vvEPA
United States
Environmental Protection
Agency
T £•;•.!•! ology (W
Washington. D C 20460
EPA 823-R-92-008a
September 1992
Water
NATIONAL STUDY OF
CHEMICAL RESIDUES
IN FISH
Volume
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EPA 823-R-92-008a
; September 1992
I
National Study of
Chemical Residues
in Fish
Volume I
Office of Science and Technology
Standards and Applied Science Division
U.S. Environmental Protection Agency
401 M Street, SW
Washington, DC 20460
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Note
This is the third printing (September 1993) of the National Study of Chemical Residues in Fish.
All revisions listed on the errata sheet from the first printing have been incorporated into the
text of Volumes I and II where appropriate.
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Table of Contents
Chapter Pjg£
VOLUME I
LIST OF FIGURES vii
LIST OF TABLES xi
ACKNOWLEDGMENTS xiii
EXECUTIVE SUMMARY xv
1 INTRODUCTION 1
BACKGROUND 1
GENERAL APPROACH 1
2 STUDY DESIGN AND APPROACH 3
POLLUTANT SELECTION SCREENING PROCESS 3
FIELD SAMPLING PROCEDURES 4
Sample Collection 4
Sample Handling/Preparation 6
Fish Length and Weight Data 6
ANALYTICAL PROTOCOLS 6
Dtoxins/Furans 7
Other Xenobiotic Chemicals 10
Mercury 12
Quality Assurance/Quality Control (QA/QC) 12
SITE SELECTION 15
3 DIOXIN AND FURAN RESULTS AND ANALYSIS 21
PREVALENCE AND CONCENTRATION SUMMARY 21
Toxicity Equivalency Concentration (TEC) 24
Comparison of TCDD and other Dioxin/Funn Compounds 30
GEOGRAPHICAL DISTRIBUTION 30
SOURCE CORRELATION ANALYSIS 30
Sources Located Near Highest Concentration* 30
Concentration Comparison Between Site Categories 39
4 OTHER XENOBIOTIC COMPOUND RESULTS AND ANALYSIS 53
PREVALENCE AND CONCENTRATION SUMMARY 53
COMPOUNDS DETECTED AT MORE THAN 50 PERCENT OF THE SITES 57
Total PCBs 57
Biphenyl 60
Mercury 64
Pentachloroanisok 67
1,23 and 1.2,4 Trichkxobenzene 70
Pesticides/Herbicides 73
iii
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Table of Contents (Cont)
Chapter Page
COMPOUNDS DETECTED AT BETWEEN 10 AND 50 PERCENT OF THE SITES 91
Hexachlocobenzene 91
Pentachlorobenzene 96
1,3,5 Trichlorobenzene 100
Tetrachlofobenzenes 100
Pesticides/Herbicides 107
COMPOUNDS DETECTED AT LESS THAN 10 PERCENT OF THE SITES 122
Octacnlorostyrene 122
Hexachlorobutadiene 122
Diphenyl Disulfide 122
Pesticides/Herbicides 125
COMPARISON WITH NATIONAL CONTAMINANT BIOMONTTORING
PROGRAM 129
5 FISH SPECIES SUMMARY AND ANALYSIS 131
SUMMARY OF FISH SPECIES SAMPLED 131
PREVALENCE AND AVERAGE CONCENTRATION OF CHEMICALS
BY SPECIES 137
HABITAT AND FEEDING STRATEGY OF MOST FREQUENTLY
SAMPLED SPECIES 137
6 ESTIMATE OF POTENTIAL HUMAN HEALTH RISKS 147
METHOD OF ESTIMATING RISKS 148
Dose-Response Assessment 148
Exposure Assessment 148
Risk Characterization 150
CARCINOGENIC RISK ESTIMATES 151
NONCARCINOGENIC RISKS 156
REFERENCES 161
GLOSSARY 165
APPENDICES
A LABORATORY QA/QC PROCEDURES AND RESULTS
A-l Analysis of Laboratory QA/QC Data
A-2 Analytical Procedures and Quality Assurance Plan for (be Determination of
PCDD/PDCF in Fish
A-3 Analytical Procedures and Quality Assurance Plan for tbe Determination
of Xenobiotic Chemical Contaminants in Fish
B ADDITIONAL DATA ANALYSES
B-l Nomographs for Estimating Cancer Risks
B-2 Nomographs for F«Hm^«"t NoacaTtinofeaic Hazard Indices
B-3 Site Description Matrix (also provided in Volume U, Appendix D)
B-4 Dioxins/Furans: Episode Numbers Used in Statistical Teitt (also provided
in Volume n. Appendix D)
B-5 Xenobiotics: Episode Numbers Used in Statistical Tests (also provided in
Volume IL Appendix D)
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Table of Contents (Cont)
VOLUME a
PROFILES OF BIOACCUMULAT1ON STUDY CHEMICALS
Dtoxins/Furans:
Dioxin: 2,3.7,8 Tetrachlorodibenzo-p-dioxin
1,2,3,7,8 Pentacblorodibenzodioxin
Hexacblorodibenzodioxins
Furans
Otfter Xenohtotics:
Bipbenyl
Cblordane
Chlorpyrifos
p,p'-DDE
Dicofol
Dieldrin
DiphenylDisulfide
Endrin
Heptachlor
Heptacblor Epoxide
Hexacblorobenzene
Alpha-BHC (a • HexadUorocyclobexaae)
Isopropalin
Gamma-BHC (y -Hexachlorocycioheuoe)
Mercury
Metbox; chlor
Mirex
Nitrofen
Nonachlor
Octachlorosytreoe
Oxyctakxdaoe
Pentachloroanisote
Peotachlorobenzene
Pentachlorotiitiobenzene
Pentachlocopbeuol
Perthane
Polychlorinated Bipbenyb (PCBs)
1,23,4 and 1,23,5 TenchkirobenBeiie
1,2,4,5 Tetracfakxobeozeae
1,23 Tricbkxobenzeoe
1,2,4 Trichlorobenzeoe
1,3,5 Trichkxobenzeoe
Trifluralin
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Table of Contents (Cont.)
VOLUME II (Cont)
DATA TABLES
D-l Site Description Matrix (also provided in Volume I, Appendix B)
D-2 Dioxins/Furans: Episode Numbers Used in Statistical Tests (also provided
in Volume I, Appendix B)
D-3 Xenobiotics: Episode Numbers Used in Statistical Tests (also provided
in Volume 1, Appendix B)
D-4 Dioxin/Furan Data by Episode Number
Concentration And Detection Limits
D-5 Xenobkxic Data by Episode Number
Set 1 Chemicals
Set 2 Chemicals
Set 3 Chemicals
D-6 Information on Fish Samples
- Percent Lipid
• Sample Wet Weight
- Number of Fish in Composite Sample
- Sampling Date
D-7 List of Confirmation Samples
D-8 List of Duplicate Samples
D-9 Comments Regarding Sample Analyses from EPA Duluth Laboratory
D-10 Risk Information for Sites Having Composite Fillet Samples with Xenobiotic Data
VI
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List of Figures
Figure
2-1 Schematic of laboratory procedures for dioxins and furans 8
2-2 S chematic of laboratory analytical procedure for otber xenobiotic chemicals I1
2-3 Schematic of laboratory analytical procedure for mercury 13
2-4 Location of bioaccumulauon study sampling sites 16
2-5 Location of targeted sites 17
2-6 Location of sites representing background conditions 18
2-7 Location of sites selected from a subset of the USGS NASQAN network 19
3-1 S ummary of dioxins/furans detected in fish tissue 23
3-2 Cumulative frequency diagrams of concentrations of six dioxin congeners in fish tissue 25
3-3 Cumulative frequency diagrams of concentrations of six furan congeners in fish tissue 26
3-4 Cumulative frequency distribution of maximum calculated TEC values in fish tissue by
percentite of sites 28
3-5 Toxicity equivalency concentrations (TEC) based on Barnes et ai., 1989 method 29
3-6 Map showing geographical distribution of various concentration ranges of
2,3,7,8 TCDD in fish tissue 31
3-7 Map showing geographical distribution of various concentration ranges of
2,3,7,8 TCDF in fish tissue 32
3-8 Map showing geographical distribution of various concentration ranges of TEC
in fish bssue 33
3-9 Example box plot with explanations of features 41
3-10 Box and whisker plot for 2,3.7,8 TCDD concentrations in fish tissue 42
3-11 Box and whisker plot for TEC concentrations in fish tissue 45
3-12 Box and whisker plot for 2,3,7,8 TCDF concentrations in fish tissue 46
3-13 Box and whisker plot for 1,2,3,7,8 PeCDD concentrations in Ash tissue 47
3-14 Box and whisker plot for 1,2,3,7,8 PeCDF concentrations in fish tissue 48
3-15 Box and whisker plot for 2.3,4,7,8 PeCDF concentrations in fish tissue 49
3-16 Box and whisker plot for total HxCDDs concentrations in fish tissue 50
3-17 Box and whisker plot for total HxCDFs concentrations in fish tissue 51
4-1 S ummary of otber xenobiotic compounds detected in fish tissue 55
4-2 Total PCBs: a) cumulative frequency distribution and b) map of geographical distribution
of various concentration ranges in fish tissue 58
4-3 Box and whisker plot for total PCBs in fish tissue 61
4-4 Biphenyl: a) cumulative frequency distribution and b) map of geographical distribution of
various concentration ranges in fish tissue 63
4-5 Box and whisker plot for biphenyl in fish tissue 65
4-6 Mercury: a) cumulative frequency distribution and b) map of geographical distribution of
various concentration ranges in fish tissue 66
4-7 Box and whisker plot for mercury in fish tissue 68
VII
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List of Figures (Cont.)
Figure Page
4-8 Pentachloroanisole: a) cumulative frequency distribution and b) map of geographical
distribution of various concentration ranges in fish tissue 69
4-9 Box and whisker plot for pentachloroanisole in fish tissue 71
4-10 Cumulative frequency distribution of a) 1,2,3 trichlorobenzene and b) 1,2,4 trichloro-
benzene in fish tissue 72
4-11 Map of geographical distribution of various concentration ranges for a) 1,2,3 trichloro-
benzene and b) 1,2,4 trichlorobenzene in fish tissue 74
4-12 Box and whisker plot for 1,2,3 trichlorobenzene in fish tissue 75
4-13 Box and whisker plot for 1,2,4 trichlorobenzene in fish tissue 76
4-14 p,p' -DDE: a) cumulative frequency distribution and b) map of geographical distribution of
various concentration ranges in fish tissue 77
4-15 Box and whisker plot for p,p' -DDE in fish tissue 79
4-16 Cumulative frequency distribution of a) total chlordane, b) cis-chlordane, c) trans-chlordane,
and d) oxychlordane in fish tissue 81
4-17 Cumulative frequency distribution of a) trans-nonachlor b) cis-nonachlor and c) total
nonachlor in fish tissue 82
4-18 Map of geographical distribution of various concentration ranges for a) total chlordane
and b) total nonachlor in fish tissue 83
4-19 Box and whisker plot for total chlordane in fish tissue 85
4-20 Box and whisker plot for total nonachlor in fish tissue 87
4-21 Box and whisker plot for oxychlordane in fish tissue 88
4-22 Dieldrin: a) cumulative frequency distribution and b) map of geographical distribution of
various concentrations in fish tissue 89
4-23 Box and whisker plot for dieldrin in fish tissue 90
4-24 Cumulative frequency distribution of a) alpha-BHC and b) gamma-BHC (lindane)
in fish tissue 92
4-25 Box and whisker plot for alpha-BHC in fish tissue 93
4-26 Box and whisker plot for gamma-BHC in fish tissue 94
4-27 Map of geographical distribution of various concentration ranges for a) gamma-BHC
(lindane) and b) alpha-BHC in fish tissue 95
4-28 Hexachlorobenzene: a) map of geographical distirbution of various concentration ranges
and b) cumulative frequency distribution in fish tissue 97
4-29 Box and whisker plot for hexachlorobenzene in fish tissue 98
4-30 Pentachlorobenzene: a) map of geographical distribution of various concentration ranges and
b) cumulative frequency distribution in fish tissue, c) Cumulative frequency distribution of
1,3,5 trichlorobenzene in fish tissue 99
4-31 Box and whisker plot for pentachlorobenzene in fish tissue 101
4-32 Box and whisker plot for 1,3,5 trichlorobenzene in fish tissue 102
vni
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List of Figures (Cont.)
