800R88100
DC 90440
May 1988
SCD# 17
Wittr
INTERIM SEDIMENT CRITERIA VALUES FOR
NONPOL AR HYDROPHOBIC ORGANIC CONTAMINANTS
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INTERIM SEDIMENT CRITERIA VALUES FOR NONPOLAR HYDROPHOBIC
ORGANIC COMPOUNDS
INTRODUCTION
Toxic contaminants in the bottom sediments of lakes, rivers and coastal
waters can degrade the environment. Available data indicate many locations
where existing sediment contaminant concentrations are now causing significant
adverse environmental effects on aquatic life, even when water column
contaminant concentrations comply with established water quality criteria
(Malins et al. I960, 1982). Since 1985, the Criteria and Standards Division
of EPA has been pursuing the Equilibrium Partitioning (EP) approach for
estimating sediment quality criteria for nonpolar and metal contaminants. .In
anticipation of favorable review of the approach by EPA's Science Advisory"
Board, interim sediment criteria values based on the EP approach for selected
nonpolar, hydrophobic organic compounds were developed. These interim criteria
values can be used to evaluate the appropriate applications of sediment criteria
in existing regulatory programs. This report describes how the interim numbers
were developed and briefly how the criteria values can be used to evaluate
the extent of sediment contamination. Preparation of this report has resulted
in a great deal of discussion regarding choice of partition coefficients and
methods for determining the uncertainty in the interim criteria values.
Therefore, it is very likely that the final values that EPA will recommend
will differ from these values although not substantially. Any user of these
numbers should be aware that these numbers are indeed interim and not final
criteria values.
The main part of this report describes the development of interim criteria
values for nonpolar organic contaminants for which chronic water quality
1
-------
criteria have been generated. In Appendix E of the report, additional interim
criteria for selected PAHs are given.
EQUILIBRIUM PARTITIONING APPROACH
Before describing how the interim criteria were estimated, the technical
approach that forms the basis for the sediment criteria development effort
will be discussed. The approach that is being pursued by the Criteria and
Standards Division for establishing sediment quality criteria, on the
recommendation of participants in the technical workshops and steering
committees, is the EP approach (Neff 1985, Cowan 1986, Cowan 1987). The EP
approach is based on two interrelated assumptions. First, that the interstitial
water concentration of the contaminant is controlled by partitioning between
the sediment and the water at contaminant concentrations well below saturation
in both phases. Thus, the partitioning can be calculated from the quantity
of the sorbent(s) on the sediment and the appropriate sorption coefficient(s).
For nonpolar organic contaminants, the primary sorbent is the organic carbon
on the sediment; therefore, the partition coefficient is called the organic
carbon normalized partition coefficient, KOC< Second, the toxicity and
accumulation of the contaminant by benthic organisms is correlated to the
interstitial, or pore water concentration and not directly to the total
concentration of the contaminant on the sediment.
When the EP approach is used to estimate sediment quality criteria, chronic
water quality criteria (WQC) are used to establish the "no-effect" concentration,
in the interstitial water. Chronic water quality criteria are used to protect
benthic organisms from effects due to their long-term exposure to low ambient
concentrations in the sediment. The use of WQC assumes that the sensitivities-
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of water column and benthic species to a compound are similar. This assumption
is being evaluated. This interstitial water concentration (Cw) is then used
with the partition coefficients (KQ(.) and the following equation
Csed * *oc
to calculate the concentration of the contaminant on the sediment (C .,) that
sed
at equilibrium will result in this interstitial water concentration. This
concentration on the sediment will be the numerical criteria value (SQC).
For compounds when, chronic water quality criteria are not available, the EP
approach can still be useful. For example, using upper-bounds effects
concentrations will give comparable (i.e, upper-bounds effects) sediment
concentrations. The interpretation of such sediment values is analogous to
the interpretations of the comparable water column values used in their
derivation.
DEVELOPMENT OF INTERIM NUMBERS
To estimate interim sediment criteria values, two sets of data are needed
for each compound for which criteria values are required. These data are the
water quality criteria and the partition coefficients.
WATER QUALITY CRITERIA VALUES
Water Quality Criteria (WQC) concentrations are available for 17 nonpolar
organic chemicals (Hansen 1987). The criteria values are summarized in Table 1
The procedures for deriving these criteria are described in Appendix A. The
WQC concentrations consist of the Criteria Maximum Concentration (CMC) and
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the Criteria Continuous Concentration (CCC). The CMC is not applicable for
derivation of SQC concentrations because it protects aquatic life from acutely
lethal effects of a chemical. The CCC is the lower of the Final Chronic Value
(FCV), the concentration protecting aquatic life from chronic toxicity, and
the Final Residue Value (FRV), the concentration protecting uses of aquatic
life. These uses include marketability of aquatic life based on FDA or other
action levels or consumption of aquatic life by wildlife. The CCC is the
appropriate value to use in deriving SQC because it protects aquatic life
from effects due to long-term exposure to contaminated sediments. Both the
FCV and FRV are presented in Table 1.
Important limitations of Table 1 should be mentioned. First, the WQC
concentrations for acenaphthene, aniline, diethylhexylphthalate, methyl-
parathion, phenanthrene, and 1,2,4-trichlorobenzene must be used with caution
•
because they are preliminary values until criteria documents have been peer
reviewed and accepted. Second, the PCB criteria is based on the FDA action
level of 5 mg/kg and bioaccumulation factors measured in th> laboratory.
