table 4-2. Water-only and sediment LCSOs used to test the applicability of the equilibrium
partitioning theory for phenanthrene.
Table 5-1. Sediment quality criteria for phenanthrene.
Table 5-2. Analysis of variance for derivation of sediment quality criteria confidence limits
for phenanthrene.
Table 5-3. Sediment quality criteria confidence limits for phenanthrene.
APPENDIX
Appendix A. - Phenanthrene: Summary of acute values for freshwater and saltwater species.
Appendix B. - The octanol-water partition coefficient, ROW for phenanthrene.
Appendix C. - Summary of data from sediment spiking experiments with phenanthrene that
were used to calcula** KOC values (Figure 2-2) and to compare mortalities of
amphipods with interstitial water toxic units (Figure 4-1) and predicted
sediment toxic units (Figure 4-2).
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FIGURES
Figure 1-1.
Figure 2-1.
Figure 3-1.
Figure 3-2.
Figure 4-1.
Figure 4-2.
Figure 5-1.
Figure 5-2.
Chemical structure and physical-chemical properties of phenanthrene.
Organic carbon-normalized sorption isotherm for phenanthrene (top) and
probability plot of KOC (bottom) from sediment toxicity tests conducted by Swartz
(1991).
Comparison of phenanthrene water only LC50 probability distributions for
freshwater (0) and saltwater (*) species (top panel). Cumulative distribution
functions for calculating the K-S statistic (bottom panel).
Comparison of phenanthrene water only LC50 probability distributions for water
column (0) and benthic (*) freshwater and saltwater species (top panel).
Cumulative distribution functions for calculating die K-S statistic (bottom panel).
Percent mortality of amphipods in sediments spiked with acenaphthene or
phenanthrene (Swartz, 1991), cadmium (Swartz et al., 1985), endrin (Nebeker
et al., 1989; Schuytema et al., 1989), or fluoranthene (Swartz et al., 1990), and
midge in kepone-spiked sediments (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 C in this SQC document, Appendix C in the
endrin, dieldrin, fluoranthene and acenaphthene SQC documents, and original
references for raw data.)
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)
relative to "predicted sediment toxic units.* Predicted sediment toxic units are
the ratios or measured treatment concentrations for each chemical in sediments
in sediments (1C*, x Water-only
), pg/L). (See Appendix C in this document and Appendix C in the dieldrin,
endrin, fluoranthene, and acenaphthene SQC documents for raw data).
Probability distribution of concentrations of phenanthrene in sediments from
streams (n=584), lakes (n=50) and estuaries (n»87) in the United States from
1986 to 1990, from the STORET (U.S. EPA, 1989c) database, compared to the
phenanthrene SQC values of 12 ug/g in freshwater sediments having TOC =
10% and 1.2 pg/g in freshwater sediments having TOC » 1%; SQC values for
saltwater sediments are 16 pg/g when TOC »10% and 1.6 ug/g when TOC=i%.
The upper dashed line on each figure represents the SQC value when TOC =
10%, the lower dashed line represents the SQC when TOC = 1%.
Probability distribution of concentrations of phenanthrene in sediments from
coastal and estuarine sites from 1984 to 1989 as measured by the National Status
and Trends Program (NOAA, 1991). The horizontal line is the SQC value of
VI
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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.
AVAILABILITY 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.
vu
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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 water quality criteria are
numerical concentration limits that axe 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 water quality criteria. 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 (SQQ makes it difficult to accurately assess the extent of
the ecological risks of contaminated sediments and to identify, prioritize and implement
appropriate clean up activities and source controls. As a result of the need for a procedure to
assist regulatory agencies in mating decisions concerning contaminated sediment problems, a
U.S. EPA Office of Science and Technology, Health and Ecological Criteria Division
(OST/HEQ research team was established to review alternative approaches (Chapman, 1987).
l-i
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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 sediment
quality criteria 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 non-ionic 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 non-ionic organic
chemicals on an organic carbon basis to pore water concentrations.
3. The distribution of sensitivities of benthic and water column organisms to
chemicals are similar; thus, the currently established water quality criteria 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
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 respiration, from sediment via ingestionr
or from a mixture of both exposure routes; (4) for non-ionic chemicals, effect concentrations
in sediments on an organic carbon basis can be predicted using the organic carbon partition
coefficient (K^ 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 (pg/goc) derived as the product of the Koc and FCV is protective of benthic organisms.
Sediment quality criteria concentrations presented in this document are expressed as pg
1-2
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chemical/g sediment organic carbon and not on an interstitial water basis because: (1) pore
water is difficult to adequately sample; and (2) significant amounts of the dissolved chemical
may be. associated with dissolved organic carbon; thus, interstitial concentrations may
overestimate exposure.
The data that support the equilibrium partitioning approach for deriving SQC for non-
ionic organic chemicals are reviewed by Di Toro et al. (1991) and in the sediment quality
criteria guidelines (U.S. EPA, 1992a). Data supporting these observations for phenanthrene are
presented in this document.
Sediment quality criteria generated using the equilibrium partitioning 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 .
5. protective of bentbic organisms.
As is the case with water quality criteria, the sediment quality criteria reflect the use of
available scientific data to: (1) assess the likelihood of significant environmental effects to
bentbic 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 bentbic organisms from
the effects of chemicals associated with sediments. SQC are intended to apply to sediments
permanently inundated with water, intertidal sediment and to sediments imin4atgd periodically
for durations sufficient to permit development of bentbic assemblages. They do not apply to
occasionally inundated soils containing terrestrial organisms. In spills, where chemical
equilibrium between water and sediments has not yet been reached, sediment chemical
concentrations in excess of SQC indicate bentbic organisms may be at risk. Tins is because for
1-3
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spills, disequilibrium concentrations in interstitial and overlying water may be proportionally
-.higher relative to sediment concentrations. In spills, sediments having concentrations less than
SQC may also pose risks to benthic 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. Environmental Protection Agency's best recommendation at this time of the
concentration of a chemical in sediment that will not unacceptably affect benthic organisms.
SQC values may be adjusted to account for future data or site specific considerations.
This document presents the theoretical basis and the supporting data relevant to the
derivation of the sediment quality criterion for phenanthrene. 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 "Guidelines for Deriving Numerical National Sediment Quality Criteria for
Non-ionic Organic Chemicals for the Protection of Benthic Organisms" (U.S. EPA, 1992a) is
necessary in order to understand the following text, tables and calculations. Guidance into the
acceptable use of SQC values is contained in U.S. EPA, 19925.
1.2 GENERAL INFORMATION: PHENANTHRENE
Phenanthrene is a member of the polycyclic aromatic hydrocarbon (PAH) group of organic
compounds. Phenanthrene is produced by fractional distillation of high-boiling coal-tar oil and
die subsequent purification of die crystalline solid (Hawley, 1981). Some uses of phenanthrene
axe in die manufacturing of dyestuffs and explosives, in the synthesis of drugs and in
biochemical research (Verschueren, 1983). Some PAHs are of environmental concern because
they are known to be carcinogens and/or mutagens (Brookes, 1977). With an increase in fossil
fuel consumption in the United States an increase in emissions of PAHs to the environment can
1-4
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be expected over the next several decades (Eadie et al., 1982).
Phenanthrene has a three ring structure and exists as colorless leaflets (Figure 1-1). It has
a solubility in water at 25 °C of 1.18 mg/L and is a solid at room temperature (melting point
of 100.85°C) (Miller et al., 1985). Phenanthrene has a reported vapor pressure of 69.3 -110,6
mPa at 25aC (Bidleman, 1984). Two significant processes which can influence the fate of
phenanthrene in the sediment are sorption and biodegradation (U.S. EPA, 1980). Sorption of
phenathrene onto solids in the water column and subsequent settling, as well as partitioning onto
organics in the sediment, can significantly affect phenanthrene transport. Bioaccumulated PAHs
with 4 rings or less are rapidly metabolized. Therefore, long-term partitioning into biota is not
considered a significant fate process (U.S. EPA, 1980). Other processes found to have little
or no effect on the fate of phenanthrene in the sediment are oxidation, hydrolysis and
volatilization (U.S. EPA, 1980).
The acute toxicity of phenanthrene ranges from 96 to > 1150 ug/L for freshwater and
21.9 to 600 jig/L for saltwater organisms (Appendix A). Differences between phenanthrene
concentrations causing acute lethality and chronic toxicity in invertebrates are small; acute-
chronic ratios range from 1.2 to 3.3 for two species. The only available acute-chronic ratio for
rainbow trout is 59 (Table 3-3). Although phenanthrene bioaccumulates in aquatic biota, the
associated health or ecological risks are unknown.