Figure Page
4-33 Cumulative frequency distribution of a) 1,2,3,4 tetrachlorobenzene,
b) 1,2,3,5 tetrachlorobenzene, and c) 1,2,4,5 tetrachlorobenzene in fish tissue 103
4-34 Map of geographical distribution of various concentration ranges for
a) 1,2,3,4 tetrachlorobenzene, b) 1,2,3,5 tetrachlorobenzene, andc) 1,2,4,5 tetrachlorobenzene
in fish tissue 105
4-35 Box and whisker plot for 1,2,3,4 tetrachlorobenzene in fish tissue 106
4-36 Cumulative frequency distribution of a) mirex and b) chlorpyrifos in fish tissue 108
4-37 Box and whisker plot for mirex in fish tissue 109
4-38 Map of geographical distribution of various concentration ranges for chlorpyrifos in 110
fish tissue
4-39 Box and whisker plot for chlorpyrifos in fish tissue 112
4-40 Cumulative frequency distribution of a) dicofol (kelthane), b) methoxychlor, and c) perthane
in fish tissue 113
4-41 Map of geographical distribution of various concentration ranges for
a) dicofol and b) methoxychlor in fish tissue 114
4-42 Box and whisker plot for dicofol in fish tissue 115
4-43 Cumulative frequency distribution of a) trifluralin and b) isopropalin in fish tissue 117
4-44 Map of geographical distribution of various concentration ranges for a) trifluralin and
b) isopropalin in fish tissue 118
4-45 Box and whisker plot for trifluralin in fish tissue 119
4-46 Box and whisker plot for isopropalin in fish tissue 120
4-47 Endrin. a) cumulative frequency distribution and b) map of geographical distribution of
various concentration ranges in fish tissue 121
4-48 Box and whisker plot for endrin in fish tissue 123
4-49 Cumulative frequency distribution of a) octachlorostyrene, b) hexachlorobutadiene,
c) diphenyl disulfide, and d) nitrofen in fish tissue 124
4-50 Cumulative frequency distribution of a) beptachlor and b) heptachlor epoxide in fish tissue 126
4-51 Map of geographical distribution of various concentration ranges for a) heptachlor and
b) heptachlor epoxide in fish tissue 127
4-52 Box and whisker plot for heptachlor epoxide in fish tissue 128
4-53 Pentachlororutrobenzene: a) cumulative frequency distribution and b) map of geographical
distribution of various concentration ranges in fish tissue 130
6-1 Graphical tool for estimating upper-bound cancer risk of p,p' -DDE or equivalents for
different fish consumption rates 158
6-2 Graphical tool for estimating upper-bound noncarcinogenic hazard index of p,p'-DDE
for different fish consumption rates 160
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List of Tables
labk Eagfi
2-1 List of Target Anaiytes 5
2-2 Internal Standard Solutions Used for PCDD/PCDF Analyses and XenobkMk Analyses 9
3-1 Summary of Dioxins/Furans Detected in Fish Tissue 22
3-2 1989 Toxicity Equivalency Factors 27
3-3 Location of Maximum Measured HxCDD and HpCDD Concentrations in Fish Tissue 37
3-4 Location of Maximum Measured HxCDF and HpCDF Concentrations in Fish Tissue 38
3-5 Mann-Whitney U Test Results for Dioxins/Furans Comparing Selected Source Categories 43
4-1 S ununary of Xenobiotic Compounds in Fish Tissue 54
4-2 Summary of PCBs in Fish Tissue 59
4-3 Results of Statistical Tests for Selected Xenobiotics and Mercury 62
4-4 Results of Statistical Tests for Selected Xenobiotics (Pesticides/Herbicides) 80
4-5 S ites with Highest Concentrations of Chlordane-Related Compounds 84
5-1 Distribution and Feeding Strategy for Fish Species Collected 132
5-2 Average Fish Tissue Concentrations of Dioxins and Furans for Major Species 138
5-3 DetailedSumrnaryof Occurrence of Prevalent Dioxins/Furans by Fish Species 139
5-4 Average Fish Tissue Concentrations of Xenobiotics for Major Species 140
5-5 Detailed Summary of Occurrence of Prevalent Xenobiotics by Fish Species 141
6-1 Dose-Response Variables Used in Risk Assessment 149
6-2 Estimates of Potential Upper-Bound Cancer Risks at Targeted Sites Based on Fillet
Samples 152
6-3 Estimates of Potential Upper-Bound Cancer Risks at Background Sites Based on Fillet
Samples 153
6-4 Fish Tissue Concentrations Used to Estimate Cancer Risks 154
6-5 Number of Sites with Estimated Upper-Bound Risks 155
6-6 Estimated Upper-Bound Risks at Three Fish Consumption Rates Based on Fillet
Samples 157
6-7 Noncarcinogenic Hazard Index Values at Targeted and Background Sites Based on
Fillet Samples 159
XI
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Acknowledgments
This report was prepared under EPA Contract No. 68-C9-0013. EPA Work Assignment
Managers for the National Study of Chemical Residues in Fish (NSCRF) were Ruth Vender, Stephen
Kroner, Richard Healy, Rod Frederick, Elizabeth Southerland, and Ryan Childs. This study required
extensive effort and coordination of many people from EPA Headquarters, EPA Regions, and States.
Planning and continuing oversight of the study were provided by the National Bioaccumulation
Work Group identified below. EPA staff involved in the planning and initial phase of the study
included Martin Brossman, Stephen Kroner, Alec McBride, and Charles Delos.
Samples were collected by staff from EPA Regions and State agencies. The tissue prepara-
tion and chemical analyses were performed by staff, identified below, at EPA's laboratory in Duluth,
Minnesota. This work was done under the direction of Nelson Thomas and Brian Butterworth.
Assistance in methods selection and QA review was provided by Robert Kleopfer and Douglas
Kuehl of EPA. Staff from the EPA Duluth laboratory also provided material for the methods section
and Q A/QC sections of the report Data evaluations and preparation of the report were accomplished
by the NBS Work Group, and their contractors. In addition, staff from other offices within EPA
provided information for the chemical profiles, in particular, the Office of Pesticide Programs, Office
of Toxic Substances, and Office of Drinking Water. Staff from these and other EPA offices reviewed
the report and provided valuable comments, which have been incorporated into the report.
NSCRF Work Group NSCRF Laboratory Staff
Daniel Granz Region I ESD U.S. EPA
Darvene Adams Region n ESD Brian Butterworth
Gerry McKenna Region n ESD Douglas Kuehl
Bob Dooaghy Region ffl ESD
Jerry Stooer Region IV ESD University of Wisconsin - Superior,
Pete Redmoo Region V ESD Center for Lake Superior Environmental Studies
Carl Young Region VI ESD
Bruce Lattell Region VTJ ESD
Tim Osag Region vm ESD
Doug Eberhardt Region DC WMD
Bruce Ckland Region X ESD
Dave Terpening Region X ESD
Evan Hornig Region X ESD
Elizabeth Soutberland OST/AWPD
Stephen Kroner OST/AWPD
Martin Brossman OST/AWPD
RuthYender OST/AWPD
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Executive Summary
This study, previously referred to as the National Bioaccumulation Study, or NBS, is a
one-time screening investigation to determine the prevalence of selected bioaccumuiative pollutants
in fish and to identify correlations with sources of these pollutants. In addition, estimates were
made of human health risks for those pollutants studied for which cancer potency factors and/or
reference doses have been established. Human health risks were not estimated for dioxins and furans
since the potency of these pollutants is the subject of an EPA review.
The study began in 1986 as an outgrowth of the U.S. Environmental Protection Agency's
(EPA's) National Dioxin Study, a nationwide investigation of 2,3,7,8 tetrachlorodibenzo-p-dioxin
(2,3,7,8 TCDD) contamination of soil, water, sediment, air, and fish. Some of the highest
concentrations of 2,3,7,8 TCDD in the National Dioxin Study were detected in fish. EPA's concern
that there may be other toxic pollutants bioaccumulating in fish was the primary reason for initiating
the National Study of Chemical Residues in Fish. Additionally, this study is considered to be part
of a response to a petition from the Environmental Defense Fund and the National Wildlife
Federation in which EPA committed to conducting an aquatic monitoring survey of the occurrence
of chlorinated dibenzodioxins and chlorinated dibenzofurans. Aquatic biota are being used fre-
quently to determine whether substances are bioaccumulating, to detect acutely toxic conditions,
and to detect stresses such as sublethal toxicity, particularly due to interactions among chemicals.
STUDY DESIGN AND APPROACH
The study design and approach for the National Study of Chemical Residues in Fish
(NSCRF) focused on pollutant selection, field sampling procedures, analytical protocols (including
Quality Assurance/Quality Control), and site selection. Chemicals were selected for analysis based
on the potential of the compound to bioaccumulate in fish, the potential for human health effects,
the persistence of the chemical in the environment, and the ability to detect the compound in fish
tissue. An initial list of 403 pollutants was screened, resulting in a final list of 60 compounds for
analysis. These compounds included 15 dioxins and furans, 10 polychlorinated biphenyls (PCBs),
21 pesticides/herbicides, mercury, biphenyl, and 12 other organic compounds.
Field sampling protocols called for the collection of three to five adult fish of the same
species and of similar size at each site. Information about the samples was recorded, including the
number of samples per composite and sampling date. Age and sex of the fish were not determined.
Weight of the sample used for analysis and percent lipid were determined in the laboratory. Lengths
and weights of the individual fish were not usually available. Sampling was not conducted during
spawning or seasonal migration runs.
At most locations, both a composite sample of a bottom-feeding fish species and a composite
sample of a game fish species were collected. Although 119 species were collected, most of the
fish samples belonged to 14 different species; carp were the most frequently collected bottom feeder
and largemouth bass were the most frequently collected game fish (Table 1). In a few cases, shellfish
were collected instead of fish.
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TABLE 1
Most Frequently Collected Fish Species
Number of Sites
Species Where Collected
Bottom Feeder Species
Carp 135
White Sucker 32
Channel Catfish 30
Redhorse Sucker 16
Spotted Sucker 10
Game Species
Largemouth Bass 83
Smallmouth Bass 26
Walleye 22
Brown Trout 10
White Bass 10
Northern Pike 8
Flathead Catfish 8
White Crappie 7
Bluefish 5
XVI
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Fish samples were analyzed at EPA's Environmental Research Laboratory (ERL) in Duluth.
Minnesota. In general, the bottom feeders were analyzed as whole-body samples to determine the
occurrence of the study chemicals and the game fish were analyzed as fillets to indicate the potential
for risks to human health from fish consumption. Selected bottom feeders of the type often used
for human consumption were analyzed as fillets at a small number of sites and used to evaluate
human health risks. To analyze fish for the 15 dioxins and furans, ERL-Duluth refined and expanded
the method for dioxin (i.e., 2,3,7,8 TCDD) analysis developed as part of EPA's National Dioxin
Study. For 44 of the remaining 45 compounds, ERL-Duluth developed an analytical method
specifically for this study. The remaining study compound, mercury, was analyzed using EPA's
standard analytical techniques.
Sites were selected for the study by EPA Regional and State staff. Sites consisted of 314
locations thought to be influenced by a variety of point and nonpoint sources (referred to as targeted
sites), 39 locations from the USGS National Stream Quality Accounting Network (NASQAN), and
35 sites representative of background levels (Figure 1). Targeted sites included locations near pulp
and paper mills, refineries using the catalytic reforming process, Superfund sites, former wood
preserving operations, other industrial sites, publicly owned treatment works (POTWs), and
agricultural and urban areas. Because the study was initiated as a follow-up to the National Dioxin
Study, many of the targeted sites selected were those thought to be producers of dioxins (e.g., pulp
and paper mills using chlorine for bleaching).
RESULTS
Prevalence and Concentration
Many of the investigated pollutants were frequently detected in the fish samples from the
targeted sites. Seven of the 15 dioxin/furan compounds and 15 of the other 45 compounds were
detected at over 50 percent of the sites (Tables 2 and 3). The two most frequently detected dioxin
and furan compounds were both found at 89 percent of the sites; these compounds are 1,2,3,4,6,7,8
heptachlorodibenzodioxin (HpCDD) and 2,3,7,8 tetrachlorodibenzofuran (TCDF). These com-
pounds were also detected at the highest concentrations; HpCDD at 249 picograms per gram (pg/g)
or 249 parts per trillion by wet weight (ppt) and TCDF at 404 parts per trillion (ppt). The average
concentrations of these two compounds were substantially lower at 10.5 and 13.6 ppt, respectively.