Since 1980 when this criteria was developed, the FDA action level has been
changed to 2 mg/kg. Furthermore, the residue values do not account for
bioconcentration in the food chain which results in bioaccumulation factors
for fish at least 10 times higher than those measured in the laboratory.
This bioconcentration has been shown to be important for DDT and PCB.
PARTITION COEFFICIENTS
For estimating the interim sediment quality criteria values presented
here, it is assumed that the sediment organic carbon partition coefficient,
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K , can be accurately calculated from the octanol-water partition coefficient,
K , using the following equation (DiToro 1985):
ow
Log10(Koc) » 0.00028 + 0.983*LoglO(KQw) (2)
The K values used in the regression analysis were carefully screened to
remove data for experiments that were conducted at high particle concentrations
and to ensure that only nonpolar organic compounds were included. This
screening is important because particle interactions at high particle
concentrations can ,-esult in errors in the K values (DiToro 1985). This
relationship is chosen to calculate K values rather than using tabulated
oc
Koc values because KQw values have been determined by more researchers and
the procedure for determining K values is simpler than that used for
ow
determining K values because interferences caused by dissolved organic carbon
and particle effects do not have to be considered or accounted for in the
experimental design and data analysis.
Because K is used to estimate K , and ultimately the interim sediment
OW OC
quality criteria, it is important that both an estimate of the mean K and a
quantification of its uncertainty be determined. To provide a preliminary
estimate of the K values and their uncertainty, for each compound in Table 1.
the following alternative methods were used.
• Review of all measured values and calculation of the geometric mean and
standard deviation of the mean from the data
• Determine recommended value from Leo-Hanch database
• Estimate log K from correlations with aqueous solubility
• Estimate log K from structure-activity relationships.
OW
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The results of the four methods are presented in Table 2. The estimates derived
from the four methods compared for overall consistency.
The review of all measured values was conducted using the database
developed by Envirosphere for the report by Pavlou et al. (1987). Because
this database has been updated since that report was prepared the values in
Table 2 may differ slightly from those presented in that report. The
recommended value for the log KQw from the Leo and Hanch Log P Database (Leo
1984) was also tabulated for comparison.
The methods used for estimating the log KQw values from the solubility
and from the chemical structure of the compound are outlined in Appendices B
and C, respectively. Estimates of KQW based on aqueous solubility, which
were corrected for solids melting point (Bowman and Sans 1983), were calculated
f»om solubility and melting point data reported in the Arizona Database of
Aqueous Solubility (Yalkowsky et al. 1987). The log mean K for solubilities
measured in the range of 15 to 25°C is reported in Table 2.
PCB Aroclor KQW values reported in the "measured" column in Table 2 were
calculated using the median of the log mean K values for the homologs and
ow
the Aroclor homolog composition as illustrated in Appendix D. Log mean K
OW
values for the homologs were compiled from six sources (Rapaport and Eisenrich
1984, Rapaport and Eisenrich 1985, Shiu and MacKay 1986, Woodburn et al. 1984,
Miller et al. 1984, Chiou et al. 1977) and the median of the reported values
determined. The Aroclor homolog composition was taken from Verschueren (1983).
The K values in Table 2 for the four methods do in general agree;
however, for some compounds the values range over several orders of magnitude.
For these compounds, the wide range in uncertainty, the disagreement between
the recommended value of Leo-Hanch and the geometric mean of all reported
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values, or lack of confirmatory data makes it difficult to chose a definitive
log KQw value. Based on the review of all the data, log K values for 11 of
the 17 nonpolar compounds, for which there are WQC, are considered acceptable
at this time and are use<3 to calculate interim criteria values. Further review
is ongoing to determine the most acceptable mean and uncertainty values to
represent the Kx values for these compounds. The accepted mean, standard
0"
deviation (S.D.), and the 95% confidence intervals for the log K value; and
WWf
the mean, S.D., and 95V confidence intervals for the log K value for each
of the 11 compounds are presented in Table 3. The 95% confidence intervals
for the K values were calculated assuming a t statistic of 1.96, which is
the value for large sample size, rather than the statistic for the specific
sample size used to estimate the mean and S.D. for the compound. The mean
log K values in this table were estimated using Equation (2) and the mean
log K value. The S.D. of the log K value was estimated using the following
ow oc
equation:
S.D. - y7 (S.D. of log Knjz + (0.3)2
OW
where 0.3 represents the standard error due to the regression relationship.
This estimate of the standard error of the regression is large because the
least squares regression method assumes that all uncertainty is in the log
K value. As part of the ongoing review, the most appropriate methods for
estimating the mean and S.D. of the log KQw values are being examined. Also,
alternative regression methods will be used to determine the most appropriate
value for the standard error due to the regression. As a result of this review,
the final log K values and the final criteria values may change slightly
OW
from those presented in this report.
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INTERIM SEDIMENT QUALITY CRITERIA
Table 4 summarizes the interim sediment criteria values calculated using
Equations (1) and (2) and the FCV and FRV criteria, respectively, for freshwater
(Table 1) as the basis of the interim criteria. Table 5 summarizes the criteria-
values using FCV and FRV criteria, respectively, for saltwater (Table 1).
When both FCV and FRV values are available for a compound, the FCV
concentrations should only be used to calculate SQC when they are lower than
the corresponding FRV concentrations. However, SQC values derived from both
FCV and FRV values are presented to permit the user to determine what end use
is being protected for.