1.3 OVERVIEW OF DOCUMENT:
• The goal of this document is to provide a brief review of the equilibrium partitioning
methodology, a summary of the physical-chemical properties and aquatic toxicity of
phenanthrene, and the technical basis for setting the SQC for phenanthrene. Section 2 reviews
a variety of methods and data useful in deriving partition coefficients for phenanthrene and
includes the K^ recommended for use in the derivation of the phenanthrene SQC. Section 3
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MOLECULAR FORMULA.
MOLECULAR WEIGHT
DENSITY
MELTING POINT
PHYSICAL FORM
VAPOR PRESSURE
C14H10
178.22
1.179 g/cc 125 C
100.85 C
colorless leaflets
5.2x10-4 to 8.3x10-4
mm Hg at 25 C
GAS NUMBER
CHEMICAL NAME
85-0108
Phenanthrene
FIGURE 1-1. Chemical structure and physical-chemical properties of phenanthrene
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reviews aquatic toxicity data contained in the phenanthrene WQC document (U.S. EPA, 1980)
and new data that were used to derive the Final Chronic Value (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 phenanthrene in the
derivation of the SQC- Section 4 reviews data on the toxicity of phenanthrene in sediments,
the need for organic carbon normalization of phenanthrene sediment concentrations and the
accuracy of the EqP prediction of sediment toxicity using K^. 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 phenanthrene and its uncertainty. The SQC for phenanthrene is then compared to
STORET (U.S. EPA, 1989b) and National Status and Trends (NOAA, 1991) data on
phenanthrene's environmental occurrence in sediments. Section 6 concludes with the criteria
statement for phenanthrene. The references used in this document are listed in Section 7.
1-7
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SECTION?
PARTITIONING
2.1 DESCRIPTION OF THE EQUILIBRIUM PARTITIONING METHODOLOGY:
. Sediment quality criteria 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; ie., the concentration-of a chemical which is protective of the intended
use such as aquatic life protection. For non-ionic organic chemicals, SQC are expressed as pg
chemical/g organic carbon and apply to sediments having ,S 0.2% organic carbon by dry
weight. A brief overview follows of the concepts which underlie the equilibrium partitioning
methodology for deriving sediment quality criteria. The methodology is discussed in detail in
the "Guidelines for Deriving Numerical National Sediment Quality Criteria for Non-ionic
Organic Chemicals for Protection of Benthic Organisms" (U.S. EPA, 1992a), hereafter referred
to as the SQC Guidelines. '
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 sediment quality
criterion based on die bioavailable chemical fraction in a sediment. For non-ionic organic
chemicals, the concentration-response relationship for the biological effect of concern can most
often be correlated with the interstitial water (i.e., pore water) concentration G*g chemical/liter
pore water) and not to the sediment chemical concentration 0*g chemical/g sediment) (Di Toro
et al., 1991). From a purely practical point of view, this correlation suggests mat 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
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chemicals between the solid and liquid phases in a sediment is a necessary component for
establishing sediment quality criteria. It is for this reason that the methodology described
below is called the equilibrium partitioning (EqP) method.
It is shown in the SQC Guidelines (U.S. EPA, 1992a), that benthic and water column
species from freshwater and saltwater environments exhibit similar sensitivities to a wide range
of chemicals. The data for phenanthrene are presented in Section 3. Thus, a sediment quality
criteria can be established using the final chronic value (FCV) derived using the Water Quality
Criteria Guidelines (Stephan et al., 1985) as the effect concentration, and the partition
coefficient can be used to relate the pore water concentration (FCV) to .the sediment quality
criteria via the partitioning equation.
The calculation is as follows: Let FCV Gig/L) be the no effect concentration in water
for the chemical of interest; then the sediment quality criteria, SQC (pg/kg sediment), is
computed using the partition coefficient, K, (L/kg sediment), between sediment and water:
SQC - K, FCV (2-1)
This is the fundamental equation used to generate the sediment quality criterion. Its utility
depends upon the existence of a methodology for quantifying the partition coefficient, K,.
For phenanthrene, and other hydrophobic non-ionic organic chemicals, the chemical
property of importance is the octanol-water partition coefficient, K^. It is empirically related
to the partition coefficient via KQC (Equation 2-5), the organic carbon partition coefficient, and
foe, the weight fraction of organic carbon in the sediment (goc/g sediment). Organic carbon
appears to be the predominant sorption phase for non-ionic organic chemicals in naturally
occurring sediments. The relationship is as follows: . . •
Kr - 4cKoc (2-2)
•N
It follows mat:
FCV (2-3)
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where SQCoc *s *« sediment quality criterion on a sediment organic carbon basis.
The next section reviews the available information for
2.2 DETERMINATION OF KOW FOR PHENANTHRENE:
Several approaches have been used to determine K<,w for the derivation of a SQC, as
discussed in the SQC Guidelines. At the U.S. EPA, Environmental Research Laboratory at
Athens, GA (ERL.A) two methods were selected for measurement and two for estimation of
KOW The measurement methods were shake-centrifugation (SQ, generator column (GCol) and
the estimation methods were SPARC and CLOGP (Appendix B). Data were also extracted from
the literature. The shake-centrifugation method is a standard procedure in the Organization for
Economic Cooperation and Development (OECD) guidelines for testing chemicals, therefore
it has regulatory precedence.
Examination of the literature reveals that the log10Kow values for phenanthrene range from
4.28 to 4.64.
Preliminary experience with the SPARC program suggests that the program can compute
values for partition coefficients for high logP chemicals which may be more reliable and
accurate than laboratory measurements which may suffer from errors inherent in many
methodologies. However, the program needs more validation by comparison with laboratory-
measured data for a wide range of chemical structures before it is recommended as a basis for
computing partition coefficients for regulatory purposes. The SPARC estimated logIOKow value
for phenanthrene is 4.58. The CLOGP program estimate of the log,pKow value for phenanthrene
using structure activity relationships is 4.49.
Two measurement methods provide additional data from which to define KOW for
phenanthrene ( Table 2-1; Appendix B). The shake-centrifugation method yielded togloKoW -
4.30, and the generator column method yielded logloKow » 4.40. There is no clear-cut best
value from the data that has been developed. Considering the agreement among the SPARC
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estimated value and the measured values using shake-centrifugatipn and generator column
methods, the recommended vaue for log10KoW is 4.36. This is the log(0KoV of the average of
shake-centrifugation and generator column measurements made under carefully controlled
conditions in the ERL, Athens Laboratory. The four shake-centrifugation measurements range
from 4.25 to 4.33 and the four generator column measurements range from 4.24 to 4.47.
TABLE 2-1. SUMMARY OF MEASURED AND ESTIMATED K^ VALUES FOR
PHENANTHRENE BY THE U.S. EPA, ENVIRONMENTAL RESEARCH LABORATORY,
ATHENS, GA.
Measurement
Technique
Shake-
Centrifugation
Generator Column
SPARC
CLQGP
Number of
Analyses
4
4
-
-
Lo]
Mean
4.30
4.40
4.58
4.49
BoKow
CV
0.075
0.190
-
-
2.3 DERIVATION OF K^ FROM ADSORPTION STUDIES:
*
Several types of experimental measurement 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 a**!™***** phenanthrene and pore water phgnanthnang concentrations are used to
compute KOC.
2.3.1 KOC FROM PARTICLE SUSPENSION STUDIES:
Laboratory studies to characterize adsorption are generally conducted using particle
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
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effect. This effect suppresses the partition coefficient relative to that observed for undisturbed
sediments (Di Tom, 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:
oe
where:,
m = particle concentration in the suspension (kg/L)
7/^x = 1-4, an empirical constant (unitless).
The other quantities are defined previously. In this expression, the organic carbon partition
coefficient is given by:
tog»Koc = 0.00028 + 0.983 log10KoW (2-5)
A sorption isotherm experiment that demonstrates the effect of particle suspensions was
found in a comprehensive literature search for partitioning information for phenanthrene (Table
2-2) (Magee et al., 1991). The experiment showed an observed KP of 12.9 L/kg for a
phenanthrene solution and sand with 0.11% organic carbon content. Calculated K, using K^.
(Equation 2-5) and f^ is 21 L/kg. The difference between the observed and calculated KP can
be explained by particle interaction effects. Particle interaction results in a tower observed
partition coefficient. The particle interaction model (Equation 2-4) predicts K, of 8.29 L/kg,
which is in agreement with the observed K,. Log10Koc computed from observed K, and f^ is
4.07. This value is lower than KQC from laboratory measurements due to particle interaction
effects. This data is presented as an example of particle interaction effects only, as 100 percent
reversibility is assumed in the absence of a desorption study and an actual KOC can not be
computed.
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TABUS 2-2. SUMMARY OF K^ VALUES FOR PHENANTHRENE
DERIVED FROM LITERATURE SORPTION ISOTHERM DATA.
Observed n
4.07 1
Solids
(g/L)
100
References
Magee et al.,
1991
In the absence of particle effects, KOC k related to KQ* via Equation 2-5, shown above.