The dioxin compound considered to be the most toxic, 2,3,7,8 tetrachlorodibenzo-p-dioxin (TCDD),
was found at 70 percent of the sites at a maximum concentration of 204 ppt and an average
concentration of 6.89 ppt. Only two of the 15 dioxin/furan compounds analyzed were detected at
fewer than 20 percent of the sites.
Toxicity equivalent concentrations (TECs) of dioxins/furans were calculated to facilitate
comparison of fish tissue contamination among sites. TEC represents a toxicity weighted total
concentration of all individual congeners using 2,3,7,8, TCDD as the reference compound. EPA's
interim method was used to determine TEC (Barnes, et. al., 1989). This is referred to in the report
as the Toxicity Equivalency Concentration (TEC) value, sometimes called TEQ (toxicity
equivalents).
xvii
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PUERTO RICO
Figure 1. Location of bioaccumulation study sampling sites.
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TABLE 2
Summary or Prevalence and Concentration
for Dioxins and Furans
Concentration
Chemical
Dioxins
1, 2,3, 4,6,7,8 HpCDD
2,3,7,8 TCDD
1,2,3 ,6,7,8 HxCDD
1, 2,3,7,8 PeCDD
1,2,3,7,8,9 HxCDD
1,2,3,4 ,7,8 HxCDD
Furans
2,3,7,8 TCDF
2,3,4,7,8 PeCDF
1,2,3, 4,6,7, 8 HpCDF
1,2,3,7,8 PeCDF
1, 2,3,4,7,8 HxCDF
2,3,4,6,7 ,8 HxCDF
1,2,3 ,6,7 ,8 HxCDF
1,2,3,4,7,8,9 HpCDF
1,2,3,7,8,9 HxCDF
TEC*
Percent of
Sites Detected
89
70
69
54
38
32
89
64
54
47
42
32
21
4
1
N/A
pg/gor ppt by wet weight
Max
249
204
101
54.0
24.8
37.6
404
56.4
58.3
120.0
45.3
19.3
30.9
2.57
0.96
213
Mean
10.5
6.89
4.30
2.38
1.16
1.67
13.6
3.06
1.91
1.71
2.35
1.24
1.74
1.24
1.22
11.1
Median
2.83
1.38
1.32
0.93
0.69
1.24
2.97
0.75
0.72
0.45
1.42
0.98
1.42
1.30
1.38
2.80
TEC represents the sura of toxicity-weighted concentrations of all dioxins and furans relative to 2,3,7,8 TCDD.
xix
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TABLE 3
Summary of Prevalence and Concentration
for 45* Other Bioaccumulative Compounds
Chemical
DDE
Mercury
Biphenyl
Total PCBs
Nonachlor, trans
Chlordane, cis
Pentachloroarusole
Chlordane, trans
Dieldnn
Alpha-BHC
1,2,4 Trichlorobenzene
Hexachlorobenzene
Gararna-BHC
1 ,2,3 Trichlorobenzene
Mirex
Nonachlor, cis
Oxychlordane
Chlorpyrifos
Pent achJorobenzene
Heptachlor Epoxide
Dicofol
1 ,2,3,4 Tetrachlorobenzene
Trifluralin
1,3,5 Tnchlorobenzene
Endrin
1,2,3,5 TECB
Octachlorostyrene
1,2,4,5 TECB
Methoxychlor
Isopropalm
Nitrofen
Hexachlorobutadiene
Heptachlor
Perthane
Pentachloronitrobenzene
Diphenyl Disulfide
Percent of
Sites Detected
99
92
94
91
77
64
64
61
60
55
53
46
42
43
38
35
27
26
22
16
16
13
12
11
11
9
9
9
7
4
3
3
2
1
1
1
Mai
14000
1800
131
124000
477
378
647
310
450
44.4
265
913
83.3
69.0
225
127
243
344
125
63.2
74.3
76.7
458
14.9
162
28.3
138
28.3
393
37.5
17.9
164
76.2
5.12
15.5
3.24
Concentration
nf/8 of ppb by wet
Mean
295
260
2.7
1890
31.2
21.0
10.8
16.7
28.1
2.41
3.10
580
2.70
1.27
3.86
8.77
4.75
4.09
1.18
2.19
0.98
0.47
5.98
0.12
1.69
0.34
1.71
0.33
1.32
0.46
0.17
0.57
0.35
0.03
0.09
0.02
weight
Median
58.3
170
064
209
9.22
3.66
0.92
2.68
4.16
0.72
0.14
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
* The number of compounds shown here is 36; the difference is the result of grouping 3 individual PCB compounds
with 1 to 10 chlorines. Five of the PCBs were found at concentrations above 50 percent; the remainder were found
between 3 and 35 percent
-------
In general, the maximum and average concentrations for the other 45 compounds are 1,000
to 10,000 times greater than those for dioxins and furans (Table 3). Of these 45 compounds, the
most frequently detected pollutant was DDE, found at over 98 percent of all sites sampled. This
compound is a metabolic breakdown product of DDT, which was a widely used pesticide and is
extremely persistent in the environment. Other compounds detected at more than 90 percent of the
sites were mercury, total PCBs, and biphenyl. The high prevalence of mercury results partly from
its many industrial uses including use in batteries, vapor lamps, and thermostats; as a fungicide in
some exterior water-based paints; and as a cathode in the electrolytic production of chlorine and
caustics. Mercury also occurs in the natural environment in both inorganic and organic compounds
and is discharged to the atmosphere from natural processes (e.g., degassing of volcanos) and from
the burning of fossil fuels. As with DDT, PCBs are very persistent in the environment and, until
1977 when they were essentially banned, were widely used as dielectric fluids in transformers and
capacitors. Total PCBs in this study refers to the sum of the concentrations of compounds with 1
to 10 chlorines. Concentrations of specific Aroclors or mono-ortho substituted compounds were
not determined in this study. The high number of low-concentration biphenyl samples (88 percent
below 2.5 ppb) most likely results from degradation of PCBs. The high-concentration samples
appear to be associated with various industrial uses such as heat transfer fluid, dye carriers, and
hydraulic fluid.
PCBs were detected at the highest concentration, with a maximum value of 124,000
nanograms per gram (ng/g) or 124,000 parts per billion by wet weight (ppb), and an average
concentration of 1,890 ppb. The next highest compound was DDE, with a maximum and average
concentration of 14,000 ppb and 295 ppb, respectively. All of the remaining 34 compounds were
found at much lower concentrations than DDE.
Prevalence was compared with the most recent (1984) results from the National Contaminant
Biomonitoring Program (NCBP), which was formerly part of the National Pesticide Monitoring
Program. The NCBP was initiated in 1964 to determine how organochlorine compound levels vary
over geographic regions and change over time. In this program, fish were sampled at 112 sites
throughout the United States and these samples were analyzed for 19 organochlorine chemicals and
7 metals. The NSCRF analyzed 15 of these 19 organochlorine compounds and mercury. In the
NSCRF, 11 compounds were found at greater than 50 percent of the sites. Eight of these were also
analyzed in the NCBP, and seven compounds were found at greater than 50 percent of the sites.
The results from these two studies track closely for the common pollutants analyzed.
Source Correlation Analysis
Concentration comparisons between selected source categories were made using various
statistical tools including a box and whisker plot. The categories used were background sites, sites
selected from the USGS NASQAN network, sites near Superfund locations , sites near pulp and
paper mills that use chlorine for bleaching, sites near other types of pulp and paper mills, sites near
former or existing wood preserving plants, sites near industrial or urban areas, sites near industrial
areas that include refineries with catalytic reforming operations, sites that could be influenced by
runoff from agricultural areas, and sites near POTWs. These categories were selected based on
probable sources of pollutants. Background sites were selected to provide a comparison with areas
JCIJ
-------
relatively free of point and nonpoint source pollution. Sites where multiple source categories could
have affected fish contamination levels were not used for the box plots or other statistical tests. For
example, sites in the chlorine paper mill category that were also near Superfund sites, other paper
mills, or reefineries were not used for the dioxin/furan box plots.
Pulp and paper mills using chlorine to bleach pulp appeared to be the dominant source of
2,3,7,8 TCDD and 2,3,7,8 TCDF. Statistical comparison, using Kruskal-Wallis tests and Mann-
Whitney U tests show that sites near pulp and paper mills using chlorine have significantly higher
concentrations of 2,3,7,8 TCDD than all other source categories. These statistical tests also show
the same results for 2,3,7,8 TCDF with the exception that fish contamination levels near sites in the
Superfund category marginally met the statistical test criteria for being similar. Analysis of the five
sites with the highest 2,3,7,8 TCDD and 2,3,7,8 TCDF concentrations also show that pulp and paper
mills using chlorine are dominant sources of these compounds at four of these sites.
Statistical correlation analyses were less definitive for the other dioxins/furans in that results
showed no dominant source for any of these chemicals (i.e., a source from which fish contamination
levels were significantly higher than all other sources). A review of dioxin/furan data limited to
median concentrations alone shows that Superfund sites are highest for penta-furans, paper mills
using chlorine are highest for penta- and hexa-dioxins, and refinery/other industry sites are highest
for hexa-furans.
Results for the other 45 chemicals studied also showed no single dominant source for any
of these chemicals. Although these compounds showed no dominant source, a number of observa-
tions can be made from review of the data. Two such examples involve pesticides and PCBs. A
comparison of 15 agricultural and 20 background sites for 10 of the pesticides evaluated showed
no significant differences between these categories. This same comparison for four other pesticides
(DDE, nonachlor, chlordane, and gamma-BHC (lindane)) showed that fish contamination levels
were significantly higher at sites near agricultural sources. The median PCB concentration for the
20 background sites was below detection compared with values of 213 to 525 ppb for in-
dustrial/urban sites, paper mills using chlorine, refinery/other industry sites, nonchlorine paper mills,
and Superfund sites.
HUMAN HEALTH RISK ESTIMATES
Potential upper-bound human cancer risk from consumption of fish was estimated using
fillet samples for 14 compounds for which cancer potency factors are available (Table 4). Human
health risks were not calculated for dioxins/furans, due to the current review of the potency of these
chemicals. Most of the fillets were game fish, but fillets from a few bottom feeders that are consumed
by humans were also included. Fillet data were available at 182 sites for mercury and 106 sites for
the remaining chemicals. The risk estimates were performed using standard EPA risk assessment
procedures and assumed lifetime exposure. Upper-bound cancer potency factors, and fish consump-
tion rates of 6.5, 30, and 140 g/day were used.
xxii
-------
The highest estimated lifetime human cancer risk levels are associated with total PCBs. The
cancer risk exceeded 10" at 42 sites for total PCBs for a fish consumption rate of 6.5 g/day (Table
4). The second highest cancer risk was associated with dieldrm where six sites had estimated cancer
risks greater than 10" for a 6.5-g/day fish consumption rate
Potential noncarcinogenic effects on human health were estimated for the 21 compounds
for which reference dose (RfD) values were available. Hazard indices based on a fish consumption
rate of 6.5 g/day exceeded a value of 1 (meaning adverse health effects may occur) at a small number
of sites due to total PCBs, mirex, and combined chlordane when the maximum fillet concentrations
were used in the analysis. No indices were exceeded when the mean or median concentrations were
used. Combined chlordane is the sum of the concentrations of cis- and trans- chlordane, cis- and
trans-nonachlor, and oxychlordane.
STUDY LIMITATIONS
The risks presented in this report represent a national screening assessment and not a detailed
local assessment of risks to specific populations. Such detailed risk assessments would consider
the number of people exposed and incorporate local consumption rates and patterns. Furthermore,
a detailed assessment would require a greater number offish samples per site than collected for this
screening study. Additionally, this study does not address all the bioaccumulative pollutants that
may be present in surface waters.
One of the original intents of the NSCRF was to further investigate dioxm/furan concentra-
tions in fish; consequently, the selection of sites was biased toward sites where these compounds
might be found. The intent of the source correlations was to identify potential sources, in addition
to pulp and paper mills using chlorine, for either dioxins/furans or the other study compounds.