Estimates of the SQCs are shown for the mean and 95% confidence interval
of the log KQC values. The confidence interval is reported to illustrate the
uncertainty in the interim criteria values and to permit the user to estimate
the likelihood that the sediment does or does not exceed the criteria value.
The confidence interval represents the range within which with 95% certainty
the sediment criteria value will fall. The lower value of the confidence
interval represents the concentration which with 97.5% certainty will result
in protection from chronic effects or of uses depending on the WQC value used
in the SQC derivation. Any contaminant in a sediment at concentrations less
than this value would not be of concern; however, the sediment can not be
considered "safe" because the sediment may contain other contaminants above
safe levels but for which criteria do not exist. The upper value of the
confidence interval represents the concentration which with 97.5% certainty
will result in hazardous long-term impacts on the benthic fauna. Thus, any
sediments with concentrations above this level are considered hazardous.
Concentrations within the confidence intervals can be considered either "safe"
8
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or hazardous with respect to that compound with certainties between 2.5 and
97.5%.
APPLICATION OF INTERIM NUMBERS
To determine if the sediment concentration of a nonpolar contaminant
exceeds the sediment criteria values, the concentration of the contaminant
and the organic carbon content of the sediment must both be known. The
analytical methodologies for measuring the concentration of nonpolar organic
compounds and the organic carbon content in sediments are described in Cowan
and Riley (1987). Because the sediment criteria values are presented as
normalized to organic carbon content (i.e., presented on a per organic carbon
weight basis), the normalized sediment concentrations of the contaminants
must be calculated. These normalized concentrations can then be directly
compared with the interim values in Tables 4 and 5. Alternatively, the sediment
criteria values could be multiplied by the lowest organic carbon content and
the total concentrations compared with these criteria values. To facilitate
this second type of comparison, Tables 6 and 7 contain the sediment criteria
values for specific organic carbon contents of 1 and 10% for fresh and
saltwater, respectively. These organic carbon contents represent the average
range over which the EP approach has been examined (Karickhoff 1984, DiToro
1985).
SAMPLE CALCULATION
To illustrate the use of the interim sediment criteria values, an example
calculation is presented.
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For example, consider a site where previous analyses have indicated that
DOT is present in the freshwater sediments at a concentration of 0.1 mg/kg of
sediment and that the organic carbon (fQC) content is 2% or 0.02 kg of C/kg
of sediment. To calculate the normalized sediment concentration in terms of
organic carbon content, the formula is as follows:
Normalized Concentration « Sediment Concentration/^
For this specific example,
Concentration (mg/kg C) - (0.1 mg/kg)/(0.02 kg C/kg)
» 5 mg/kg C
Comparing this value to the values in Table 4, the normalized concentration
exceeds the criteria values based on the FRV for freshwater.
Alternatively, the criteria value in Table 4 could be multiplied by the
organic carbon content of the sediment to calculate the criteria value for a
specific organic carbon content. The formula is as follows:
Sediment Concentration - (SQC)(foc)
The calculation for this same case (i.e., 2% organic carbon) using the lower
confidence interval value would be
SQC at 2V O.C. (mg/kg) - 0.183 mg/kg C x 0.02 kg C/kg
• 3.66E-3 mg/kg
Comparison of this value with the measured concentration indicates that the
criteria value is again exceeded. Using the upper confidence interval value
also indicates that the criteria are exceeded.
The first calculation method would be most appropriately used when several
contaminant concentrations are available across a site that varies in organic
carbon content. In that case, the calculation of the organic carbon normalized
values and contours of concentration could be used to indicate the approximate"
10
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area or sampling sites that are above the criteria value. The second
calculation method would be most appropriate when several contaminant
concentrations are available, but the organic carbon content of the sediment
is constant.
11
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REFERENCES
Bowman, B. T. and W. W. Sans. 1983. "Determination of Octanol-Water
Partitioning Coefficients (K ) of 61 Organophosphorus and Carbamate
Insecticides and Their Relationship to Respective Water Solubility (S)
Values." J. Environmental Science and Health B18(6): 667-683.
Call, D. J., L. T. Brooke, M. L. Kasuth, S. H. Poirier, and M. 0. Hogland.
1985. "Fish Subchronic Toxicity Prediction Model for Industrial Organic
Chemicals that Produce Narcosis." Environ. Tox. and Chem. 4:335-341.
Chiou, C. T., V. H. Freed, D. W. Schmedding and R. L. Kohner. 1977. "Partition
Coefficient and Bioaccumulation of Selected Organic Chemicals."
Environmental Science and Technology 11:475-478.
Cowan, C. E. 1986. Updated Sediment Criteria Integrated Work Plan: May 1986.
Prepared by Battelle, Pacific Northwest Laboratories, Richland, Washington.
For Criteria and Standards Division, Environmental Protection Agency,
Washington, D.C. Submitted by Battelle, Washington Environmental Program
Office, Washington, D.C.
Cowan, C. E. 1987 Updated Sediment Criteria Integrated Work Plan: September
19B/. Prepared by Battelle, Pacific Northwest Laboratories, Richland,
Washington. For Criteria and Standards Division, Environmental Protection
Agency, Washington, D.C. Submitted by Battelle, Washington Environmental
Program Office, Washington, D.C.
Cowan, C. E. and R. G. Riley. 1987. Guidance for Sampling of and Analyzing
for Organic Contaminants in Sediments. Prepared by Battelle, Pacific Northwest
Laboratories, Richland, Washington. For Criteria and Standards Division,
Environmental Protection Agency, Washington, D.C. Submitted by Battelle,
Washington Environmental Program Office, Washington, D.C.