For log10Kow = 4.36 (ERL,A, mean measured value), this egression results in an estimate of
log10Koc - 4.29.
2.3.2 KOC FROM SEDIMENT TOXICTTY TESTS:
Measurements of K^ are available from sediment toxicity tests using phenanthrene
(Swartz, 1991). These tests represent freshwater sediments having a range of organic carbon
contents of 0.82 to 3.6 percent (Table 4-1; Appendix Q. Phenanthrene concentrations were
measured in the sediment and pore waters providing the data necessary to calculate the partition
coefficient for an undisturbed sediment.
Figure 2-1 is a plot of the organic carbon-normalized sorption isostherm for
phenanthrene, where the sediment phenanthrene concentration (pg/goc) i* plotted versus pore
water concentration G*g/L). The data used to make this plot are included in Appendix C. The
line of unity slope corresponding to the log10Koc = 4.29 is compared to the data. The intercept
at a pore water concentration of 1 pg/L is equivalent to logJCoc.
A probability plot of the observed experimental loguKoe values is shown in Figure 2-
1. The log^Koc values are approximately normally distributed with a mean of log^Koc - 4.33
and a standard error of die mean of 0.016. This value is «mti^«iny indistinguishable from
4-29, which was computed from the experimentally determined phenanthrene
4.36 (Equation 2-5). Complexation with pore water DOC has not been accounted
2-6
-------
3 100000§—i i i inn
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for in the experimentally based estimate of log^R^ = 4.33. Though it is not expected to be
a major factor, consideration of DOC effect would increase the estimate of logl<^oc relative
i
to the value based on total pore water concentrations. If this uncorrected value was used to set
SQC, the SQC concentration would tend to be environmentally conservative.
2.4 SUMMARY OF DERIVATION OF KOC FOR FHENANTHRENE:
The KOC selected to calculate the sediment quality criteria for phenanthrene is based on
the regression of log10Koc to loguKow (Equation 2-5), using the phenanthrene loguKov of 4.36
recently measured by ERL,A. This approach 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 K<,w and f^. The regression equation yields logIOKoc
= 4.29. This value is in agreement with the loguKoc of 4.33 measured in the sediment toxicity
2-8
-------
SECTION 3
TOXICITY OF PHENANTHRENE: WATER EXPOSURES
3.1 TOXICITY OF PHENANTHRENE IN WATER: DERIVATION OF PHENANTHRENE
WATER QUALITY CRITERIA:
The equilibrium partitioning method for derivation of sediment quality criteria uses the
phenanthrene water quality criterion Final Chronic Value (FCV) and partition coefficients (Koc)
to estimate the maximum concentrations of non-ionic organic chemicals in sediments, expressed
on an organic carbon basis, that will not cause adverse effects to benthic organisms. For this
document, life stages of species classed as benthic are either species that live in the sediment
(infauna) or primarily on the sediment surface (epibenthic) and obtain their food from either the
sediment or water column (U.S. EPA, 1989c). The toxicological basis for derivation of the
final chronic value and the justification for use of this value as the effects concentration or
sediment quality criteria derivation ace discussed in this section.
3.2 ACUTE TOXICrTY - WATER EXPOSURES:
Fourteen standard toxicity tests with phenanthrene have been conducted on 9 freshwater
species from 8 genera (Appendix A). Overall genus mean acute values (GMAVs) range from
96 to > 1,150 pg/L. The acute values for all species tested, except for fathead minnows,
differed by only a factor of 5; 96 to 490 pg/L. Three tests on three benthic species from three
genera are contained in this 419 pg/L) and
the midge, Chironomiis tCTtMr" (LC50 = 490 pg/L)., The Final Acute Value derived from the
overall GMAVs (Stephan et al., 1985) for freshwater organisms is 59.63 pg/L (Table 3-3).
Fourteen acute tests have been conducted on 11 saltwater species from 11 genera
3-1
-------
L\J rn&nna nirva
RANK'
c
HMAV LIFE1* HAB-
GEHUS COMMON/ SCI. HAKE STAGE ITAT SPECIES0 GENUS
FRESHWATER SPECIES
Amphipod, " X E 126 126
Gammarus osaudol iranaeua
Annelid, X I >419 >419
varieoatus
Midge, XI 490 490
Chironomua tantans
SALTWATER SPECIES
Mysid, J B 21.9 21.9
MvBidoosifl bahia
Grass shrimp, A E,W 145 145
Palaetnonetas ouoio
Hermit crab, -At 164 164
Paourua lonqicarpus
Archiann«lid, J ^ I 185 185
DinophiluB gyroeiliatus
Amphipod, J X 198 198
Lentochalrua
8 Mud snail, A I,E >24S >245
Hasaarius obsolatus
8 Blu« muss«l, A B,W >24S >245
Mvtilus adulis
8 Soft-shall clam, A I >245 >24S
Mya fgf*<«g^«
10 ShMpahMd minnow, J B,H 429 429
Cvprlnodon aji
*Rank of HMAV* by g»nus ar« from Appendix A which included bentbic and water column
spscias.
A » adult, J « juv*nil«, L • larva*, S » ambry o, 0 » li£««tag« and habitat
unknown, X - lif«stag« unknown but habitat known.
cHabitat: Z - infauna, E * «pib«nthic, H * water column.
3-2
-------
species. {See Appendix A).
*HHAV genu»t Geometric mean of HMAV for species within a genus.
3-3
-------
(Appendix A). Overall genus mean acute values (GMAVs) range from 21.9 to 600 /*g/L,
similar to the range for freshwater genera. Fish and crustaceans were the most sensitive.
Within this database there are results from nine tests on benthic life-stages of nine species from
nine genera (Table 3-1; Appendix A). Benthic organisms were among both the most sensitive,
and most resistant, saltwater genera to phenanthrene. The most sensitive benthic species is the
mysid, Mvsidopsis bjhja, with an average flow-through 96 hour LC50 of 21.9 pg/L based on
two tests with measured concentrations. Other benthic species for which there are data appear
less sensitive; GMAVs range from 145 to 429 pg/L. The Final Acute Value derived from the
overall GMAVs (Stephan et al., 1985) for saltwater organisms is 16.61 /ig/L (Table 3-3).
3.3 CHRONIC TOXKTTY - WATER EXPOSURES:
Chronic toxicity tests have been conducted with phenanthrene using a freshwater
cladoceran rDaphnia magnaj and rainbow trout fOncorhynchua myldgft and a saltwater mysid
(Mvsidopsis fegbja). The cladoceran and mysid were tested in life-cycle exposures. Rainbow
trout embryos, sac fry and swim-up benthic (intergravel) stages were tested in an early life-
stage toxicity test.
Call et al. (1986) conducted both freshwater tests. EapJsaia magaa exposed 21 days to
a mean phenanthrene concentration of 163 pg/L experienced 98 % reduction in reproduction and
83 % reduction in survival relative to controls (Table 3-2). There was no statistically significant
effect on survival or reproduction of daphnids in phenanthrene concentrations from 46 to 57
Mg/L. Rainbow trout exposed to phenanthrene for 90 days in an early life-stage toxicity test
were not affected in 5 pg/L. Duration of incubation and hatching success were not affected
in any treatment However, the percentage of .abnormal and dead fry at hatch was significantly
increased at the highest exposure (66 ftg/L). Sac fry were underdeveloped from hatching until
lest termination and swim-up delayed in >. 14 pg/L. At test termination, wet weights and
standard lengths were reduced in >. 32 pg/L. Survival was reduced in ^. 8 pg/L.
3-4
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Saltwater mysids exposed to phenanthrene in a life-cycle toxicity test (Kuhn and Lussier,
1987) were affected at phenanthrene concentrations similar to those affecting the the rainbow
trout (Table 3-2). Survival, growth and reproduction were not affected in <. 5.5 pg/L. At the
4
highest concentration of phenanthrene (11.9 pg/L) all mysids died.
Derivation of the Final Chronic Value (FCV) for phenanthrene is complicated because
Acute-Chronic Ratios (ACR) differ in the three species tested by a factor of almost 50 (Table
3-3). The final ACR, therefore, can not be the mean of these three values (Stephan et al.,
1985). The difference between concentrations of phenanthrene acutely and chronically toxic to
invertebrates is small. ACR are 1.214 for the freshwater cladoceran maphnia magna) and .