-------
TABLE 4
Number of Sites with Estimated Upper-Bound Risks
TARGETED SITES
Chemical
PCBs
Dieldrin
Combined Chlordane
DDE
Heptachlor Epoxide
Alpha-BHC
Mirex
HCB
Gamma-BHC
Heptachlor
Dicofol
Hexachlorobutadiene
Pentachloroanisole
Trifluralin
No. of Sites
with Fillet
Data
106
106
106
106
106
106
106
106
106
106
106
106
106
106
RISK LEVEL (Cumulative)
10-6
(>1 in 1,000,000)
89
53
44
40
9
11
8
5
0
0
0
0
0
0
10-5
(>1 in 100, 000)
79
31
10
10
2
1
2
0
0
0
0
0
0
0
10-4
(>1 in 10,000)
42
6
0
0
0
0
0
0
0
0
0
0
0
0
10-3
(>1 in 1,000)
10
0
0
0
0
0
0
0
0
0
0
0
0
0
BACKGROUND SITES
Chemical
PCBs
DDE
No. of Sites
with Fillet 10-6
10-5
Data (>1 in 1,000,000) (>1 in 100, 000)
Basis: 1)
2)
3)
Combined chlordane
ane.
4 I
4 1
1
0
10-4
(>1 in 10,000)
0
0
Used EPA (i.e., upper-bound) cancer potency factors.
Used consumption rate of 6.5 grams/day.
Used average fillet concentrations at the few sites with
multiple samples.
is the sum of cis- and trans-chlordane isomers, cis- and trans-nonacblor isomers,
10-3
(>1 in 1,000)
0
0
and oxychlord-
XJUV
-------
Chapter 1 - Introduction
BACKGROUND
This report presents the results of the U.S. Environmental Protection Agency's (EPA's)
National Study of Chemical Residues in Fish (NSCRF), previously referred to as the National
Bioaccumulation Study (NBS). The study was initiated in 1986 as an outgrowth of EPA's National
Dioxin Study. The National Dioxin Study was a 2-year, nationwide investigation of 2,3,7,8
tetrachlorodibenzo-p-dioxin (2,3,7,8 TCDD) contamination in soil, water, sediment, air, and fish.
Some of the highest concentrations of 2,3,7,8 TCDD discovered in the environment during that
effort were detected in fish. EPA's concern that there may be other pollutants with properties similar
to 2,3,7,8 TCDD bioaccumulating in fish was a primary reason for initiating the NSCRF. Addi-
tionally, in response to a petition from the Environmental Defense Fund and the National Wildlife
Federation, EPA committed to conducting an aquatic monitoring survey of the occurrence of
chlorinated dibenzodioxins and chlorinated dibenzofurans. Aquatic biota are frequently being used
to determine whether substances are bioaccumulating, to detect acutely toxic conditions, and to
detect stresses such as sublethal toxicity, particularly due to interactions among chemicals.
The objectives of this one-time screening investigation were to determine the prevalence of
selected bioaccumulative pollutants in fish and to identify correlations with sources of these
pollutants. In addition, estimates were made of human health risks for those pollutants studied for
which cancer potency factors and/or reference doses have been established. Human health risks
were not estimated for dioxins and furans since the potency of these pollutants is the subject of an
EPA review.
Bioaccumulation is the uptake and retention of chemicals by living organisms. Aquatic
organisms such as fish are exposed to pollutants through contaminated water, sediment, and food.
A pollutant bioaccumulates if the rate of intake into the living organism is greater than the rate of
excretion or metabolism. This results in an increase in the tissue concentration relative to the
exposure concentration in the ambient environment. Consequently, analysis offish tissue can reveal
the presence of pollutants in waterbodies that may escape detection through routine monitoring of
water alone. Contaminants detected in fish not only indicate pollution impact on aquatic life and
other wildlife (i.e., through biomagnification up the food chain), but also can represent a significant
route of human exposure to toxic chemicals through consumption of fish and shellfish.
GENERAL APPROACH
Composite fish samples were collected primarily in 1987 at 388 locations nationwide and
analyzed for concentrations of 60 contaminants by EPA's Environmental Research Laboratory
(ERL) in Duluth, Minnesota. EPA's Office of Science and Technology personnel, Regional
Coordinators, and State personnel selected the sampling sites. Locations selected included targeted
sites near potential point and nonpoint pollution sources; background sites in areas relatively free
of pollution sources; and a small subset of sites selected from the U.S. Geological Survey's (USGS)
-------
National Stream Quality Accounting Network (NASQAN) for nationwide coverage. Targeted sites
included areas near significant industrial, urban, or agricultural activities. Over 100 sampling sites
near pulp and paper mills using chlorine to bleach pulp were added to the study after results of the
National Dioxin Study indicated a correlation between 2,3,7,8 TCDD occurrence in fish and
proximity to pulp and paper mill discharges. Some samples collected from the National Dioxin
S tudy sites were reanalyzed as part of this study to obtain information on concentrations of pollutants
other than 2,3,7,8 TCDD.
EPA Regional Coordinators managed the collection of composite samples, accomplished
primarily by State agencies. In general, a representative bottom-fee ding species, whole-body
composite sample was collected and analyzed for each site to determine general occurrence of each
contaminant in any portion of the fish. A representative game fish fillet composite sample was
analyzed at a limited number of the study sites, usually where whole-body concentrations were high,
to indicate the potential risk to human health from consumption of the edible portion. A few
bottom-feeding species composite samples were also analyzed as fillets and used to estimate human
health risks.
Target analytes were selected on the basis of their potential to bioaccumulate, human
toxicity, and analytical feasibility. Hundreds of potential chemicals of concern were screened for
inclusion in the study. The final list of 60 contaminants included 15 chlorinated dibenzodioxins
and dibenzofurans and 45 other xenobiotic chemicals, primarily polychlorinated biphenyls. and
chlorinated organic pesticides. The final list did not represent a comprehensive list of all
bioaccumulative pollutants of concern.
Three methods were employed for laboratory analyses. ERL-Duluth refined and expanded
the method for dioxin analysis developed for the National Dioxin Study to include 14 polychlori-
nated dibenzodioxins and polychlorinated dibenzofurans in addition to 2,3,7,8 TCDD. ERL-Duluth
developed a second method specifically for this study to measure concentrations of 44 of the other
xenobiotic study analytes. Mercury was analyzed separately from the other study chemicals using
EPA's standard analytical techniques.
-------
Chapter 2 - Study Design and Approach
This chapter provides an overview of the development of the design and analytical approach
for this national study of chemical residues in fish. Prior to undertaking the study, a Work/Quality
Assurance Project Plan (U.S. EPA, 1986a) was prepared that described the overall goals for the
study, the data quality objectives, and the Quality Assurance/Quality Control (QA/QC) procedures
to meet the objectives. This study, to a large extent, built upon experience gained during the
multimedia EPA National Dioxin Study (U.S. EPA, 1987b), which investigated contamination from
2,3,7,8 tetrachlorodibenzo-p-dioxin (2,3,7,8 TCDD). Unlike the National Dioxin Study, however,
this study was intended to screen for a wider range of chemicals with high potential to bioaccumulate
in fish (or shellfish) tissue. Consequently, new or modified analytical methods had to be developed.
ERL-Duluth was responsible for developing and verifying the analytical methods, determining
compliance with precision and accuracy targets, and achieving minimum detection limits to meet
the objectives of the study.
POLLUTANT SELECTION SCREENING PROCESS
A screening process was undertaken by EPA to select the pollutants for the study. Four
hundred and three chemicals were initially identified as candidate study compounds. Sources from
which these chemicals were identified included:
1. List of priority pollutants. Priority pollutants are the 126 pollutants derived from the
65 classes of compounds listed in Clean Water Act section 307(a). Some of the
priority pollutants were included on the screening list for this study based on their
potential human health or aquatic life effects and exposure potential (Tobin, 1984).
2. Pesticides detected in effluents from pesticide manufacturing plants (Dorman, 1985).
3. The Carcinogen Assessment Group's (CAG's) List of Chemicals Having Substantial
Evidence of Carcinogenicity (U.S. EPA, 1980b).
4. Semivolatile organic compounds identified by the Office of Toxic Substances in 1980
to be in human adipose tissue (U.S. EPA, 1980c).
5. Chemicals considered by the international Agency for Research on Cancer (IARC) to
have substantial evidence of carcinogenicity (evaluated after CAG 1980 list was
completed).
6. National Toxicology Program (NTP) chemicals classified as carcinogens in Annual
Reports on Carcinogens (NTP, 1982a,b).
1 Specific pollutants are listed in 44 FR 34393 (1979), as amended by 46 FR 2266 (1981), and 46 FR 10723 (1981).
-------
7. Clean Water Act 4(c) Program pollutants, other than priority pollutants, identified in
industrial and POTW effluents as nonbiodegradable.
8. Additional suggestions from Agency experts.
The resulting list of candidate chemicals was first screened for bioaccumulation potential.
Compounds with calculated or experimental Bioconcentration Factors (BCFs) greater than 300 were
selected because they have greater potential to bioaccumulate and because the projected human
exposure from fish consumption would be greater than the projected exposure from drinking water.
The list of chemicals was further screened based on human toxicity, exposure potential, persistence
in the aquatic environment, and biochemical fate in fish. For example, compounds that are quickly
hydrolyzed or metabolized were identified and eliminated from further consideration. Finally,
screening of the remaining chemicals was undertaken with regard to analytical feasibility by
chemists at ERL-Duluth. Chemicals presenting significant analytical difficulties, such as not being
amenable to generalized isolation procedures, were removed from the list. For example, low
recovery from the silica gel column eliminated chlorbenzilate, triphenyl phosphate, and
trichloronate. Kepone was deleted due to inconsistent mass spectral response.
A final list of 15 dioxin and furan congeners and 45 other xenobiotic chemicals resulted
from the screening process (Table 2-1). The 2,3,7,8 substituted dioxins and furans were selected
for analysis due to their toxicity. For these analytes, maximum target detection levels were
determined based on potential fish tissue concentration levels of concern, i.e., those associated with
a given level of toxicity (10" risk of cancer). The latter were derived following Agency guidelines
(U.S. EPA, 1986a).
FIELD SAMPLING PROCEDURES
Sample Collection
The EPA Regional Offices were responsible for the collection of the fish samples and for
transport to ERL-Duluth for analysis. Procedures for sample fish collection, handling, preservation,
and transport were described in the Work/Quality Assurance Project Plan (U.S. EPA, 1986a, 1984)
and are noted below. Two composite fish samples per site were collected, where possible:
1. A representative bottom-feeding fish composite to be analyzed whole, as an overall
indication of pollutant levels at each site.
2. A representative game fish composite to be analyzed as a fillet to provide an indication
of potential human health risk from consumption of fish.
Approximately three to five adult fish of similar size and from the same species were
collected for each composite at a given site allowing for a minimum sample size of 500 grams.
All fish in the composite sample were obtained from the same site. The fish species targeted
for sampling were considered to be good bioaccumulators and/or were routinely consumed by
humans. For bottom-feeding fish, target fish in order of preference were 1) carp, 2) channel
catfish, and 3) white sucker. Suggested target species for game fish included 1) white bass,
2) northern pike, 3) walleye, 4) smallmouth bass, 5) largemouth bass, and 6) crappie. (A
-------
TABLE 2-1
List of Target Analytes
DIOXINS
2,3,7,8 Tetrachlorodibenzodioxin (TCDD)
1,2,3,7,8 Pentachlorodibenzodioxin (PeCDD)
1,2,3,6,7,8 Hexachlorodibenzodioxin (HxCDD)
1,2,3,7,8,9 Hexachlorodibenzodioxin(HxCDD)
1,2,3,4,7,8 Hexachlorodibenzodioxin(HxCDD)
1,2,3,4,6,7,8 Heptachlorodibenzodioxin(HpCDD)
FURANS
2,3,7,8 Tetrachlorodibenzofuran (TCDF)
1,2,3,7,8 Pentachlorodibenzofuran (PeCDF)
2,3,4,7,8 Pentachlorodibenzofuran (PeCDF)
1,2,3,6,7,8 Hexachlorodibenzofuran (HxCDF)
1,2,3,7,8,9 Hexachlorodibenzofuran (HxCDF)
1,2,3,4,7,8 Hexachlorodibenzofuran (HxCDF)
2,3,4,6,7,8 Hexachlorodibenzofuran (HxCDF)
1,2,3,4,6,7,8 Heptachlorodibenzofuran (HpCDF)
1,2,3,4,7,8,9 Heptachlorodibenzofuran (HpCDF)
OTHER XENOBIOTICS
Biphenyl Mirex
Chlordane, cis Nitrofen
Chlordane, trans Nonachlor, cis
Chlorpyrifos Nonachlor, trans
p,p'-DDE Octachlorostyrene
Dicofol Oxychlordane
Dieldrin Pentachloroanisole
Diphenyl Disulfide Pentachlorobenzene
Endrin Pentachloronitrobenzene
Heptachlor Perthane
Heptachlor epoxide Polychlorinated Biphenyls
Hexachlorobenzene (Mono-Decachlorinated)
Hexachlorobutadiene 1,2,4,5 Tetrachlorobenzene
alpha-BHC 1,2,3,4 Tetrachlorobenzene
gamma-BHC (lindane) 1,2,3,5 Tetrachlorobenzene
Isopropalin 1,2,3 Trichlorobenzene
Mercury 1,2,4 Trichlorobenzene
Methoxychlor 1,3,5 Trichlorobenzene
Trifluralin
-------
summary of the types of fish actually collected and analyzed and a comparison of the observed fish
tissue concentrations detected are included in Chapter 5, "Fish Species Summary and Analysis.")