DiToro, D. M. 1985. "A Particle Interaction Model of Reversible Organic
Chemical Sorption." Chemosphere 14: 1503-1508.
Hansen, D. J. 1987. Memorandum to Organizers of Presentation to the SAB
[Science Advisory Board] on SQC [Sediment Quality Criteria].
Karickhoff, S. W. 1984. "Organic Pollutant Sorption in Aquatic Systems."
J. Hydraulic Eng. 110(6):707-735.
Leo, A. 1984. Medicinal Chemistry Project. Pomona College, Pomona, CA.
Lyman, W. L., Reehl, W. F. and D. H. Rosenblatt. 1982. "Handbook of Chemical
Estimation Methods." McGraw-Hill Book Co. pp. 16-25.
Mai ins, D. C., B. B. McCain, D. W. Brown, A. K. Sparks and H. 0. Hodgins.
1980. Chemical Contaminants and Biological Abnormalities in Central and
Southern Puget Sound. NOAA Technical Memo OMPA-2, National Oceanic and
Atmospheric Administration, Boulder, CO.
12
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Malins, 0. C.r B. B. McCain, 0. W. Brown, A. K. Sparks, H. 0. Hodgins and S.
L. Chan. 1982. Chemical Contaminants and Abnormalities in Fish and
Invertebrates from Puget Sound. NOAA Technical Memo OMPA-19, National Oceanic
and Atmospheric Administration, Boulder, CO.
Miller, M. M., S. Ghodbane, S. P. Wasik, Y. B. Tewari and 0. E. Martire.
1984. "Aqueous Solubilities, Octanol-Water Partition. Coefficients, and
Entropies of Wetting of Chlorinated Benzenes and Biphenyls." Journal
of Chemical Engineering Data 29:184-190.
Miller, M. M., Wasik, S. P., Huang, G-L., Shiu, W-Y., and D. McKay. 1985.
"Relationship Between Octanol-Water Partition Coefficient and Aqueous
Solubility." Environmental Sci and Technol 19(6): 522-529.
Neff, J. M. 1985. Sediment Criteria Integrated Work Plan. Prepared by
Battelle. For Criteria and Standards Division, Environmental Protection Agency,
Washington, D.C. Submitted by Battelle, Washington Environmental Program
Office, Washington, D.C.
Pavlou, S., R. Kadeg, A. Turner, and M. Marchlik. 1987. Sediment Quality
Criteria Methodology Validation: Uncertainty Analysis of Sediment Normalization
Theory for Nonpolar Organic Contaminants. Prepared by Envirosphers Company,
Bellevue, Washington. For Criteria and Standards Division, Environmental
Protection Agency, Washington, D.C. Submitted by Battelle, Washington
Environmental Program Office, Washington, D.C.
Rapaport, R. A. and S. J. Eisenrich, 1984. "Chromatographic Determination
of Octanol-Water Partition Coefficients (K *s) for 58 Polychlorinated
Biphenyl Congeners." Environmental Science and Technology 18:163-170.
Rapaport, R. A. and S. J. Eisenrich. 1985. "Corrections." Environmental
Science and Technology 19:376.
Shiu, W. Y. and D. Mackay. 1986. "A Critical review of Aqueous
Solubilities, Vapor Pressures, Henry's Law Constants and Octanol Water
Partition Coefficients of the Polychlorinated Biphenyls." Journal of
Physical Chemistry, submitted for publication.
Stephan, C. E., D. I. Mount, D. J. Hansen, J. H. Gentile, G. A. Chapman, and
W. A. Brungs. 1985. Guidelines for Deriving Numerical National Water Quality
Criteria for the Protection of Aquatic Organ-isms and Their Uses. National
Technical Information Service, Springfield, VA. PB85-227049. 98pp.
Veith, G. D., Call, D. J., L. T. Brooke. 1983. "Structure-Toxicity
Relationships for Fathead Minnow, Pimeohales promelas; Narcotic Industrial
Chemicals." Can J. Fish and Aquatic Sci. 40:743-748.
Verschueren, K. 1983. "Handbook of Environmental Data on Organic
Chemicals." Van Nostrand Reinhold Company, New York.
13
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l!f!!J2HAnASvS!L0: ^h"1"9*^ 1986' "SMILES' A Modern Chemical «>d Language
Information System." Chemical Design Automation News.
Woodburn, K. B., W. J. Doucette and A. W. Andren. 1984. Generator Column
Determination of Octanol /Water Partition Coefficients for Selected
C°ngeners-" Environmental Science and
Yalkowsky, S. H. S. C. Valvani, W. Y. Kuu (eds). 1987. "Arizona Database
of Aqueous Solubility," College of Pharmacy, University of Arizona
14
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TABLE 1. Final Residue Values (FRV) and Final Chronic Values (FCV) for
Nonpolar Organic Compounds
Freshwater /*g/L Saltwater
Compound (Pub. Date) C.