3.333 for the saltwater mystd fMysidopsis bjhja); mean ratio 2.012. The ACR of 59.29 for
rainbow trout (Call et al., 1986) probably should not be used to derive the final ACR or chronic
values for untested fishes because (1) it is over 10 x the ratio for tested invertebrates, (2) the
trout 96 hr LC50 of 375 pg/L would be 50 pg/L if based on immobilization (Call et al., 1986),
thus the ACR would be 7.905 and (3) the chronic value may be conservative based on tests with
other fish species. In non-standard chronic exposures, sensitivities of early life-stages of
largemouth bass fMJcropterus almftifeft and rainbow trout (Black et al., 1983; Milkman et
al., 1984) were less than observed by Call et al. (1986). These chronic exposures lasted from
fertilization Co four days alter hatching, about 7 days for bass and 27 days for trout. Hatching
and survival of trout were reduced in 38 pg/L but not in 31 pg/L; in contrast to the effect
concentration of 8 pg/L was observed by Call et al. (1986). The LC50 for these tests was 40
pg/L for trout and 180 pg/L for bass (Black et al., 1983; Milkman et al., 1984). Because the
most acutely sensitive species to phenanthrene were invertebrates, the Final Acute Value (FAV),
59.63 pg/L for freshwater and 16.61 pg/L for saltwater, was divided by the invertebrate mean
ACR of 2.012 to derive an initial estimate of the FCV. These initial FCVs were 29.64 pg/L
for freshwater and 8.255 pg/L for saltwater aquatic life. The initial freshwater FCV was
lowered to 6.325 pg/L the chronic value from the rainbow trout early life-stage test for this
3-6
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3-7
-------
important species. The initial saltwater FCV of 8.25S pg/L was not lowered because the
chronic sensitivitie of saltwater fishes is not known and should not be estimated using the ACR
for trout which is probably not appropriate for other fish species. The initial FCV for saltwater
aquatic life is used as the FCV because it is 13 to 52 times lower than acute values for tested
saltwater fishes and approximately equal to the chronic value of 8.129 pg/L for the mysid.
Although this procedure to derive the FCV is complicated and does not follow exactly the WQC
Guidelines (Stephan et al.,1985) for idealized databases, the procedure is consistent with the
guidelines requirement that the criterion be consistent with sound scientific evidence.
3.4 APPLICABILITY OF THE WATER QUALITY CRITERION AS THE EFFECTS
CONCENTRATION FOR DERIVATION OF THE PHENANTHRENESEDIMENT
QUALITY CRITERION:
The use of the Final Chronic Value (the chronic effects-based water quality criteria
concentration) as the effects concentration for calculation of the equilibrium partitioning-based
sediment quality criterion assumes similar sensitivities of benthic (infauna and epibenthic)
species and species tested to derive the water quality criteria concentration. Data supporting
the reasonableness of this assumption over all chemicals for which there are published or draft
water quality criteria documents are presented in Di Toro et al. (1991) and U.S. EPA (1989c,
1992a). The conclusion of similarity of sensitivity is supported by comparisons between acute
values: (1) for the most sensitive benthic and water column species for all chemicals; (2) all
species across all chemicals after standardizing the LC50 values; and (3) individual chemical
comparisons for benthic and water column species. Only in this last comparison are
phenanthrene-specific comparisons in sensitivity of benthic and water-column species conducted.
The following paragraphs examine the data for phenanthrene.
An initial test of the difference between the probability distributions of freshwater and
saltwater phenanthrene LCSOs for all species (water column and benthic) is presented in Figure
3-1. The top panel is a log probability plot of the two LC50 distributions on a log scale versus
3-8
-------
01
O
in
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1000
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E t 1 llllHI 1 1 1 1 1 Mil
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1 1 1 Mill 1 111 HIM 1 1 1 1 1 III
100 1000 10000
(ug/U
gun 3*1. Comparison of phenanthrene water only LCSO probability distribute
freshwater (0) and saltwater (*) species (top panel). Cumulative distr
functions for calculating the K-S statistic (bottom panel).
3-9
-------
the rank order on a probability scale. The natural way to judge the equality of these
distributions is to compare the LCSOs at a particular probability, for example a comparison of
the medians at 50% probability. The Kolmogorov-Smirnov test compares another difference
(Conover, 1980). This is illustrated on the bottom plot which presents the same data but in a
slightly different way. The rank order, as a percent, is plotted versus the LCSOs. The points
are connected with straight lines to form the empirical cumulative distribution functions from
the two data sets. The Kolmogorov-Smirnov test is based on the maximum difference in
probability between these two distributions, as indicated on the figure. Note that this difference
is the horizontal distance on the top plot in Figure 3-1 (if the probability scale were linear).
Table 3-4 presents the number of LCSOs in each distribution, the nqnrimniq difference (0.346),
and the probability (0.568) that a value of this magnitude or less cannot occur given that these
two samples came from the same distribution. The method of computation for this probability
value is given in Massey (1951). Since the probability is less than 0.9S, the hypothesis that
freshwater and saltwater LC50 values came from the same distribution is accepted at a 95%
confidence level. Therefore, for phenanthrene comparisons of LCSOs for benthic and water
column species are conducted using combined freshwater and saltwater LCSO values.
The probability distributions of combined freshwater and saltwater phenanthrene LCSOs
for the water column and benthic species are presented in Figure 3-2. Table 3-4 presents the
number of LCSOs in each distribution, the maximum difference, and the probability that a value
of this magnitude or less cannot occur given that these two samples came from the same
distribution. For combined freshwater and saltwater species the maximum difference and the
probability that a value of this magnitude or less cannot occur given that these two samples
came from die same distribution were 0.361 and 0.655 respectively. This analysis of the
relative sensitivities of combined freshwater and saltwater benthic and water column organisms
that have been tested indicates that they are from the same probability distributions of LCSO's.
Therefore, benthic and water column organisms have similar acute sensitivities. This suggests
3-10
-------
F
P
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MAXIMUM
OPFENCNCC
111 iiini i t it mil i t i t mil i -i i i HIM i i iiim
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to too
LCSO (ug/U
1000 10000
Figure 3-2. Comparison of phenanduene tvuer only LCSO notability distributions for water
column ((^ and bcnthic (•) freshwater and saltwater species (top panel).
Cumulative distribution functions for filftiatjiig the K-S statistic (bottom panel).
-------
that the final chronic value (FCV) for phenanthrene is an appropriate effects concentration for
both benthic and water column organisms.
TABLE 3-4. KOLMOGOROV-SMIRNOV TEST FOR THE
EQUALITY OF FRESHWATER AND SALTWATER LC50
DISTRIBUTIONS FOR PHENANTHRENE. KOLMOGOROV-
SMIRNOV TEST FOR THE EQUALTTY OF BENTHIC AND WATER
COLUMN LC50 DISTRIBUTIONS.
Compar-
ison Habitat or Water Type* K-S Statistic* Probability'
Fresh
vsSalt
Fresh (8) Salt (13) 0.346
Benthic Benthic (12) Water (9) 0.361
vs Water Column
Column
(Freshwater
and
saltwater)
O.S68
0.655
"Values in parentheses are the number of LC50 values used in the comparison.
*K-S statistic = maximum difference between the cumulative
distribution functions for benthic and water column species.
°Pr(K-S theoretical £ K-S observed) given that the samples
came from the same population.
3-12
-------
SECTION 4
TOXICTTY OF PHENANTHRENE (ACTUAL AND PREDICTED):
SEDIMENT EXPOSURES
4.1 TOXICTTY OF PHENANTHRENE IN SEDIMENTS:
The toxicity of phenanthrene spiked into sediments has been tested with two saltwater
amphipod species. Freshwater benthic species have not been tested in phenanthrene-spiked
sediments. All concentrations of phenanthrene in sediments or interstitial water where effects
were observed in benthic species (Table 4-1) are greater than SQC or FCV concentrations
reported in this document. Details about exposure methodology axe 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. Therefore, insights into relative sensitivities of aquatic species to phenanthrene
can only be obtained from results of water-only tests (Section 3). Data are available from a
number of experiments using both field and laboratory sediments contaminated with mixtures
of PAHs and other compounds which include phenanthrene. Data from these studies have not
been included here because it is not possible to determine the contribution of phenanthrene to
toxicity observed.
Swartz (1991) exposed the amphipods Eohaustorius e^tnarf"!8 and Leptocheims
piymiilnais to three phenanthrene-spiked sediments with total organic carbon content (TOC) of
1.0%t 2.6%, and 4.4%. Sediments were rolled (1) for two hours in phenanthrene-coated
bottle; (2) stored at 4°C for 72 hours; (3) rolled for an additional two hours, and (4) then
stored for 7 days at 4°C. In some of these experiments the concentration of phenanthrene was
not sufficient to cause 50% mortality hi any of the concentrations tested. In these cases
experiments were performed with sediments from the same locations with similar
4-1
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TCC concentrations as were used in the original experiments, but with one or two treatments
with higher phenanthrene concentrations and the appropriate controls (Tables 4-1, 4-2). When
there was a difference between the control mortality in one of the original experiments and in
the follow up experiment with the corresponding sediment and species, Abbott's correction was
performed on the data for each treatment separately using the appropriate control mortality.