Sample Handling/Preparation
After collection, the fish were individually wrapped in aluminum foil, labeled, dry-iced, and
shipped frozen to Duluih. Chain-of-custody procedures were followed for each sample using a
centralized sample control system. Once fish samples were received by ERL-Duluth, the staff
completed the chain-of-custody forms and placed the frozen samples in a freezer. Fish tissue was
ground frozen and homogenized in a stainless steel meat grinder. For whole-fish samples (e.g.,
bottom feeders), the entire fish including organs and muscle tissue was ground. For game fish,
fillets with the skin off were prepared and then ground. Most filleting (skin-off) was done at
ERL-Duluth. All equipment and the stainless steel table were cleaned after each use. The ground
tissue was stored at -20°C until extracted.
Fish Length and Weight Data
Length and weight data for individual fish in the bioaccumulation data set were not usually
available. Information on the number of samples per composite and sampling date was recorded,
along with the weight of the sample and percent lipid (see Appendix D, Vol. II). Age and sex were
not determined for this study. To minimize potential differences, fish were not collected during or
soon after spawning or during seasonal migration. The dates of sample collection are included in
Appendix D, Vol. II. In future studies, it is recommended that length and weight data be obtained
for all samples and that enough samples be aged to develop age vs. length and weight relationships.
In some cases, only mean lengths and weights were available for the fish from which fillet and
whole-body samples were prepared for analysis. A preliminary review of the data indicated that
some samples consisted of individual specimens with widely differing lengths and weights. This
probably resulted from limited availability of fish. Assuming thai length and weight are a
reasonable indicator of age for most fish species, then the likely use of different age fish could bias
some of the various bioaccumulation study analyses. In general, it may be assumed that older fish
would have had a longer exposure to contaminants either through direct contact with substrates
(e.g., demersal species) or as predators, having consumed large quantities of contaminated prey.
Changes in metabolism related to age and other age-dependent factors may also affect tissue
contaminant levels. In general, samples prepared for tissue analyses requiring multiple specimens
should, to the extent possible, include only those fish which are essentially the same length and
weight and, hence, approximate age.
ANALYTICAL PROTOCOLS
Three analytical procedures were employed during the laboratory analysis of the sample
composites. The summaries that follow have been abstracted from U.S. EPA, I990b, EPA/600/3-
90/022 (PCDD/PCDF); U.S. EPA, 1990c, EPA/600/3-90/023 (xenobiotic chemical contaminants);
and U.S. EPA, 1989a (mercurv).
-------
Dioxins/Furans
A schematic of the analytical procedures used for the tissue extraction of polychlorinated
dibenzodioxins and polychlorinated dibenzofurans (PCDD/PCDF) is shown in Figure 2-1. Specific
details of the analytical procedures used are provided in U.S. EPA, 1990b (included in Appendix
A). After spiking a dry tissue sample with internal standard solutions, the sample was extracted
with a mixture of hexane and methylene chloride and the eluent was collected in a Kuderna-Danish
(KD) apparatus. The internal standards added at this point consisted of 11 different C labeled
compounds and four PCDD/PCDF compounds (see Solutions A and B in Table 2-2.). The KD
apparatus was then placed in a 60°C water bath under a dry carbon filtered air flow. After the solvent
had evaporated, the lower tube and contents were weighed. The lipid was then quantitatively
transferred to an acid-celite macro-column, and the lower empty tube and contents were weighed.
The percent lipid was calculated based on the difference in weights. The acid-celite column was
eluted with benzene/hexane. Isooctane was added and the sample volume reduced for transfer to
the activated florisil/sodium sulfate column. The column was eluted with methylene chloride and
hexane and the eluate discarded. The column was then washed with methylene chloride, which
flowed directly onto a carbon silica gel column for PCDD/PCDF isolation. Benzene/methylene
chloride was added to the carbon column, and then the carbon column was inverted. The
PCDD/PCDF were eluted with toluene and another internal standard, Solution C in Table 2-2, prior
to gas chromatography/mass spectrometry (GC/MS) analysis.
During the course of this study, changes were made to the PCDD/PCDF methodology. In
1987, toluene was replaced with tridecane as the solvent for the standard PCDD/PCDF recovery
and calibration solutions. The new standards included more compounds than the original set. In
addition, the procedure for determining the minimum level of detection was modified to better reflect
actual instrumental analysis. Consequently, results generated after July 1987 reflect a minimum
level of detection (MLD) defined as the concentration predicted from the ratio of the baseline noise
area to the labeled internal standard area plus three times the standard error of the estimate from the
weighted initial calibration curve. Before this procedure, the MLD was determined according to
the Analytical Procedures and Quality Assurance Plan for the Analysis of 2,3,7,8 TCDD in Tier 3-7
Samples of the U.S. Environmental Protection Agency National Dioxin Study (EPA/600/3-85-019).
Prior to the addition of the florisil column in July 1988, polychlorinated diphenylethers
interfered with the quantification of some of the biosignificant furans (2,3,4,7,8 PeCDF; 1,2,3,4,6,7
HxCDF; 1,2,3,4,7,8 HxCDF; and 2,3,4,6,7,8 HxCDF). The reported values for these compounds
may have been overestimated due to the interference. The samples with interferences were flagged
in the data reports with a comment. In addition, a flag has been added to the data tables indicating
that 1,2,3,4,7,8 HxCDF coelutes with 1,2,3,4,6,7 HxCDF on the GC column (DBS 30M).
All GC/MS analyses were done using high-resolution GC/high-resolution MS
(HRGC/HRMS). Before the analyses, each sample was spiked with a standard solution and the
sample volume adjusted to 20 |iL with tridecane. Sample analyses were done in sets of twelve
consisting of:
-------
SOXHLET
EXTRACTION
GROUND TISSUE
13C LABELED
SURROGATE ANAL VIES
FLOfilSJL
CHROMATO-
GRAPHY
ELUTION
1. WTERFERENT REMOVAL
20ML OF 2%
CH2CL2 / HEXANE
2. ANALYTE FRACTION
50ML CH
SOLVENT
REMOVAL
XENOBJOTIC CHEMICAL,
ISOLATION
SULFURJC ACD/CELfTE
POTASSIUM SUCATE
SUCAQEL
|
KUDERNA DAMSH
APPARATUS
100ML5%OF
BENZENE/HEX ANE
CARBON
CHROMATO-
GRAPHY
1. INTERFERENT REMOVAL
20ML OF 25%
BENZENE / CH2CL2
2. ANALYTE FRACTION
25ML TOLUENE
ADO SECOND NTERNAL STANDARD
13 C121,2.3,4-TCDD M TROEC ANE
HRGC/HRMS
PCDD/PCDF QUANTITATION
Figure 2-1. Schematic of laboratory procedures for dioxins and furans.
8
-------
TABLE 2-2. Internal Standard Solutions Used for PCDD/PCDF Analyses
Concentration Concentration
Compound in Solution (pg/(jL) in tissue (pg/g*)
Internal Standard Soluimn A (lOO^I .^
37cu 2.3.7,8 TCDD 2.0 10.0
13ci2 2.3,7.8 TCDD 5.0 25.0
1 3ci2 2.3.7,8 TCDF 5.0 25.0
13ci2 1,2,3,7 .8 PeCDD 5.0 25.0
13ci2 1,2.3,7,8 PeCDF 5.0 25.0
13ci2 1,2,3.4.7.8 HxCDD 12.5 62.5
13C12 1.2,3,4,7.8 HxCDF 12.5 62.5
13ci2 1,2.3,4,6.7.8 HpCDD 12.5 62.5
13ci2 1,2.3,4,6.7,8 HpCDF 12.5 62.5
13ci:OCDD 25.0 125.0
37cu 2,3,7,8 TCDF 2.0 10.0
Internal Stanrtajtl Sjo|ution B.
1,2,3,4 TCDD 1.0 5.0
1,2,4,7,8 PeCDD 1.0 5.0
1,2,3,4 TCDF 1.0 5.0
1,2,3,6,7 PeCDF 1.0 5.0
Internal Stanford Solution C.
13ci2l,2.3,4TCDD 50.0 50.0
* Assumes a 20-g sample.
Reference. U.S. EPA, 1990b.
Surrogate Standard and Internal Standard Solutions
Used for Other Xenobiotic Compound Analyses
Compound Concentration
Surroeate Standard Solution A (25iiL)
lodobenzene 125
1-Iodonaphtbalene 125
4,4'-Diiodobiphenyl 125
Internal Standard Solution (10uL)
Biphenyl-Dio 50
Phenanthrene-Dio 75
Chrysene-Di2 75
-------
1. One method blank;
2. One additional fortified matrix (blank) spiked with native analytes;
3. One detection limit verification sample—an environmental sample with a detectable
amount of native analyte (determined from a previous analysis), spiked with native
analytes, and analyzed with the next sample set (used for only the first three sample
sets of a matrix type to establish that the calculated MLD was achievable);
4. One duplicate sample; and
5. Eight (if detection limit verification sample used) or nine environmental samples.
Quantification of analytes was accomplished by assigning isomer identification, integrating
the area of mass-specific GC peaks, and calculating an analyte concentration based upon an ion
relative response factor between the analyte and the appropriate standard. For the tetrachloro- to
heptachloro-congeners/isomers of PCDD/PCDF, analytical results were reported as concentration
in picograms per gram (pg/g) (ppt wet weight) for each GC peak in a congener class by making the
assumption that the response for the molecular ion of all isomers in that class was equal to the
response observed for the isomer for which ERL-Duluth had a standard. Target MLD are noted
below:
TCDD, TCDF 1 pg/g
PeCDD, PeCDF 2 pg/g
HxCDD.HxCDF 4 pg/g
HpCDD, HpCDF 10 pg/g
The specific detection limits for each sample with concentrations below detection were
recorded in the data base (see Appendix D, Volume n). The actual detection limits achieved were
often lower than the above targeted values.
Other Xenobiotic Chemicals
A schematic of the analytical procedures used for the tissue extraction of the other xenobiotic
chemicals is shown in Figure 2-2. More specific details are provided in U.S. EPA, 1990c, included
in Appendix A. Before extraction, each sample was fortified with a surrogate standard solution
(Table 2-2) to evaluate the recovery of target analytes. To isolate the xenobiotic chemical
contaminants, a gel permeation chromatography (GPC) system was first used to remove fish lipid
interferences. Then a Kontes column packed with silica gel was used to remove naturally occurring
cholesterol and fatty acids. Finally, the samples were spiked with an internal standard solution, also
listed in Table 2-2, used to quantify target analytes before GC/MS analysis.
In August 1988, two important changes were made in the xenobiotics methodology. The
amount of silica gel used was doubled, and the maximum amount of lipid placed on the GPC system
was decreased from 1.0 g to 0.8 g. These changes were made to obtain better recovery of the target
analytes and to decrease interferences. The quantitative results (concentrations) obtained with the
two methods were comparable.