Acenaphthene*
Aniline*
Chlordane (1980)
Chlorpyrifos (1986)
DDT (1980)
Dieldrin (1980)
Di ethyl hexy 1 phthal ate*
Endosulfan(1980)
Endrin (1980)
Ethyl Parathion (1986)
Hepatachlor (1980)
Hexach 1 orocycl ohexane
(1980)***
Methyl Parathion*
Phenanthrene*
Polychlorinated Biphenyl
(1980)
Toxaphene (1986)
1 ,2,4-Trichlorobenzene*
A.S. Number
83-32-9
62-53-3
57-74-9
2921-88-2
50-29-3
60-57-1
117-81-7
115-29-7
72-20-8
56-38-2
76-44-8
608-73-1
298-00-0
85-01-8
s
8001-35-2
120-82-1
FCV
57
7.2
0.17
0.041
-
0.29
360
0.056
0.045
0.013
-
0.080
0.15
6.3
-
<0.039
23
FRV -
—
-
0.004
-
0.0010
0.0019
-
.
0.0023
-
0.0038
•
-
-
0.014
0.0002**
•
FCV
—
27
0.0064
0.0056
-
0.084
360
0.0087
0.0093
-
.
-
0.076
4.6
-
0.21
™
FRV
.
_
0.004
.
0.0010
0.0019
.
0.0023
-
0.0036
-
-
.
0.030
0.0002**
•
* Draft criteria documents.
** See criteria document for explanation of this residue-based value.
*** Also known as Lindane
15
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TABLE 2. K Values for Compounds in Table 1
ow
LOG K
CHEMICAL (PUB DATE)
ACENAPHTHENE
ANILINE
CHLORDANE(IMB)
CHLORPYRIFOS(1986)
001(1980)
DiaORIN(1980)
OinHYLHEXYLPHTHAUTE
ENDOSULFAH(IMI)
OKMIN(I980)
ETHYL PARAIHION(1966)
HEPTACHLOR
H£XACHLOROCYCLOHEXANE(l«al)*
METHYL PARATHIOM
PHENANTHRENE
POLYCHLORINATED BIPMENVLS:
AROCLOR 1242
AROCLOR 12S4
AROCLOR 1261
TOXAPHfNE(1906)
1.2.4-TRICHLQROBENZENE
C.A.S. Ho
•3-32-0
82-63-3
17-74-9
2921-00-2
60-29-3
60-IM
117-01-7
116-29-7
72-21-8
S0-38-2
78-44-8
008-73-1
296-U-l
86-11-8
6001 36-2
120-02-1
LEO-HANCH
MEASURED
3 92
• 90
-
4 96
• 37
4 32
-
3 83
-
3 83
-
3 72
2.86
4 46
6.10
a 73
694
-
4.02
LEO-HANCH PAVLOU ET AL (1987)
FRAGMENT
ANALYSIS
4.07
0.92
I 14
4.69
6.91
2 92
6 66
4 87
2 92
3 47
4 61
37$
2.79
4.49
-
-
-
-
4.26
AQUEOUS GEOMETRIC
SOLUBILITY MEAN
3 72
0 63
4 76
(.11
6 16
4 40
(70
-
3 01
3 94
6 18
3.41
3 34
4 14
-
-
-
4.77
3 30
4 18
090
4 81
4 98
6.62
4.92
4 44
3 86
4.64
3 36
4.42
0 26
. 3.26
SO
.0032
.03(0
.407
0141
.1479
490
0 366
0 196
8.329
0.063
0.116
0.190
0.1263
9UCI
4 02
0 91
• Ob
4 96
(.73
3 96
3 74
0 47
S 89
3 23
4 19
(.87
3 26
- 4 34
- 1 16
- 4 97
- 6 11
- 6 31
- ( 88
- 6 14
- 4.26
- 6 19
- 3 47
- 4 86
- 6.63
- 4.77
* Also knoMi •• LindMM
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TABLE 3. K and K Values for Selected Nonpolar Organic Compounds
ow oc
Log K
ow
Compound
Acenaphthene
Aniline
Chlorpyrifos
DDT
Dieldrin
Endrin
Ethyl-parathion
Heptachlor
Lindane
Phenanthrene
PCB (1254)
Mean(a)
4.18
0.98
4.98
6.02
4.92
4.44
3.86
4.54
3.35
4.42
6.25
S.D.
0.0832
0.0350
0.0141
0.148
0.490
0.355
0.197
0.329
0.063
0.116
0.196
95% (b)
Confidence
4.02
0.91
4.95
5.73
3.96
3.74
3.47
3.90
3.23
4.19
5.87
Interval
4.34
1.05
5.01
6.31
5.88
5.14
4.25
5.18
3.47
4.65
6.63
Mean
4.11
0.96
4.90
5.92
4.84
4.36
3.79
4.46
3.29
4.35
6.14
S.O.(c)
0.311
0.302
0.300
0.334
0.574
0.465
0.359
0.445
0.306
0.322
0.358
95% (b)
Confidence
3.50
0.37
4.31 *
5.26
3.71
3.45
3.09
3.59
2.69
3.71
5.44
Interval
4.73
1.56
5.49
6.58
5.97
5.29
4.51
5.34
3.90
4.98
6.85
(a) Geometric Mean*
(b) 95% confidence interval calculated assuming log normal distribution of K values and 1.96
for t(P95%). °"
(c) Standard error of log K calculated using following formula:
OC
S.O. = V(S.D. of log KOW)^^0.3F
where 0.3 *s the standard error from regression relationship
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TABLE 4. Sediment Quality Criteria Values for Selected Nonpolar Organic Compounds for Freshwater
Sediment Quality Criteria (/»g/gC)
Sediment Quality Criteria (/*g/gC)
Freshwater
Compound FCV
Acenaphthene
Aniline
Chlorpyrifos
DDT
Dieldrin
Endrin
Ethyl Parathion
Heptachlor
Lindane
Phenanthrene
PCB (1254)
57
7.2
0.041
0.29
0.045
0.013
0.08
6.3
Mean
732
0.0662
3.22
19.9
1.04
0.0810
0.157
139
95%
Confidence Interval
180
0.0169
0.831
1.49
0.128
0.0160
0.0394
32.6
3,030
0.262
12.7
273
8.68
0.416
0.636
605
Freshwater
FRV
0.001
0.0019
0.0023
0.0038
0.014
Mean
0.828
0.130
0.0532 .