Then the data for both experiments were pooled. The pooling of the data appears justified by
the similarity of the dose-response relationships in the original and the follow up experiments
(Appendix C). The 10-day LCSO's for both species increased with increasing organic carbon
concentration when the phenanthrene concentration was expressed on a dry weight basis, but
decreased when concentration was expressed on an organic carbon basis. LCSO's normalized
to dry weight differed by a factor of 3.1 (39.2 to 122 pg/g) for IL. estuarius over a 3.3-fold
range of TOC and a factor of 2.8 (92.4 to 255 pg/g) for Li plumuiosus over a 1.8-fold range
of TOC. The organic carbon normalized LCSO's for fi. estuaruiS differed by a factor of 1.1
(3,820 to 4,050 pg/goc) while for L- plumulosus they differed by a factor of 1.3 (6,490 to
8,200 Mg/goc).
Overall, the need for organic carbon normalization of the concentration of non-ionic
organic chemicals in sediments is presented in the SQC Guidelines (U.S. EPA, 1992a). The
need for organic carbon normalization for phenanthrene is also supported by the results of
spiked-sediment toxkity tests described above. 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 effects concentrations for phenanthrene and other non-ionic organic
chemicals on an organic carbon bas*s for a range of sediments. Evidence supporting thi$
prediction for phenanthrene and all SQC chemicals follows1 in Section 4.3.
4-3
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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, 1989a). Pore-
water LC50 values are available for two species (Table 4-1; 4-2), Swaitz (1991) found 10-
day LC50 values based on pore-water concentrations varied by a factor of 1.1 (138 to 146
pg/L) for IL ftstfflmus and by a factor of 1.3 (306 to 387 jtg/L) for L- plumulosus. This
variability is somewhat less than that shown when dry weight (factors of 3.1 and 2.8)
normalization is used to determine LCSOs based on phenanthrene concentration in sediments,
but similar to that shown when organic carbon (factors of 1.1 and 1.3) normalization is used.
A more detailed evaluation of the degree to which the response of benthic organisms can
be predicted from toxic units of substances in pore water can be made utilizing results from
toxicity tests with sediments spiked with other substances, including acenanphthene and
phenanthrene (Swaitz, 1991), cadmium (Swaitz et al., 1985), endrin (Nebeker et al., 1989;
Schuytema et al., 1989), fluoranthene (Swartz et al., 1990), or kepone (Adams et al., 1985)
(Figure 4-1; Appendix Q. Tests with acenaphthene and phenanthrene used two saltwater
amphipods (L. plumulosus and Ej. egtlfflT""'* and marine sediments. Tests with eaAiphm and
fhioranthene used the saltwater amphipod fRhepoxvnius abroniiis'l and marine sediments.
Freshwater sediments spiked with endrin were tested using the amphipod HyalaMa azteca: while
the midge, Chironomous tentans. was tested using kepone-spiked sediments. Figure 4-1
presents the percentage mortalities of the benthic species tested in individual treatments for each
chemical versus "pore water toxic units" for all sediments tested. Pore water toxic units are
the concentration of the chemical in pore water Gig/L) divided by the water only LC50 (pg/L).
In this normalization, 50% mortality should occur at one interstitial water toxic unit. In
general, 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 pore
water normalization was not used to derive sediment quality criteria, in this document because
4-5
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of the compiexation of non-ionic organic chemicals with pore water DOC (Section 2) and the
difficulties of adequately sampling pore waters. Data from the dieldrin experiments (Hoke
and Ankley, 1991) are not included because more knowledge of the pore water DOC will be
required .because dieldrin has a high K^ value.
4.3 TESTS OF THE EQUILIBRIUM PARTITIONING PREDICTION OF SEDIMENT
TOXXOTY:
Sediment Quality Criteria derived using the equilibrium partitioning approach utilize
partition coefficients and final chronic values from water quality criteria documents to derive
the sediment quality criteria concentration for protection of benthic organisms. The partition
coefficient (Koc) is used to normalize sediment concentrations and predict biologically available
concentrations across sediment types. Data are available to test the normalization for
phenanthrene in sediments. Testing of this component of SQC derivation requires three
elements: (1) a water-only effect concentration, such as a 10-day LC50 value in pg/L, (2) an
identical sediment effect concentration on an organic carbon basis, such as a 10-day LC50 value
in /xg/goc. and (3) a partition coefficient for the chemical, KOC in L/kgoc- This section presents
evidence that toe observed effect concentration in sediments (2) can be predicted utilizing the
water effect concentration (1) and the partition coefficient (3).
The observed 10-day LC50 values from phenanthrene-spiked sediment tests on a
basis with &. ftiffliarinft and L. ptoimitoffllS were predicted (Table 4-2) using the value
(10*") from Section 2 of this document and the 10-day water-only LC5Q values in Swartz
(1991). Ratios of predicted to actual LCSOs for phenanthrene averaged 1.54 (range 1.50 to
1.59) for E,. ffjffliariiifl and 2.10 (range 1.80 to 2.27) for L* plunMlfflMS The overall mean for
both species was 1.80.
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 toxkity tests with amphipods
exposed to sediments spiked with acenaphthene, phenanthrene, dieldrin , endrin, or
fluoranthene. Data from the kepone experiments are not included because we do not have a
4-7
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for kepone from ERL, Athens. Swartz (1991) exposed the saltwater amphipods E.
restuarius and 2*. plumulosus to acenaphthene and phenanthrene in three marine sediments
having 1.02, 2.61 and 4.37% organic carbon. Swartz et al. (1990) exposed the saltwater
amphipod 2L abronius to fluoranthene in three marine sediments having 0.18, 0.31 and 0.48%
organic carbon. Hoke and Ankley (1991) exposed the amphipod Hvalella aaissa to three
dieldrin-spiked freshwater sediments having 1.7, 3.0 and 8.5% organic carbon. Nebeker et al.
(1989) and Schuytema et al. (1989) exposed IL az$e^ 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" for
each sediment treatment. Predicted sediment toxic units are the concentration of the chemical
in sediments (pg/goc) divided by the predicted LC50 Otg/goc) in sediments (the product of KOC
and the 10-day water-only LC50). In this normalization, 50% mortality should occur at one
predicted sediment toxic unit. Endrin and fluoranthene data indicate a slight under prediction,
and dieldrin, acenaphthene and phenanthrene a slight over prediction, of the observed mortality.
In general, however, this comparison illustrates that the EqP method can account for the effects
of different sediment properties and properly predict the effects concentration in sediments using
the effects concentration from water only exposures. These are two fundamental propositions
that underlie the EqP method for deriving sediment quality criteria.
4-9
-------
-------
SECTIONS
CRITERIA DERIVATION FOR PHENANTHRENE
5.1 CRITERIA DERIVATION:
• ,
The equilibrium partitioning method for calculating sediment quality criteria is based
on the following procedure. If FCV (pg/L) is the Final Chronic Value which is the chronic
effects concentration from the water quality criteria for the chemical of interest, then the
**•'.
sediment quality criteria, SQC 0*g/g sediment), is computed using the partition coefficient, K,
(L/g sediment), between sediment and pore- water.
SQC « Kp FCV (5-1)
On a sediment organic carbon basis, the sediment quality criteria, SQCoc (ng/goc). is:
SQCOC=KOCFCV (5-2)
where KQC is the organic carbon partition coefficient for the chemical. Since this quantity is
presumably independent of sediment type for non-ionic organic chemicals, so also is
Table 5-1 contains the calculation of the phenanthrene sediment quality criteria.
TABLE 5-1. SEDIMENT QUALITY CRITERIA FOR PHENANTHRENE
Type of
Water Body
FreshWater
Saltwater
TjOff /JC y /><> JT Ff^V
(L/kg) (L/kg) (Mg^>)
4.36 4.29 6.32
4.36 4.29 8.26
Otg/gtt)
123'
161*
•SOCv. * dO4-" L/taLv-Wia* ktvVav.X6.32 ue ohenanthrene/L) - 123 u
phenanthrene/goc
"SQCoc = (lO4^ L/kgoc)«(10'J kgoc/goc)*(8.26 /tg phenanthrene/L) = 161 fig
phenanthrene/goc
5.2 UNCERTAINTY ANALYSIS:
Some of the uncertainty in the calculation of the phenanthrene sediment quality criteria can
5-1
-------
be estimated from the degree to which the equilibrium pardoning 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 from sediments is equal on an organic carbon
basis, and (2) that the effects concentration in sediment G*g/goc) can be estimated from the
product of the effects concentration from water only exposures Gtg/L) and the partition
coefficient KOC (L/kg). The uncertainty associated with the sediment quality criteria 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 the water-only and sediment toxicity tests that
have been conducted in support of the sediment criteria development effort. These freshwater
and saltwater tests span a range of chemicals and organisms; they include both water-only and
exposures and they are replicated within each ch^m*eg*-*>'^»»iCT'i-^xppinirg media
treatment. These data were analyzed using an analysis of variance (ANOVA) to estimate the
uncertainty (i.e. the variance) associated with varying the exposure media and that associated
with experimental error. If the EqP model were perfect, then mere 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 the LCSOs from the water-only and sediment
exposures illustrated in Figure 4.2 in Section 4. The EqP model can be used to normalize the
data in order to put it on a common basis. The LC50 for «*K™«* on an organic carbon basis,
LC50i.oc» is related to the LC50 obtained from a water-only exposure, LCSOy via the
partitioning equation:
LCSQwc - KocLCSGw (5-3)
Therefore, K^ can be used to define the equivalent sediment toxicity based on free
concentration in pore water?