10
-------
ENVtflQNMENTAL SAMPLES
A) NET COLLECTION
B) SHOCK COLLECTION
ADD SURROQATE ANALYTES
WOOBENZENE
1-WDONAPTHALENE
4,4'-DKDOBPHENYL
RESCUE STORAGE
TOTAL LESS 1 GRAM
2.1flSUCAOEL
PREP FISH
A) GRND FliET Ofl
B) QRffO WHOLE
EXTRACTION
A) BLEND 2Og TISSUE
Apt) JfTERNAL STAMJARDS
B) EXTRACT WITH
HEXANE/CHjClj
SOLVENT REMOVAL
A) KUDERNA-OAMSH
APPARATUS
B) FLTERED AR
C) DETERMNE TOTAL
UPC
DurPHENANTHRENE
DU-CHRYSENE
SI 1C A fy CHRQMATQGBApHY
A) ACTIVATE 13Ot, OVERNIGHT
B) DEACTIVATE 1% ^O
C) ELUTE AMALYTES WTTH
COM. 15% WCHLOflOMETHANE/
HEXANE
SOLVENT REMOVAL
A) ADD 1rrt TOLUEJC
B) CONCENTRATE TO SOOuL
fTNAL VOLUME ADJUSTMENT
lOOuL
PEL PEPJyCATION CHROMATOQRAPY
COUECT FRACTION 1.7 TWES THE
DISTANCE FROM APEX OF DEHP
TO THE APEX OF PYRENE
QC/MS ANALYSIS
ELECTRON MPACT (OfiZATION
POSTT1VE CHEMICAL lOMZATION
NEGATIVE CHEMCAL IOMZAT10M
OUAMTLBT
= •=.
= imr
- •.— '
LBMAArCEMO
CMTO HT
- - - ~
= ~ ~
RESCUE
ill, .1,1
ill, .1,1
1,1. nli
COLLECT AND REDUCE
Figure 2-2. Schematic of laboratory analytical procedure for other xenobiotic chemicals.
-------
Samples were analyzed by GC/MS as referenced in U.S. EPA, 1990c. The positive
identification of analytes using the MS was based upon a reverse library search threshold value and
relative retention time: quantification was based on the response factors relative to one of three
internal standards. Sample analyses were done in sets of 12 consisting of:
1. One method blank,
2. One additional fortified matrix (blank) spiked with one of eight mixtures of the target
analytes,
3. One duplicate sample, and
4. Nine environmental samples.
All target xenobiotic analytes were quantified as unique values (ng/g-ppb wet weight),
except PCBs, which were reported by total congener at each degree of chlorination. Specific
detection limits were not determined for individual samples so they have been operationally set at
zero. Target quantitation limits for these analytes were:
Target Analytes (except PCBs) 2.5 ng/g
Polychlorinated Biphenyls
Level of Chlorination: 1-3 1.25 ng/g
4-6 2.50 ng/g
7-8 3.75 ng/g
9-10 6.25 ng/g
Mercury
A schematic of the equipment arrangement for mercury analyses is shown in Figure 2-3.
More specific details are provided in Olson et al., 1975; Horwitz, 1983; APHA, 1985; and Glass et
al., 1990. The analytical procedure for mercury was based on a standard flameless atomic absorption
method. Fish tissue samples were digested in a mixture of nitric acid, sulfuric acid, potassium
permanganate, and potassium persulfate as the digestion reagent. The resulting solution was treated
with a sodium chloride-hydroxylamine sulfate solution and aqueous stannous chloride. Liberated
mercury was measured using an atomic absorption spectrophotometer equipped with a cold mercury
vapor apparatus. Data for mercury are reported as microgram per gram (|ig/g)(ppm wet weight).
The detection limit for mercury was 0.05 jig/g for samples analyzed prior to 1990 and 0.0013 u.g/g
for the 195 samples analyzed in 1990. The sample size was decreased from 1.0 g to 0.2 g to obtain
results within the instrument's calibration range established at the lower detection limit.
Quality Assurance/Quality Control (QA/QC)
Specific laboratory QA procedures were established by ERL-Duluth, and are summarized
in Appendix A, Table A-l. The PCDD/PCDF QA requirements for accuracy, method efficiency,
precision, and signal quality (signal-to-noise [S/N] ratio) are shown in Appendix A, Table A-2.
Limits for recovery of standards were also set. Values that were below 40 percent recovery were
12
-------
Quartz Cell
j
Magntshun
~^"
glass wool
250 ml Flask
air pump
to Laboratory
vacuum Una
2 L Flask
(Solution of HNOa, H2SO4,
KMnO4, and
Figure 2-3. Schematic of laboratory analytical procedure for mercury.
13
-------
flagged with a QR designation in the data base. These values represent minimum concentrations
and are included with the data hut were not used in the data analyses.
Xenobiotic and mercury data QA requirements are listed in Appendix A, Table A-4 and
Appendix A, Table A-7. If more than 2Q7c of the analytes were outside the QA for accuracy and
precision, the sample set was reanalyzed. QC charts were maintained by the laboratory for each
analyte displaying quantitative bias and precision. Bias and precision were calculated at the
completion of the study and are presented in Appendix A. For QA factors outside of the above
criteria (Appendix A for xenobiotics), corrective actions were undertaken (e.g., adjust GC or MS
parameters, flush/replace GC column, clean MS, reextract and reanalyze samples). An overall data
completeness criterion of 80 percent was set for the study. As discussed in Appendix A, this criterion
was met.
General guidance for data quality including QA/QC requirements was provided in the
Work/Quality Assurance Project Plan (U.S. EPA, 1986a). As stated in this Project Plan:
"The expected quality of the data will be specified in terms of precision, bias, and detection
limits. In general, the bias requirements will be 30% (i.e., the reported values will be within 30%
of the true values) and the precision requirement will be 50% .... The detection limit for fish will
be based on consideration of levels of concern...."
The target for completeness of the data was originally set at 80 percent in the study workplan.
This target was the minimum percent of verified data as a percent of total reported data. In fact,
this target was exceeded. For the dioxin/furan analyses 96 percent of all analyses met QA/QC
criteria. Those analyses which did not are tlagged with "QR" in the database (Vol. n. Appendix
D) and were not used for any data analyses. All other data met the QA/QC criteria, i.e., the percent
of total reported data classified as valid.
Specific protocols were developed in this study for controlling data quality and ensuring
data comparability, including:
1. Standardized written sampling and analytical procedures,
2. Standardized handling and shipping procedures,
3. The use of blanks (reagent and field),
4. The use of fortified samples to control accuracy and internal standards to quantify
target analytes.
5. Specified calibration procedures to control accuracy and verify detection limits,
6. Replicate analyses to evaluate laboratory precision, and
7. Standardized data reduction and validation procedures.
14
-------
Procedures for documentation, data reduction and validation, and reporting were specified
in the Analytical Procedures and Quality Assurance Plan Manuals (U.S. EPA, 1990b, 1990c, 1989a).
SITE SELECTION
Fish collected from 388 unique sites were analyzed for this study (Figure 2-4). The types
of sites sampled included targeted sites near potential point and nonpoint sources (shown separately
in Figure 2-5), background sites (shown separately in Figure 2-6), and a subset of sites from the
USGS NASQAN (shown separately in Figure 2-7):
Number
Type of Site Sampled
Targeted Sites 314
Background Sites 35
USGS NASQAN Sites (Subset) _39_
TOTAL 388
A subset of samples that had been collected at 103 sites during the National Dioxin Study
(U.S. EPA, 1987b), and that had been analyzed for 2,3,7,8 TCDD only, were reanalyzed for the
other study dioxin/furan congeners and xenobiotic compounds. These sites have episode numbers
from 1994 to 2776. The new sites have episode numbers beginning with 3000.
Targeted sites were selected by EPA Regional and State staff based on proximity to potential
sources (Figure 2-5). Fish and other aquatic biota were sampled near industrial dischargers, urban
areas, or agricultural runoff areas. The number of sites was not allocated equally among types of
sources. Some of the targeted sites were selected based on potential chlorinated dioxin and furan
contamination, including areas near pulp and paper mills (mills that use chlorine to bleach pulp and
other types of mills), wood preservers, users of such contaminated products as polychlorinated
phenols and phenoxides, PCB dischargers, organic chemical and pesticide manufacturers, and
combustion sources (sewage sludge incinerators, municipal incinerators). Two reasons for selecting
these types of sites were:
1. The major sources of chlorinated dioxins and furans are suspected to be similar to the
sources of 2,3,7,8 TCDD investigated in the National Dioxin Study, and
2. Certain organic chemicals and pesticide compounds (primarily polychlorinated phe-
nols and polychlorinated phenoxides) had been identified as having chlorinated dioxin
or furan contamination. In addition, several PCB mixtures had been reported to
contain furan contamination.
More sites with potential dioxin/furan contamination were selected than for other compound
groups to follow up the results of the National Dioxin Study. Some targeted sites were also selected
for sampling based on the potential for hexachlorobenzene (HCB) contamination. Potential sources
of HCB include fugitive emissions from manufacturing plants, impurities in pesticides (e.g.,
pentachloronitrobenzene [PCNB], dacthal, chlorothalonil, picloram), and previous application of
HCB as a fungicide. Production facilities for certain chemicals (e.g., chlorobenzenes, carbon
tetrachloride, chlorine) are known to generate HCB as a contaminant (U.S. EPA, 1986a). The ten
largest direct dischargers (by production volume) of the chemicals of concern were recommended
15
-------
Q 0>
^cr^>
-------
>00'
HAWAII
PUERTO RICO
Figure 2-5. Location of targeted sites.
-------
a
HAWAII
PUERTO RICO
Figure 2-6. Location of sites representing background conditions.
18
-------
Figure 2-7. Location of sites selected from a subset of the USGS NASQAN Network.
PUERTO RICO
19
-------
for sampling. In addition, a site within each of the 10 U.S. counties with the highest combined
applications of the pesticides PCNB, picloram, and chiorothalonil (Resources for the Future. 1986)
were selected by the EPA Regions and targeted for sampling.
The following categories were used for targeted sites: background, paper mills using
chlorine, other types of pulp and paper mills, wood preserving plants, refineries/other industries,
Superfund sites, industry/urban, agriculture, and POTW. The two broad categories, industry/urban
and refineries/other industries, were used to accommodate the sites having multiple point sources.
Background sites, shown in Figure 2-6, were selected by EPA Regional and State staff in
areas generally free of influence from industrial releases, urban activities, or agricultural runoff.
Results from these background sites were to be compared with concentrations of pollutants found
in samples from the targeted, potentially more polluted sites.
A subset of sites were selected based upon hydrologic subdivision of major river basins,
from the USGS NASQAN sites for nationwide coverage (Figure 2-7). The sampled sites were
intended to represent a larger number of sites from the network.
20
-------
Chapter 3 - Dioxin and Furan Results and Analysis
This chapter presents the results from analysis of fillet and whole-body samples for dioxin
and furan compounds. The first section contains a summary of the prevalence and concentration
of all dioxins and furans analyzed, as well as a summary of theToxicity Equivalency Concentration
(i.e., a toxicity-weighted concentration of all dioxins and furans). Additional information presented
in this chapter consists of a geographical distribution summary and a source correlation analysis.
The latter analysis identifies point and nonpoint sources in the vicinity of the highest concentration
fish samples and compares concentrations between various site categories.
Chemical profile data for dioxins and furans can be found in Appendix C, Volume II. These
data include physical/chemical properties, sources, standards and criteria, and human health effects.
The raw concentration data, specific detection limits for dioxin/furan congeners, and location
information on the fish samples and other sampling data including sample weight, percent lipid,
number of fish per composite, and date of sample collection are included in Appendix D, Volume
II. The number of samples taken and analyzed by site can be determined by counting the samples
for a given site (episode number) in the data tables (Appendix D, Volume II). The number of fish
in each composite sample is provided in Appendix D-6 (Volume II). Other values for a given site
can be reviewed by identifying the episode number for the site from the site matrix (Table B-3,
Appendix B, in Volume I or Table D-l, Appendix D, in Volume II) and then looking at the data in
the raw data tables (Appendix D, Volume II).