0.110
19.5
95%
Confidence Interval
0.183
0.00976
0.00654
0.0148
3.87
3.80
1.79
0.443
0.840
99.9
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TABLE 5. Sediment Quality Criteria Values for Selected Nonpolar Organic Compounds for Saltwater
Sediment Quality Criteria (/ig/gC)
Sediment Quality Criteria (/ig/gC)
Compound
Acenaphthene
Aniline
Chlorpyrifos
DDT
Dieldrin
Endrin
Ethyl Parathion
Heptachlor
Lindane
Phenanthrene
PCB (1254)
Saltwater
FCV
27
0.0056
0.084
0.0093
4.6
Mean
0.248
0.440
5.77
0.215
102
95%
Confidence
0.0635
0.114
0.431
0.0264
23.8
Interval
0.984
1.73
79.2
1.793
442
Saltwater
FRV
0.001
0.0019
0.0023
0.0038
0.030
Mean
0.828
0.130
0.0532
0.104
"
41.8
95%
Confidence
0.183
0.00976
0.00654
0.0140
8.29
Interval
3.80
1.79
0.443
0.796
214
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TABLE 6. Sediment Quality Criteria Values for Selected Nonpolar Organic Compounds for Freshwater
at 1 and 10% Organic Carbon Content (all criteria with units of ppm or mg/kg)
FCV FRV
Compound
Acenaphthena
Am 1 in*
Chlorpyrifoa
DDT
Dialdrin
Endrin
Elhyl Par»thion
Hcptachlor
Lindan*
Phenanthrena
PCB (12S4)
Uean
7.33
1 66E-3
1 1322
1 199
1 111
I.616E-3
1 57E-3
1.39
11
961 CI
MI
1 169E-3
I.31E-3
1 Ilk
1 ME 3
9 180E-3
1 394E-S
1.326
si a
J.63E-I
1.127
2 73
1 1667
4.16E-3
6 38E-3
6. IS
Heart
73.3
6 61E-S
1.322
1 M
1 1114
a.iK-s
1.117
13 9
101
951
U.I
l.ME 3
I.M3
1.149
1 II2B
l.«K-3
3 ME 3
3.26
CI
313
1.1262
1.27
27.3
1 666
1 1416
1.6636
61. i
Ha an
6 JBE 3
1 30E-3
1 S33E-3
1.10E-3
I 19S
11
9SICI
1.63E3 1.1366
1 697BE-3 1 1179
1 6664E-3 4.43E-3
I.14IE-3 8 46E-3
1.1387 1.999
Mean
1 1626
1 1131
1.326E-3
1 I116E-3
1 8S
101
961 CI
I. 1112
1 976E-3
1 664E-3
1 466E-3
1 367
1366
1.179
1.1443
6 6841
9 99
-------
TABLE 7. Sediment Quality Criteria Values for Selected Nonpolar Organic Compounds for Saltwater
at 1 and 10% Organic Carbon Content (all criteria with units of ppm or mg/kg)
FCV FRV
'expound II III
Item 9SI CI HIM 961 C
Acenaphthcna
AniliM 2.46E-3 1 63SE-S 9 ME-9 1.1248 6.3SE-3
Chlorpynfo* 4.48E-3 1.14E-3 1.1173 1 1441 11114
DOT
Diddrin 8.8577 4 31E-3 0 792 I.t77 1 1431
fndrin J 1SE 3 0 M4E-3 01179 I.I2U 2 64E-3
ithyl Parathion
Heptachlor
I indan*
Phenanthr.n. 1.02 0.231 4.42 11 2 2 36
PCB (12(4)
[ bean
0 OM4
0.173
• ME 3
792 1 30E 3
0 179 I H3E-3
1 04E-3
44 2
0 418
11
9SI CI
1.I3E-3
0 M76E 3
I.MS4E 3
0.14K-3
0 M29
1 0380
1 0179
4 43E-3
7.96E-3
2.14
atean
1 M2I
0 1131
» 328E-3
O.III4E-3
4.11
1M
9Ui
I 1112
0 976C-3
0 6S4E-3
1 40E-3
1 829
CI
• 388
8 179
9 9443
8 8790
21 4
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Appendix A. Water Quality Criteria Derivation Procedures
The water quality criteria listed in Table 1 were obtained from
published or draft aquat'ic-life water quality criteria documents. These
numerical water quality criteria concentrations were derived using the
"Guidelines for Deriving Numerical National Water Quality Criteria for
the Protection of Aquatic Organisms and Their Uses" (Stephan et al.
1985). These "National Guidelines" specify minimum data requirements
and data synthesis procedures which allow calculation of numerical
criteria concentrations to protect the presence and uses of aquatic life.