5-2
-------
LC50SOC
LC50W * _ (5-4)
The EqP model asserts that toxicity of sediments expressed as the free pore water concentration
equals toxicity in water only tests.
LC5CW = LC50W (5-5)
Therefore, either LC50,*, or LCSO* are estimates of the true LC50 for this chemical - organism
pair. In this analysis, the uncertainty of K^ 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 5-5 are subject to various sources
of random variations. A number of chemicals and organisms have been tested. Each chemical
- organism pair was tested in water-only exposures and in different sediments. Let or represent
the random variation due to this source. Also, each experiment is replicated. Let 6 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
a represents the uncertainty due to the approximations inherent in the model and € represents
the experimental error. Let (
-------
measurement error, (
-------
TABLE 5-3. SEDIMENT QUALITY CRITERIA
CONFIDENCE LIMITS FOR PHENANTHRENE
Sediment Quality Criteria
95% Confidence Limits (ue/e~-)
Type of
Water Body
Fresh Water
Saltwater
Mg/goc
120
160
Lower
56
74
Upper
260
340
5.3 COMPARISON OF PHENANTHRENE SQC TO STORET DATA FOR
PHENANTHRENE:
A STORET (U.S. EPA, 1989a) data retrieval was performed to obtain a preliminary
assessment of the concentrations of phenanthrene in the sediments of the nation's water bodies.
Log probability plots of phenanthrene concentrations on a dry weight basis in sediments are
shown in Figure 5-1. Phenanthrene is found at varying concentrations in sediments from rivers,
lakes and near coastal water bodies in the United States. Median concentrations are generally
about 0.1 pg/g in each of the three water bodies. There is significant variability with
phenanthrene concentrations in sediments ranging over seven orders of ipagqfa'dg within the
country.
»
The SQC for phenanthrene can be compared to existing concentrations of phenanthrene
in sediments of natural water systems in the United States as contained in the STORET database
(U.S. EPA, 1989a). 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 compared to phenanthrene's distribution in sediments as
examples only. For fresh water sediments, SQC; values are 1.2 pg/g in sediments having 1 %
organic carbon and 12 pg/g dry wt. in sediments .having 10% organic carbon; for marine
sediments SQC are 1.6 pg/g and 16 Mg/g, respectively. Figure 5-1 presents the comparisons
of these SQC to probability distributions of observed sediment phenanthrene levels for streams
5-5
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Figure 5-1. Probability distribution of
nations of phenanthreae in sediments from
riinnaniiij uuuusuuvu wi vuiibeuuauwiH u» UJMTJMIIMIWII^ «* «««Mui%>uid MWI»
streams (n-584), lakes (n-50) and estuaries (n-87) in the United States from
1986 to 1990, from the STORET (U.S. EPA, 1989e) database, compared to the
phenanthrene SQC values of 12 ug/g in freshwater sediments having TOC -
10% and 1.2 jiftVt in freshwater sediments having TOC - 1%; SQC values for
saltwater sediments are 16 ug/g when TOC -10% and 1.6 ug/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%.
S-6
-------
and lakes (fresh water systems, shown on the upper panels) and estuaries (marine systems,
lower panel). For streams (n = 584) the SQC of 1.2 jtg/g for 1% organic carbon sediments
is exceeded for 10% of the data and the SQC of 12 /*g/g for sediments having 10% TOC is
exceeded by 2% of the data. For lakes (n = SO) the SQC for 1 % organic carbon sediments
is exceeded for almost 20% of the data and data for sediments with 10% organic carbon exceed
the SQC 2% of the time. In estuaries, the data (n = 87) indicate that the criteria of 1.6 ug/g
dry weight for sediments having 1 % organic carbon is exceeded for about 5 % of the data while
h.
the criteria of 16 pg/g dry weight for sediments having 10% organic carbon are not exceeded
by the post 1986 samples. .
A second database developed as part of the National Status and Trends Program (NOAA,
1991) is also available for assessing contaminant levels in marine sediments that are
representative of areas away from sources of contamination. The probability distribution for
these data, which can be directly expressed on an organic carbon basis, is compared to the
saltwater SQC for phenanthrene (160 pg/goc) °n Figure 5-2. Data presented are from sediments
with 0.20 to 31.9 percent organic carbon. The median organic carbon normalized phenanthrene
concentration (about 5.0 Mg/goc) is a factor of 32 below the SQC of 160 pg/goc- About 2% of
these samples (n - 900) exceeded the criteria. Hence, these results are consistent with the
preceding comparison of the marine SQC to STORET data.
Regional differences in phenanthrene 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), or die relative frequencies and intensities of sampling in different
study areas. It is presented as an aid in assessing the range of reported phenanthrene sediment
concentrations and the extent to which they may exceed the sediment quality criteria.
5-7
-------
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-------
SECTION 6
CRITERIA STATEMENT
The procedures described in the "Guidelines for Deriving Numerical National Sediment
Quality Criteria for Nonionic Organic Chemicals for the Protection of Benthic Organisms" (U.S.
EPA, 1992a) indicate that, except possibly where a locally important species is very sensitive
or sediment organic carbon is < 0.2%, benthic organisms should be acceptably protected in
freshwater sediments containing <. 120 pg phenanthrene/g organic carbon and saltwater
sediments containing <. 160 /tg phenanthrene/g organic carbon.
These concentrations are the U.S. EPA's best scientific judgement at this time of the
acceptable concentration of phenanthrene in sediments. Confidence limits of 56 to 260 pg/gbc
: for freshwat
er sediments and 74 to 340 pg/goc for saltwater sediments are provided as an estimate of the
! uncertainty associated with the degree to which the observed concentration in sediment. G*g/&c)>
which may be toxic can be predicted using the 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 phenanthrene, and sound judgement are required in the
regulatory use of sediment quality criteria and their confidence limits. The upper confidence
limit might be interpreted as a concentration above which impacts on benthic species would be
highly likely. The lower confidence limit might be interpreted as a concentration below which
impacts on benthic species would be unlikely.
6-1
-------
-------
SECTION 7
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7-1
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7-3
-------
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' Railway, NJ. 1463 pp + appendices.
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APPENDIX B: THE OCTANOL-WATER PARTITION COEFFICIENT, K™ FOR
PHENANTHRENE.
B.I GENERAL INFORMATION:
Partitioning between water and natural soils, sediments, and aquifer materials is an
important process affecting transformation rates, toxicity, and the ultimate disposition of organic
chemicals in the environment. Extensive research, focusing on the partitioning of neutral
organic compounds, has shown that adsorption of these compounds generally is controlled by
hydrophobic interactions. As a result, the affinity that a natural sorbent has for neutral organic
solutes, in most cases, can be reliably estimated from the hydrophobicity of the solute and the
sorptive capacity of the sorbent. Organic carbon content has been used almost exclusively as
a measure of the sorptive capacity of natural sedimentary material. (Organic matter or volatile
solids content has also been used but not as widely.) To quantitatively characterize the
hydrophobic nature of organic compounds, researchers have used various measurable
parameters, including octanol/water partition coefficients (Kg*), water solubility (corrected for
crystal energy), reverse phase HPLC retention, and topological parameters of the compounds
such as calculated surface area. Generally, octanol/water partition coefficients have been used
more extensively, not only for estimating the partitioning of organic compounds to sedimentary
materials, but also for estimating bioaccumulation of organic compounds to aquatic organisms.
The Km is defined as the ratio of the equilibrium concentration of a dissolved substance
in a system consisting of n-octanol and water and is ideally dependent only on temperature and
pressure:
Kow-CWC* (B-l)
where C^ is the concentration of the substance in n-octanol and C» is the concentration of the
substance in water. The KW is used in estimating the organic-carbon- normalized sediment-
water partition coefficient (Koc) and is frequently reported in the form of its logarithm to base
ten as log P.