PREVALENCE AND CONCENTRATION SUMMARY
Six dioxin congeners and nine furan congeners were measured in the fish tissue and shellfish
samples. Summary data regarding the prevalence and concentration of these 15 compounds can be
found on Table 3-1 and Figure 3-1. Mean concentrations were calculated using one-half of the
detection limit for tissue concentrations below detection. The total number of sites sampled and
the percent of sites where at least one sample had a detected concentration are also shown. Each of
the dioxin congeners was detected in samples ranging from 32 percent (1,2,3,4,7,8 HxCDDj to 89
percent (1,2,3,4,6,7,8 HpCDDJ of the sites (Figure 3-1). The occurrence of furans by site showed
more variability, ranging from 1 percent (1,2,3,7,8,9 HxCDF) to 89 percent (2,3,7,8 TCDF). The
dioxins and furans detected in samples from more than 50 percent of the sites included:
Compound Percent of Sites Detected
1,2,3,4,6,7,8 HpCDD 89
2,3,7,8 TCDF 89
2,3,7,8TCDD 70
1,2,3,6,7,8 HxCDD 69
2,3,4,7,8 PeCDF 64
1,2,3,4,6,7,8 HpCDF 54
1,2,3,7,8 PeCDD 54
21
-------
TABLE 3-1
Summary of Dioxins/Furans Detected in Fish Tissue
Chemical
2378 TCDF
1234678 HpCDD
2378 TCDD
123678 HxCDD
23478 PeCDF
1234678 HpCDF
12378 PeCDD
12378 PeCDF
123478 HxCQF
123789 HxCDD
123478 HxCDD
234678 HxCDF
123678 HxCDF
1234789 HpCDF
123789 HxCDF
TEC
Percent of
Sites Where
Detected
89.4
89.0
70.3
68.8
64.3
53.8
53.5
47.3
42.0
37.9
32.3
31.7
20.8
4.0
1.3
N/A
Max*
403.9
249.1
203.6
100.9
56.37
58.3
53.95
120.3
45.33
24.76
37.56
19.30
30.86
2.57"
0.96**
213.05
Mean*
13.61
10.52
689
430
306
191
2.38
1.71
2.35
1.16
1.67
1.24
r 1.74
1.24
1.22
11.08
Standard
Deviation
40.11
25.30
19.41
9.25
6.47
4.41
4.34
7.69
4.53
1 74
2.39
1,51
2.34
0.33
0.41
2377
Median*
2.97
2.83
1.38
1.32
0.75
072
093
045
1.42
0.69
1.24
0.98
1.42
1.3
1.38
2.8
Total Number
ot Sites
388
354
388
375
387
353
385
387
379
375
375
379
379
353
379
388
D
7
6
1
4
9
14
2
8
10
5
3
13
11
15
12
* Concentrations are picograms per gram (pfl/g) or parts p«r trillion (ppt) by wet weight. The mean, median, and standard deviation were calculated using one-half the detection
limit for samples which were below the detection limit. In cases where multiple samples were analyzed per site, the value used represents the highest concentration.
"Detection limits were higher than the few quantified values for 1,2,3,4,7,8,9 HpCDF and 1,2,3,7,8,9 HxCDF. Maximum values listed are measured values.
TEC » Toxidty equivalency concentration based on method of Barnes et a!., 1989.
Not*. D is designation of chemical on histogram (Figure 3-1) of the percent of sites with concentrations above detection.
22
-------
Percent of Sites with Detected Levels
OQ
§
U>
§.
I.
D.
n
8
I
**•
ED
SS-
2378 TCDF
1234678 HpCDD
2378 TCDD
123678 HxCDD
23478 PeCDF
1234678 HpCDF
12378 PeCDD
12378 PeCDF
123478 HxCDF
123789 HxCDD
123478 HxCDD
234678 HxCDF
123678 HxCDF
1?34789 HpCDF
123789 HxCDF
23
-------
The maximum levels of the four most frequently detected compounds and 1,2,3,7,8 PeCDF
were greater than 100 ppt. The highest mean and median concentrations were for 2,3,7,8 TCDF
at 13.6 and 2.97 ppt, respectively.
The lower median value reflects the lognormal type distribution as shown in the cumulative
frequency distributions for the six dioxins (Figure 3-2) and for selected furans (Figure 3-3). These
graphs were prepared using the maximum detected value at each site. When the duplicate sample
value was higher than the original sample, the duplicate value was used. In a similar manner, values
for samples from duplicate sites (i.e., resampled locations) were compared and the maximum
measured value used. The graphs show that the dioxins 2,3,7,8 TCDD and 1,2,3,4,6,7,8 HpCDD
were present at higher concentrations than the other dioxin congeners. For 2,3,7,8 TCDD, 18
percent of the sites had measured concentrations greater than 7 pg/g. A similar pattern was observed
for the furans, although the maximum concentration for 2,3.7,8 TCDF was considerably higher than
any of the other furan congeners, and this was the only furan congener with a median concentration
greater than 2 pg/g.
Toxicity Equivalency Concentration (TEC)
Toxicity equivalent concentrations (TECs) of dioxins/furans were calculated to facilitate
comparison of fish tissue contamination among sites. TEC represents a toxicity weighted total
concentration of all individual congeners using 2,3,7,8, TCDD as the reference compound. EPA's
interim method was used to determine TEC (Barnes, et. al., 1989). This is referred to as the Toxicity
Equivalency Concentration (TEC) value, sometimes called TEQ (toxicity equivalents). The TEC
method was developed under an international project and advocated by EPA. Under this method,
2,3,7,8 TCDD is used as the reference toxicity compound with all other dioxins and furans compared
to this compound through the use of a Toxicity Equivalency Factor (TEF). The factors for
determining the relative toxicities are shown in Table 3-2. Octa-dioxins and furans were not
analyzed because at the time this study began in 1986, the TEFs were zero for these congeners.
Under the 1989 interim method, the TEF was increased to 0.001. Consequently, TEC values may
be underreported for samples collected at sites with sources of octa-dioxins, e.g., wood preservers.
The largest TEF used to compute TEC is for 2,3,7,8 TCDD (a value of 1). The next largest
factor is for the 2,3,7,8 PeCDDs (i.e., penta-dioxins that have a chlorine atom in each of the 2,3,7,8
molecular positions and the fifth chlorine atom is in any of the remaining positions) and 2,3,4,7,8
PeCDF (both 0.5). The compound 2,3,7,8 TCDF has a TEF of 0.1, but because it is frequently
detected it is a significant contributor to the TEC values. The cumulative frequency distribution
of TEC values shows that these values exceeded 1 pg/g in at least one sample at 70 percent of the
sites (Figure 3-4). The proportion of the TEC contributed by 2,3,7,8 TCDD using the 1989 interim
method is over 50 percent in 50 percent of the samples (Figure 3-5a). Four compounds (2,3,7,8
TCDD; 2,3,7,8 TCDF; 1,2,3,7,8 PeCDD; and 2,3,4,7,8 PeCDF) account for a little more than 80
percent of the TEC in three-fourths of the samples (Figure 3-5b). Levels of hepta- and hexa-dioxins,
detected in a high percentage of study samples, have gained significance because the factors for
these compounds, though low relative to the tetra- and penta-dioxins, have increased from 0.001
under the U.S. EPA's 1987 method to 0.01 for the 2,3,7,8 HpCDDs under the 1989 method and
from 0.04 to 0.1 for 2,3,7,8 HxCDDs.
24
-------
2378 TCDD
f
T5tti OWCOTOI*
SOffi nmnoto
iMSim
20 40 60 BO
Percermie ol Sites
12378PeCDD
/
MS SUM
0 20 40 60 M 100
Percentiie of Site*
1 23478 HxCDD
/
x:
f 375 Sim
20 40 60 M 100
Percentiie of Sites
100
123678 HxCDD
j
SOti pxo*n«*
^
371 S*M
20 40 M SO 100
Pcrcemiie ol Site*
I
123789 HxCDD
r
jo *c eo ao
Perc«ntii« ol Site*
100
1 234678 HpCDD
20 40
tO
Perctntt* of SitM
354 MM
__ .^
Figure 3-2. Cumulative frequency diagrams of concentrations of six dioxin congeners in fish
tissue. Points display values above detection. The bars along the x axis indicate
values below detection (ND). The total number of sites is also listed on the
graph. Concentrations used are maximum values at each site.
25
-------
I
o
o
20 40 SO M
Ptrc«ntil« of Sitaa
i
12378PeCDF
Mlh p*rc*n«*
387 San
20 40 60 90 KX>
Percantile ot Sites
lOOOr
23478 PeCDF
•
90f< piremM
M to »o 100
Percenole ol Stes
100}
a I
! I
i
123478 HxCDF
379 Sun
W 40 60 M
Percentile of Sites
90ti
75»i
234678 HxCDF
40 eo to
P«rc«nM« ot SitM
100
1234678 HpCDF
sot.
SOtl
0 JO
Pwcwitil* of SitM
3431
M
Figure 3-3. Cumulative frequency diagrams of concentrations of six furan congeners in fish
tissue. Points display values above detection. The bars along the x axis indicate
values below detection (ND). The total number of sites is also listed on the
graph. Concentrations used are maximum values at each site.
26
-------
TABLE 3-2
1989 Toxicity Equivalency Factors
Compound
Mono-, Di-, and Tri-CDDs
2,3,7,8 TCDD
Other TCDDs
2,3,7,8 PeCDD
Other PeCDDs
2,3,7,8 HxCDDs
Other HxCDDS
2,3,7,8 HpCDD
Other HpCDDs
OCDD
Mono-, Di-, and Tri-CDFs
2,3,7,8 TCDF
Other TCDFs
1,2,3,7,8 PeCDF
2,3,4,7,8 PeCDF
Other PeCDFs
2,3,7,8 HxCDFs
Other HxCDFs
2,3,7,8 HpCDFs
Other HpCDFs
OCDF
TEFs/89
0
1
0
0.5
0
0.1
0
0.01
0
0.001
0
0.1
0
0.05
0.5
0
0.1
0
0.01
0
0.001
Reference: Barnes et al., 1989.
27
-------
1000?
75th percentile
50th percentite
20
40 60
Percentile of Sites
80
100
Figure 3-4. Cumulative frequency distribution of maximum calculated TEC values in fish
tissue by percentile of sites. Bar on x-axis indicates sites where concentrations
of PDCC/PCDF congeners were below detection for all samples from those sites.
28
-------
a) 100
o
in
Q
Q
O
R
-Q
O
O
0)
Q.
o
CD
"o
3
o
I
S.
40 60
Percent of Samples
80
100
Percent of Samples
Figure 3-5. Toxicity Equivalency Concentrations (TEC) based on Barnes et al., 1989 method,
a) the percent TEC contributed by 2,3,7,8, TCDD, and b) the percent of TEC
contributed by 2,3,7,8, TCDD; 2,3,7,8 TCDF: 1,2,3,7,8 PeCDD and 1,2,3,7,8,
PeCDF. (Values below the detection have been deleted from the plots.)
-------
Comparison of TCDD and Other Dioxin/Furan Compounds
A comparison by site was made to determine whether any correlations existed between
2,3,7,8 TCDD and detectable levels of the other congeners. This comparison indicated that in most
cases detected levels of other dioxin/furan isomers did not occur without detectable levels of 2,3,7,8
TCDD. The principal exception occurred for four congeners, penta-dioxins and furans and 2,3,7,8,
TCDF, in less than 15 percent of the samples. Correlation plots of 2,3,7,8 TCDD versus 2,3,7,8
TCDF in the same sample were made to see whether there was a quantitative relationship between
these congeners. No such predictive relationships were found based on linear or higher order
regressions for these or the other congeners.
GEOGRAPHICAL DISTRIBUTION
The geographical distribution of dioxin and furan levels in fish tissue from the sites sampled
is indicated on maps of the continental United States, Alaska, Hawaii, and Puerto Rico, showing
the ranges of observed concentrations by site for 2,3,7,8 TCDD, for 2,3,7,8 TCDF, and for TEC.
(Concentration ranges for these and all other maps were selected to identify locations with the higher
concentrations and for ease of presentation. The first concentration range usually represents values
up to the limit of quantification.) The maps depict the maximum values measured at a given location
among all species sampled. In most cases, this was a whole-body sample. The maximum fillet
concentration was used where no whole-body concentrations were available or where the highest
value at a site was a fillet value. The number of cases where fillet data were used as the maximum
value is shown on the maps. The specific type of sample at a particular site can be determined using
the episode number from the site matrix (Appendix B-3) and the data tables in Appendix D.