Water quality criteria concentrations to protect the presence of
aquatic life are derived using the following procedure. First, all
available data on the toxicity of the chemical are collected, reviewed
for acceptability, and sorted by test type. If minimum database
requirements for acute and chronic toxicity as specified in the "National
Guidelines" are met, Criteria Maximum Concentrations (CMC) and Criteria
Continuous Concentrations (CCC) are calculated to protect important
aquatic life from acute and chronic toxicity, respectively. If the
toxicity of the chemical is dependent on a water quality characteristic,
then the CMC or CCC values are derived as a function of the appropriate
characteristic. Because aquatic ecosystems can tolerate some stress
and occasional adverse additions, protection of all species at all times
and places is not necessary. Therefore, criteria derivation procedures
result in criteria concentrations intended to protect most species most
of the time but not all of the species all of the time.
22
-------
Water quality criteria concentrations to protect the uses of aquatic
life are derived using the following procedure. A Criteria Continuous
Concentration to limit residues in aquatic life can be derived if maximum
permissible tissue concentrations and data on bioaccumulation or
bioconcentration factors are available. Maximum permissible tissue
concentrations are based on either (a) a FDA action level for fish oil
or edible portions of fish or shellfish, (b) a maximum acceptable dietary
intake based on a wildlife feeding study, or (c) residue-effects data
for aquatic life. Either bioconcentration or bioaccumulation factors
are required to calculate the water concentrations expected to limit
chemical uptake by organisms to below the permissible tissue
concentration. Bioconcentration factors, the concentration of the
chemical in the organism divided by the concentration In the exposure
water, are calculated from laboratory studies where steady-state
conditions are achieved. Bioaccumulation factors, the concentration of
chemical in the organism from all sources (e.g., food, water) divided by
the concentration in the water, are calculated from data obtained in
field studies. It is important to note that if food-chain transfer is
an important uptake route, criteria concentrations derived using
bioconcentration factors, such as those for DDT and PCBs, will probably
be underprotective.
The water quality criteria statement contains a concentration limit,
averaging period, and return frequency and is stated as follows: "The
procedures described in the "Guidelines for Deriving National Water
Quality Criteria for the Protection of Aquatic Organisms and Their Uses"
indicate that, except possibly where a locally important species is
23
-------
very sensitive, (1) aquatic organisms and their uses should not be
affected unacceptably if the four-day average concentration of (2) does
not exceed (3) ng/l more than once every three years on the average and
if the one-hour average concentration does not exceed (4) /ig/L more
than once every three years on the average." In this statement insert
either "freshwater" or "saltwater" at (1), the name of the chemical at
(2), the lower of the chronic-effect or residue-based concentrations as
the Criteria Continuous Concentration at (3) and the acute effect-based
Criteria Maximum Concentration at (4).
The Criteria Continuous Concentration based on either chronic effect
or residue data can be used to derive sediment quality criteria for
nonpolar organic chemicals using the equilibrium partitioning approach.
Detailed knowledge of the National Guidelines and the water quality
criteria document as a basis for understanding the water quality criteria
that are used in the derivation of sediment quality criteria is highly
recommended.
24
-------
Appendix B. Aqueous Solubility and Octanol-Water Partition Coefficient
Estimates of KQW from solubility are based on a thermodynamically
inspired correlation developed for 61 organophosphorus and carbamate
insecticides (Bowman and Sans 1983). The relationship includes a melting
point (MP) correction for chemicals that are solids at room temperature.
The regression analysis using K and the estimated aqueous solubility
of the liquid (or supercooled liquid- for solids) yields the following
relationship (Bowman and Sans 1983):
Log KQw = 0.280 - 0.839 log S$cl
where S , is the molar aqueous solubility of the supercooled liquid.
The relationship between the molar solubility of the solid, S i-d, and
the supercooled liquid, S ^, is given by the following relationship
(Bowman and Sans 1983, Miller et al . 1985):
W Tm
(
. ,
where AHf"/Tm « AS, the entropy of fusion, is reported to be 13.5 cal/mole
a°K for most low melting point compounds and R « 1.987 cal/mole °K.
25
-------
Appendix C. Estimating K using CLOGP
ow
The CLOGP program, based on Leo's Fragment Constant Method (Lyman
et al. 1982), estimates Tog K using fragment constants (fj) and
structural factors (F-j) that have been empirically derived for many
molecular groups. The estimated K is obtained from the sum of constants
and factors for each of the molecular subgroups comprising the molecule
as follows:
"ow ' t
The method assumes that log KQw is a linear additive function of
the structure of the solute and its constitutive parts, and that the
most important structural effects are described by available factors.
The structure of the compound is specified using the Simplified Molecular
Interactive Linear Entry System (SMILES) notation (Weininger and Weininger
1986). The notation uniquely describes the empirical formula and
molecular structure of the compound of interest.
26
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Appendix 0. Example Calculation of Aroclor KQW
Aroclor
Aroclor 1242
Homo log Homo log
Homolog Fraction log K
ow
mono 0.03 4.33
di 0.13 5.12
tri 0.28 5.57
tetra 0.30 5.84
penta 0.22 6.35
hexa 0.04 7.05
For Aroclor 1242:
log KQw » log1Q [0.03(104'33) + 0.13(105*12) + 0.28(105'57)
+ 0.30(105'84) + 0.22(106'35) + 0.04(107'05)
- log1Q [1,270,684]
log KQw * 6.10
27
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Appendix E. Interim Sediment Criteria Values for Polycyclic
Aromatic Hydrocarbons
In the main part of this report, interim sediment criteria values
are shown for 11 nonpolar organic compounds for which chronic water
quality criteria have been generated. During visits to regional Superfund
offices to discuss the application of these interim criteria values,
the need for interim criteria for several of the polycyclic aromatic
hydrocarbons (PAHs) was identified. The PAHs are Fluoranthene, Pyrene,
Benzo(a)pyrene and Benzo(a)anthracene. This appendix describes how
those interim criteria values were developed and provides all supporting
data for their calculation.