B-l
-------
B.2 LITERATURE DATA:
An extensive literature search was performed for phenanthrene and two standard reference
compounds, biphenyl and pyrene. Generally, problems encountered in compiling and reporting
fate constants from published data and from databases during the last several years have ranged
from retrieval of misquoted numbers to resolution of nested citations (Kollig, 1988). Some
citations were three or more authors removed from the original work or contained data that
were referenced as unpublished data or as personal communication. The same problems were
experienced during this literature search. The largest difference in misquoting numbers was six
«
orders of magnitude. For these reasons, ERL- Athens obtains data from the primary sources
and releases values coming only from these primary sources. Unpublished data or data which
originated through personal communication are rejected as well as data that are insufficiently
documented to determine their credibility and applicability or reliability.
Tables B-l and B-2 show the measured and estimated KQW values, respectively, retrieved
by this literature search. Each of the measured values was experimentally determined by the
researcher using one of several laboratory methods. The individual experimental methods are
not identified here. The estimated literature values were computed by the researchers by one
of several published techniques. The individual computational techniques also are not identified
here.
fi.3 ERL-ATHENS MEASURED DATA:
To enhance confidence in the measured K^ values, two independent experimental methods,
[shake-centrifugation (SQ, generator column (GCol)], were used to determine a KQW value for
phenanthrene at the U.S. EPA laboratory at Athens, Georgia. The SC method is routinely used
to measure the partitioning of compounds with K^ values on the order of l(f to 10*. The
method involves adding a layer of octanol containing the compound of interest onto the surface
of water contained in a centrifuge tube. Both phases are mutually presaturated before beginning
B-2
-------
the measurements. Equilibration is established by gentle agitation and any emulsions formed
are broken by centrifugation. The concentration in each phase is determined usually by a
chromatographic method and the K<,w value calculated using Equation B-l.
TABLE B-l. MEASURED LOGloKoW VALUES FOUND IN THE LITERATURE
Chemical
value
Reference
Phenanthrene
Biphenyl
Pyrene
4.28
4.46
4.562
4.57
4.63
3.16
3.63
3.75
3.76
3.79
3.89
4.008
4.01
4.04
4.09
4.10
4.96
5.05
5.09
5.18
5.22
5.52
Haky and Young, 1984
Hansch and Fujita, 1964
De Bruijn et al., 1989
Karickhoffetal., 1979
Bruggeman et al., 1982
Rogers and Cammarata, 1969
De Kock and Lord, 1987
Veith et al., 1979
Miller et al., 1984
Rapaport and Eisenreich, 1984
Woodbum et al., 1984
De Bruijn et al., 1989
Eadsforth, 1986
Banerjee et al., 1980
Ellington and Stancil, 1988
Bruggeman et al., 1982
Rapapaport and Eisenreich, 1984
Ellington and Stancil, 1988
Means et al., 1980
Karickhoffetal., 1979
f^M. .a. ri^jMinFl A* «I 1 QQ^
tsniggenian et ai.t 1.70*
Burkhard et al., 1985
The original GCol method, limited to compounds with KOW values of less than 10* was
modified (Woodbum et al., 1984) and used to determine K^ values up to 10*. Briefly, the
method requires the packing of a 24-cm length of tubing with silanized Chromosorb W.
Octanoi, containing the chemical in a known concentration, is then pulled through the dry
support by gentle suction until the octanol appears at the exit of the column. Water is then
B-3
-------
pumped through the column at a rate of less than 2 ml per minute to allow equilibration of the
chemical between the octanol and water. The first 100 ml are discarded followed by collection
of an amount of water sufficient to determine the chemical concentration. The KOW is calculated
using Equation B-l.
TABLE B-2. ESTIMATED LOG,bKoW VALUES FOUND IN THE LITERATURE
Chemical
Phenanthrene
Biphenyl
Pyrene
Log10KoW value
4.44
4.45
4.63
4.64
3.79
3.95
3.98
4.14
4.25
4.42
4.50
4.85
4.88
4.90
5.12
5.22
5.32
Reference
Kamletetal., 1988
Mabey et al., 1982
Mackay et al., 1980
Yalkowsky et al., 1983
Yalkowsky et al., 1983
Miller etal., 1985
Kamlet et al., 1988
Mackay et al., 1980
Arbuckle, 1983
Doucette and Andren, 1987
D'Amboise and Hanai, 1982
Kamlet et al., 1988
Lyman et al., 1982
Mabey et al., 1982
Mackay et al., 1980
Yalkowsky et al., 1983
Callahan et al., 1979
When repetitive measurements are made in the Athens laboratory, a protocol is established
to assure compatibility with future experiments. These protocols describe the entire
experimental scheme including planning, sample requirements, experimental set up and chemical
analysis, handling of data, and quality assurance. Only established analytical methods for solute
concentration measurement are applied and the purity and identity of- the chemical are
determined by spectroscopic means. The name on the label of the chemical's container is not
proof of the identity.
Standard reference compounds (SRCs) are tested with each experiment. SRCs are
compounds mat are used as quality assurance standards and as references in inter-laboratory
B-4
-------
generation of data. The value of the process constam(s) has been established by repetitive
measurements for an SRC and serves as baseline information for evaluating all experimental
techniques and all aspects of quality assurance. Because the SRC is taken through the entire
experimental scheme, its acceptable result will assure the experimenter that equipment and
measurement methods are functioning satisfactorily. Table B-3 shows the KQW values for
phenanthrene and the SRCs, biphenyl and pyrene, measured at the Athens laboratory by the
SC methods. The SRCs were not measured by the GCol method.
TABLE B-3. LOG10Kow VALUES MEASURED BY SHAKE-
CENTRIFUGATION (SC) AND GENERATOR COLUMN (GCOL).
FOR PHENANTHRENE AND CONCURRENTLY ANALYZED
STANDARD REFERENCE COMPOUNDS.
Chemical
SC
GCol
Phenanthrene 4.30
Biphenyl 4.06
Pyrene 5.17
4.40
The logto of the average of eight previous measurments of KOW by the shake-centrifugation
method for biphenyl is 4.09. The log10Kow of the average of thirteen previous measurements
by the shake-centrifugation method for pyrene is S.05. These are in good agreement with the
SQC shake-centrifugation measurements made concurrently with the phenanthrene
measurements.
B.4 ESTIMATED DATA:
A promising new computational method for predicting chemical reactivity is the computer
expert system SPARC (SPARC Performs Automated Reasoning in Chemistry) being developed
by Samuel W. Karickhoff, at ERL-Athens, and other scientists at the University of Georgia
(Karickhoff et al., 1989). The system has the capability of crossing chemical boundaries to
B-S
-------
cover all organic chemicals and uses algorithms based on fundamental chemical structural theory
to estimate parameters. Organic chemists have, in the past established the types of structural
groups or atomic arrays that impart certain types of reactivity and have described, in
"mechanistic" terms, the effects on reactivity of other structural constituents appended to the
site of reaction. To encode this knowledge base, Karickhoff and his associates developed a
classification scheme that defines the role of structural constituents in affecting or modifying
reactivity. SPARC quantifies reactivity by classifying molecular structures and selecting
appropriate "mechanistic" models. It uses an approach that combines principles of quantitative
structure-activity relationships, linear free energy theory (LFET), and perturbed molecular
orbital (PMO) or quantum chemistry theory. In general, SPARC utilizes LFET to compute
thermal properties and PMO theory to describe quantum effects such as delocalization energies
or polarizabilities of pi electrons.
SPARC computes KOW values from activity coefficients in the octanol( - y and water ( ~ U)
phases using Equation B-2. " .
Log^Kow - loglo (- V-lo) + loglo (Mo/Mw) (B-2)
where MQ and Mw are solvent molecularities of octanoi and water, respectively. SPARC
computes activity coefficients for any solvent/solute pair for which the structure parser can
process the structure codes. Ultimately, any solvent/solute combination can be addressed. New
solvents can be added as easily as solutes by simply providing a Simplified Molecular
Interactive Linear Entry System (SMILES) string (Anderson et al., 1987, Weininger, 1988).
Activity coefficients for either solvent or solute are computed by solvation models that are built
from structural constituents requiring no data besides the structures.
A goal fa SPARC is to compute a value that is as accurate as a value obtained
experimentally for a fraction of the cost required to measure it. Because SPARC does not
depend on laboratory operations conducted on compounds with structures closely related to that
of the solute of interest, it does not have the inherent problems of phase separation encountered
B-6
-------
in measuring highly hydrophobia compounds (logwKow > 5). For these compounds, SP ARC'S
computed value should, therefore, be more reliable than a measured one. Reliable experimental
data with good documentation are still necessary, however, for further testing and validation
of SPARC.
CLOGP (Chou and Jurs, 1979) is a computerized program that estimates the log,,,!^,
based on Leo's Fragment Constant Method (Lyman et al., 1982). CLOGP provides an estimate
of logioKow using fragment constants (Q and structural factors (FJ that have been empirically
derived for many molecular groups. The estimated log^R^ is obtained from the sum of
constants and factors for each of the molecular subgroups comprising the molecule using
Equation B-3.
n
= Eft + Fi) ' (B-3)
The method assumes that loguKo* is a linear additive function of the structure of the solute
and its constituent parts and that the most important structural effects are described by available
factors. The structure of the compound is specified using the SMILES notation. The CLOGP
algorithm is included in the database QSAR1 located at EPA's Environmental Research
Laboratory at Duluth, Minnesota. All CLOGP values reported here were obtained through
QSAR.