The freshwater chronic water quality criteria values for the four
PAHs given in Table E.I were determined by Mr. Anthony (Ron) Carlson of
EPA-Duluth using the computer automated method system developed by that
laboratory. The calculated criteria values for Phenanthrene and
Acenaphthene are given for comparison. Accepted chronic criteria for
these compounds are 0.006 mg/L and 0.057 mg/L, respectively. The
computerized method which uses the K and solubility values for the
compound to calculate both the acute and chronic water quality criteria
is based on the work of Veith et al. (1983) and Call et al. (1985).
The values given are based on toxicity to chronically exposed fathead
minnows. This method is estimated to provide acute and chronic toxicity
values that are within a factor of 3 and 5, respectively, of the actual
values for approximately 80% of the known industrial compounds.
The log K values for the four PAHs given in Table E.2 were developed
3 ow
as described in the main part of the report. The log KQC values and
28
-------
Table E.I. Predicted Fathead Minnow Toxicity Values
Compound
Name
Phenanthrene
Acenaphthene
Fluoranthene
Pyrene
Benzo(a)pyrene
Benzo(a)anthracene
I* * A* J •
Nuaber
85018
83329
206440
129000
50328
56553
Mode of
Action(a)
NN
NN
NN
NN
NN(?)
NN(?)
L°9 Kow
4.49
4.07
4.95
4.95
6.12
5.66
Solubility
(mg/1)
1.26
4.44
0.24
0.13
0.004
0.014
Acute
Chronic
(mg/1)
0.6
1.3
0.25
0.25
0.025
0.061
0.035
0.086
0.013
0.013
0.0012
0.0030
a) NN = Nonpolarnarcosis. The question nark indicates that the mode of action is not known with certainty.
-------
the 95% confidence interval for the log KOC values given in Tabl$ E.3
were also estimated using the same methods and assumptions described
previously.
The final criteria values are given in Table E.4 on an organic carbon
normalized basis and for 1% and 10% organic carbon in Table E.5. These
interim criteria values can be used in the same way as the interim values
in the main part of the report to determine if a sediment sample exceeds
or does not exceed the criteria values.
29
-------
Table E.2. Log K values for the four PAHs in Table 1
ow
Log Kow
Compound
Fluoranthene
Pyrene
Benzo(a)pyrene
Benzo( a) anthracene
Leo-Hanch
Measured
5.2
4.88
5.97
Fragment
Analysis
4.95
4.95
6.12
5.66
Aqueous
Solubil ity
4.61
4.44
5.81
6.34
Geometric
Mean
5.25
5.09
6.05
5.74
S
0
0
0
0
.0.
.139
.187
.168
.264
9f
Confidence
4.98
4.72
5.72
5.22
>V
Interval
5.52
5.46
6.38
6.26
-------
Table E.3. Log K and log K values for the for PAHs.
ow oc
Compound
Geometric
Mean
Log Kow
s.o.
95%
Confidence Interval
Log Koc
Mean S.D.
95%
Confidence Interval
Muoranthene 5.25
Pyrene 5.09
Bcnzo(a)pyrene 6.05
Benzo(a)anthracene 5.74
0.139
0.187
0.168
0.264
4.98
4.72
5.72
5.22
5.52
5.46
6.38
6.26
5.16
5.00
5.95
5.64
0.33
0.35
0.34
0.40
4T51
4.31
5.27
4.86
5.81
5.70
6.62
6.43
-------
Table E.5. Interim Sediment Quality Criteria values for four PAHs for 1 and 10% Organic Carbon Contents.
(All criteria with units of ppm or mg/kg.)
1% 10%
Compound
Fluoranthene
Pyrene
Benzo(a)pyrene
Benzo ( a) anthracene
Mean
18.8
13.1
10.6
13.2
95% Confidence Interval Mean
4.24
2.66
2.25
2.17
83.8
64.6
50.2
80.0
188
131
106
132
95% Confidence Interval
42.7
26.6
22.5
21.7
838
646
502
800
-------
Table E.4. Interim Sediment Quality Criteria values for four PAHs.
Compound
Fluoranthene
Pyrene
Benzo(a)pyrene
Benzo(a) anthracene
WQC
13
13
1.2
3
Sediment Quality Criteria
(ug/g C)
Mean 95% Confidence Interval
1,883 423 8,375
1,311 265 6,465
1,063 225 5,018
1,317 217 7,999
33
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CONTRIBUTORS
Dr. Oom DiToro, Mr. Paul Paquin, and Mr. Benjamin Wu of HydroQual,
Inc., tabulated Kow and K0c values for the nonpolar contaminants,
with assistance from Or. Spyros Pavlou and Mr. Roger Kadeg of
Envirosphere Co, Inc.
Mr. David Hansen of EPA's Narragansett Laboratory, and Mr. Nelson
Thomas and Mr. Ron Carlson of EPA's Duluth Laboratory provided water
quality criteria for nonpolar contaminants, the QSAR based criteria
for PAHs, and the appendix on criteria development procedures.
All of the above people as well as Or. Herb Allen of Drexel
University, Ms. Alexis Steen and Dr. James Fava of Battelle, and
Mr. Chris Zarba, the EPA Work Assignment Manager, provided valuable
comments on the draft of this report.
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