Table B-4 shows the estimated log10Kow values that were computed with SPARC and
CLOGP.
'Quantitative Structure-Activity Relationships (QSAR) is an interactive chemical database
hazard assessment system designed to provide basic information for the evaluation of the
and effects of chemicals in the environment. QSAR was developed jointly by the U.S.
EPA Environmental Research Laboratory, Duluth, Minnesota, Montana State University Center
for Data System and Analysis, and the Pomona College Medicinal Chemistry Project.
B-7
-------
TABLE B-4. LOG10KoW VALUES ESTIMATED BY SPARC AND CLOGP
Chemical
SPARC CLOGP
Phenanthrene 4.58
Biphenyl 4.25
Pyrene 5.13
4.49
4.03
4.95
B-8
-------
REFERENCES (APPENDIX B)
Anderson, E.; G.D. Veith, and D. Weininger. 1987. SMILES: A line notation and
computerized interpreter for chemical structures. U.S. EPA, Duluth, MN, EPA/600/M-
87-021.
Arbuckle, W.B. 1983. Estimating activity coefficients for use in calculating environmental
parameters. Environ. Sci. Technol. 17(9):537-542.
Banerjee, S., S.H. Yalkowsky, and S.C. Valyani. 1980. Water solubility and octanol/water
partition coefficients of organics: Limitations of the solubility-partition coefficient
correlation. Environ. Sci. Technol. 14(10): 1227-1229.
Bruggeman, W.A, J. Van der Steen, and O. Hutzinger. 1982. Reversed-phase thin-layer
chromatography of polynuclear aromatic hydrocarbons and chlorinated biphenyls:
Relationship with hydrophobicity as measured by aqueous solubility and octanol-water
partition coefficient. J. Chromatogr. 238:335-346.
Burkhard, L.P., O.W. Kuehl, and G.D. Veith. 1985. Evaluation of reverse phase liquid
chromatography/massspectrometry for estimation of n-octanol/water partition coefficients
for organic chemicals. Chemosphere 14(10): 1551-1560.
Callahan, M.A., M.W. Slimak, N.W. Gabel, I.P. May, C.F. Fowler, J.R. Freed, P. Jennings,
R.L. Durfee, F.C. Whitmore, B. Maestri, W.R. Mabey, B.R. Holt, and C. Gould.
1979. Water-related environmental fate of 129 priority pollutants. Volume II:
Halogenated aliphatic hydrocarbons, halogenated ethers, monocyclic aromatics, phthalate
esters, polycycUc aromatic hydrocarbons, nitrosamines, and miscellaneous compounds.
U.S. EPA, Office of Water Planning and Standards, Office of Water and Waste
Management, Washington, DC, EPA-440/4-79-029b.
Chou, J.T. and P.C. JUTS. 1979. Computer-assisted computation of partition coefficients from
molecular structures using fragment constants. J. Chem. Inf. Comput. Sci. 19(3): 172-
178.
D'Amboise, M. and T. Hanai. 1982. Hydrophobicity and retention in reversed phase liquid
chromatography. J. Liq. Chromatogr. 5(2):229-244.
De Bruijn, J., F. Busser, W. Seinen, and J. Hermens. 1989. Determination of octanol/water
rtition coefficients for hydrophobic ""
viron. Toxicol. Chem. 8:499-512.
De Kock, A.C., and D.A. Lord. 1987. A simple procedure for determining octanol-water
partition coefficients using reverse phase high performance liquid chromatography
(RPHPLQ. Chemosphere 16(1): 133-142.
Doucette, W.J., and A.W. Andren. 1987. Correlation of octanol/water partition coefficients
and total molecular surface area for highly hydrophobic aromatic compounds. Environ.
Sci. Technol. 21(8):821-824.
B-9
-------
Eadsforth, C.V. 1986.. Application of reverse-phase h.p.l.c. for the determination of partition
coefficients. Pest. Sci. 17:311-325.
Ellington, J.J., and F.E. Stancil, Jr. 1988. Octanol/water partition coefficients for evaluation
of hazardous waste land disposal: Selected chemicals. U.S. EPA, Environmental
Research Laboratory, Athens, GA, Environmental Research Brief; EPA/600/M-88/010.
Haky, J.E. and A.M. Young. 1984. Evaluation of a simple HPLC correlation method for the
estimation of the octanol-water partition coefficients of organic compounds. J. Liq.
Chromatogr. 7(4):675-689.
Hansch, C. and T. Fujita. 1964. A method for the correlation of biological activity and
chemical structure. J. Am. Chem. Soc. 86:1616-1626.
Kamlet, M.J., R.M. Doherty, P.W. Carr, D. Mackay, M.H. Abraham, and R.W. Taft. 1988.
Linear solvation energy relationships: Parameter estimation rules that allow accurate
prediction of octanol/water partition coefficients and other solubility and toxic properties
of polychlorinated biphenyls and polycyclic aromatic hydrocarbons. Environ. Sci.
Technol. 22(5):503-509.
Karickhoff, S.W., D.S Brown, and T.A. Scott. 1979. Sorption of hydrophobic pollutants on
natural sediments. Water Res. 13:241-248.
Karickhoff, S.W. and D.S. Brown. 1979. Determination of octanpl/water distribution
coefficients, water solubilities, and sediment/water partition coefficients for hydrophobic
organic compounds. U.S. EPA, Environmental Research Laboratory, Athens, GA,
EPA-600/4-79-032.
Karickhoff, S.W., L.A. Carreira, C. Melton, V.K. McDaiuel, A.N.VeUino, and D.E. Mute.
1989. Computer prediction of chemical reactivity- The ultimate SAR. U.S. EPA,
Environmental Research Laboratory, Athens, GA, Environmental Research Brief;
EPA/600/M-89/017.
Kollig, H.P. 1988. Criteria for evaluating the reliability of literature data on environmental
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Inc.,. Great Britain. 17:287-311.
Lyman, W.J., W.F. Rheel, and D.H. Rosenblatt. 1982. Handbook of Chemical Property
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Inc., NY, Table 1-4.
Mabey, W.R., J.H. Smith, R.T. Podoll, H.L. Johnson, T. Mill, T.W. Chou, J. Gates. I.W.
Partridge, H. Jaber, and D. Vandenberg. 1982. Aquatic fate process data for organic
priority pollutants. U.S. EPA, Office of Water Regulations and Standards, Washington,
DC, Final Report, EPA-440/4-81-014.
Mackay, D., A. Boon, and W.Y. Shui. 1980. Relationships between aqueous solubility and
octanol-water partition coefficients. Chemosphere 9:701-711.
Means, J.C., S.G. Wood, J.J. Hasset.and W.L. Banwart 1980. Sorption of polvnuclear
aromatic hydrocarbons by sediments and soils. Environ. Sci. Technol. 14(12): 1524-
1528.
B-10
-------
Miller, M.M., S. Ghodbane, S.P. Wasik, Y.B. Tewari, and D.E. Martire. 1984. Aqueous
solubilities, octanol/water partition coefficients, and entropies of melting of chlorinated
benzenes and biphenyls. J. Chem. Eng. Data 29(2): 184-190.
Miller, M.M., S.P. Wasik, G. Huang, W. Shui, and D. Mackay. 1985. Relationships between
octanol-water partition coefficient and aqueous solubility, environ. Sci. Technol.
19(6):522-529.
Rapaport, R.A. and S.J. Eisenreich. 1984. Chromatographic determination of octanol-water
partition coefficients (K^J for 58 polychlorinated biphenyls congeners. Environ. Sci.
Technol. 18(3): 163-170.
Rogers, K.S., and A. Cammarata. 1969. Superdelocalizability. and charge density: A
correlation with partition coefficients. J. Med. Chem. 12:692-693.
Vtith, G.D., N.M. Austin, and R.T. Morris. 1979. A rapid method for estimating log P for
organic chemicals. Water Res. 13:43-47.
Weininger, D., 1988. SMILES, a chemical language and information system. 1. Introduction
to methodology and encoding rules. J. Chem. Inf. Comput. So. 28:31-36.
Woodburn, K.B., W.J. Doucette, and A.W. Andren. 1984. Generator column determination
of octanol/water partition coefficients for selected polychlorinated biphenyls. Environ.
Sci. Technol. 18(6):457-459.
Yalkowsky, S.H., S.C. Valvani, and D. Mackay. 1983. Estimation of the aqueous solubility
of some aromatic compounds. Residue Rev. 85:43-55.
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