Comparison of the maps for 2,3,7,8 TCDD (Figure 3-6) and 2,3,7,8 TCDF (Figure 3-7)
shows that both are detected at many of the same sites. For example. Ship Creek in Anchorage near
a former salvage yard with PCB contamination, now a Superfund site, had a 2,3,7,8 TCDF
concentration of 3.1 pg/g, 2,3,7,8 TCDD of 0.51 pg/g, and TEC of 0.91 pg/g. However, 2,3,7,8
TCDF was detected at high concentrations at more sites. The percent of sites greater than 10 pg/g
was 13 percent for 2,3,7,8 TCDD and 23 percent for 2,3,7,8 TCDF. Comparison of the map for
2,3,7,8 TCDD and TEC shows a similar pattern, and that there are some sites where the TEC value
is greater than 1 pg/g due to the presence of additional congeners (Figure 3-8).
SOURCE CORRELATION ANALYSIS
Sources Located Near Highest Concentrations
Information on the types of point and nonpoint sources in the vicinity of each site was
obtained from the selection criteria in the original study workplan, from the sample collection forms,
and from information provided by EPA Headquarters, Regional Coordinators, and State staff
involved in collecting the samples. Using these descriptions, a site matrix was prepared showing
whether the site had been designated as a targeted site or a background site, or was one of the sites
that had been selected from the USGS NASQAN (Appendix B-3). For targeted sites, the matrix
indicates the predominant types of sources present and other available information.
30
-------
2,3,7.8 TCOO
• - > 10
A -> 1 to 10
O - Otol
13*
42
Total Sites: 388
FHtet Only Sites: 31
Maximum was Fillet: 18
'Percent of sites in category
O
Hawaii
O
Puerto Rico
:r
Figure 3-6. Map showing geographical distribution of various concentration ranges of 2,3,7,8
TCDD in fish tissue.
31
-------
o<
c
r
Alaska
2.3,7,8 TCDF (pg/fc):
• - >10 23*
A - > 1 to 10 48
O - Olo1 29
'Percent of sites in category
Total Sites: 388
Fillet Only Sites: 32
Maximum was Fillet: 30
Hawaii
Puerto Rico
Figure 3-7. Map showing geographical distribution of various concentration ranges of 2,3,7,8
TCDF in fish tissue.
32
-------
TEC (pg/g):
>50
> 1 to 50
Oto1
5'
65
30
Total Sites: 388
Fillet Only Sites: 33
Maximum was Fillet: 23
*P0rcenf of silos in category
Hawaii
O
Figure 3-8. Map showing geographical distribution of various concentration ranges of TEC
in fish tissue.
33
-------
Tetra-Dioxins/Furans
The sites with the top 10 percentile concentrations (39 out of 388) were identified for each
of the dioxin and furan congeners studied. Sites near paper and pulp mills using chlorine for
bleaching accounted for 28 out of the top 39 sites for 2,3,7,8 TCDD and 31 out of the top 39 sites
for 2,3,7,8 TCDF. For both 2,3,7,8 TCDD and 2,3.7,8 TCDF, four of the top five sites are located
near pulp and paper mills using chlorine. The fifth and highest concentration site (3078) for 2,3,7,8
TCDD is located near a Superfund site with known dioxin contamination. The fifth and highest
concentration site (3162) for 2,3,7,8 TCDF is located in a heavily industrialized area with a pulp
and paper mill and a Superfund site in the vicinity. The top five sites for both compounds are shown
below:
Cone.
(PPt)
Episode
Number
2,3,7,8 TCDD
Type of Sample
Location
203.6
160.4
143.3
104.1
98.9
3078 WB Sm Buffalo
3425 WB Carp
3346 WB Creek Chubsucker
3348 WB Blue Catfish
3340 WB Channel Catfish
Bayou Meto, Jacksonville, AR
Wham Brake, Swartz, LA
Roanoke R., Plymouth, NC
Sampit R., Georgetown, SC
Leaf R., New Augusta, MS
Cone.
pg/g(ppt)
Episode
Number
2,3,7,8 TCDF
Type of Sample
Location
403.9
320.7
273.8
261.3
207.5
3162 Hepatopancreas crab
3221 WBCarp
3395 WB Redhorse Sucker
3087 WB Carp
2721 WB Sucker
Hylebos Waterway, Tacoma, WA
Columbia R., Walla Walla, WA
Neuse R., New Bern, NC
Wham Brake, Swartz, LA
Androscoggin R., Turner Falls, ME
The above sites with the highest 2,3,7,8 TCDD concentrations also had the highest TEC
values. Other sources near the remaining top 10 percentile sites included historical PCB contamina-
tion, chemical manufacturing plants, automobile manufacturing, a refinery, and an incinerator.
34
-------
Penta-Dioxins/Furans
The sites with the highest 10 percentile concentrations for 1,2,3,7,8 PeCDD were near a
variety ot" sources. Sites near paper mills using chlorine for bleaching accounted for 13 out of the
39 sites. Sites near Superfund waste disposal areas accounted for 8 sites, 4 were former wood
preserving plants, 2 had PCB contamination, 1 had dioxin contamination, and 1 was a former dump
with an unknown mixture of chemicals. Six of the sites were located near chemical manufacturing
plants. The top 5 out of 385 sites are listed below:
1,2,3,7,8 PeCDD
Cone. Episode
pg/g (ppt) Number Type of Sample Location
53.9 3355 WB Carp Old Mormon Slough, Stockton, CA
27.2 3098 WB White Sucker Red Clay Cr., Ashland, DE
22.4 3141 WBCarp Milwaukee R., Milwaukee, WI
15.9 3162 Hepatopancreas Crab Hylebos Waterway, Tacoma, WA
14.3 2290 WB Spotted Sucker Savannah R., Augusta, GA
The highest concentration was from a site located on the San Joaquin River system near a
former wood preserving plant, now a Superfund site. This site also had the highest concentrations
of four other dioxin/furan congeners (1,2,3,4,7,8 HxCDD; 1,2,3,7,8,9 HxCDD; 1,2,3,4,6,7,8
HpCDD; and 1,2,3,4,7,8,9 HpCDF) and was one of the top five sites for three other congeners
(1,2,3,6,7,8 HxCDD; 1,2,3,6,7,8 HxCDF; and 1,2,3,4,6,7,8 HpCDF). Of the next four sites, one is
near a dump, one is near a highly industrialized area with known PCB contamination, and two are
near paper mills. High levels of other congeners were detected at these locations as well.
The top 10 percentile sites out of 387 for the PeCDFs included those near paper mills using
chlorine for bleaching (19 out of 39 for 1,2,3,7,8 PeCDF and 9 out of 34 for 2,3,4,7,8 PeCDF),
chemical/pesticide manufacturing plants, Superfund sites, and refineries (although other industries
were often present). As shown below, three of the top five sites for both of these congeners are the
same (3162, 3163, and 3085).
35
-------
1,2,3,7,8 PeCDF
Con.
pg/g(ppt)
Episode
Number
Type of Sample
Location
120.3
68.4
54.3
20.3
17.2
3162 Hepatopancreas Crab
3163 Hepatopancreas Crab
3206 Crayfish
3085 PF Back Drum
2290 WB Spotted Sucker
Hylebos Waterway, Tacoma, WA
Commencement Bay, Tacoma, WA
Willamette R., Portland, OR
Brazos R. Freeport, TX
Savannah R., Augusta, GA
Cone.
pg/g (ppt)
Episode
Number
2,3,4,7,8 PeCDF
Type of Sample
Location
56.37 3162 Hepatopancreas Crab
45.51 3085 WB Sea Catfish
42.58 3299 WB White Sucker
34.48 3163 Hepatopancreas Crab
33.25 3086 WB Catfish
Hylebos Waterway, Tacoma. WA
Brazos River, Freeport, TX
Niagara River, N. Tonawanda, NY
Commencement Bay, Tacoma, WA
Bayou D'Inde, Sulfur, LA
The two sites near Tacoma are in a heavily industrialized area with paper mills, refineries,
and other industries that have been designated as one Superfund site. This site also had the highest
concentration of 2,3,7,8 TCDF and of two hexa-furans. The Brazos River site is close to the outfall
of a pesticide manufacturing plant. The other two sites listed are also near chemical manufacturing
plants.
Hexa- and Hepta-Dioxins/Furans
The major sources near the top 10 percentile sites for the hexa- and hepta-dioxins included
wood preserving plants, paper mills, Superfund sites, and chemical manufacturing plants. Three of
the top five sites (3355, 3167, and 3185) are near wood preserving plants or former plants, one is
near multiple urban/industrial sources (3444) and the remainder are near paper mills (Table 3-3).
The major sources at the top 10 percentile sites for the hexa- and hepta-furans were similar
to the hexa-dioxins, except that HCB contamination appears to be an important potential source for
HxCDFs. Several of the sites had high levels of more than one congener. The top five sites out of
379 listed in Table 3-4 for 1,2,3,7,8,9 HxCDF were the only ones with detectable levels of this
compound. Only 14 sites out of 353 had detectable levels of 1,2,3,4,7,8,9 HpCDF. The most
common sources near the sites with detectable concentrations of HxCDFs and HpCDFs were paper
mills using chlorine for bleaching, Superfund sites, and chemical manufacturing sites.
36
-------
TABLE 3-3
Location of Maximum Measured HxCDD and HpCDD Concentrations in Fish Tissue
Compound
Maximum
Concentration Episode
pg/g Number
Type of Fish
Location
123478 HxCDD
(375 sites)*
123678 HxCDD
(375 sites)
123789 HxCDD
(375 sites)
1234678 HpCDD
(354 sites)
37.6
14.3
11.6
9.9
8.7
100.9
89.1
50.8
47.3
41.9
24.8
9.5
8.5
7.8
6.8
249.1
171.0
150.8
141.2
138.1
3355
3167
2304
3092
3444
2290
3355
3185
3377
3376
3355
3185
3167
3377
3098
3355
3377
3444
2290
3376
WBCarp
WPBluegill
WBCarp
WBCarp
WBCarp
WB Spotted Sucker
WBCarp
WB Channel Catfish
WBCarp
WBCarp
WBCarp
WB Channel Catfish
WPBluegill
WBCarp
WB White Sucker
WBCarp
WBCarp
WBCarp
WB Spotted Sucker
WBCarp
Old Mormon Slough, Stockton, CA
Medlins Pond, Morrisville, NC
Alabama R., Claibome, AL
Dugdemona R., Hodge, LA
Nonconnah Creek, Memphis, TN
Savannah R., Augusta, GA
Old Mormon Slough, Stockton, CA
Bernard Bayou, Gulfport, MS
Chattahoochee R., Franklin, GA
Chattahoochee R., Whitesburg, GA
Old Mormon Slough, Stockton, CA
Bernard Bayou, Gulfport, MS
Medlins Pond, Morrisville, NC
Chattahoochee R., Franklin, GA
Red Clay Cr., Ashland, DE
Old Mormon Slough, Stockton, CA
Chattahoochee R., Franklin, GA
Nonconnah Creek, Memphis, TN
Savannah R., Augusta. GA
Chattahochee R., Whitesburg, GA
* Number shown is total number of sites.
WB = whole-body bottom-feeding composite sample.
PF = predator fillet composite sample.
WP = whole-body predator composite sample.
37
-------
TABLE 3-4
Location of Maximum Measured HxCDF and HpCDF Concentrations in Fish Tissue
Compound
Maximum
Concentration Epiaode
Number
Type of Fish
Location
123478 HxCDF
(379 sites)*
123678 HxCDF
(379 sites)
123789 HxCDF
(377 sites)
234678 HxCDF
(379 sites)
1234678 HpCDF
(353 sites)
1234789 HpCDF
(353 sites)
45.3
37.9
34.3
30.8
20.0
30.9
16.2
14.0
13.8
13.1
0.96
0.51
0.44
0.41
0.23
19.3
11.8
9.6
8.4
7.8
58.3
29.4
25.7
25.4
16.4
2.57
1.76
1.26
0.97
0.91
3162
3297
2410
3299
3086
3162
3085
3301
3297
3355
3085
3150
3112
3107
3206
3167
3185
2290
2225
2383
3167
3185
3086
3355
3377
3355
3206
3085
3377
3376
WB
WB
WB
WB
WB
WB
WB
WB
WB
WB
WB
WB
WP
WB
WB
WB
WB
WP
WB
WB
WB
WB
WB
WB
WB
WB
Heoatopancreas Crab
Carp
Carp
White Sucker
Catfish
Hepatopancrcas Crab
Sea Cat fish
Carp
Carp
Carp
Sea Catfish
White Sucker
Carp
Carp
Crayfish
Bluegffl
Channel Catfish
Spotted Sucker
Sborthead Redborse
Carp
BluegiU
Channel Catfish
Catfish
Carp
Carp
Carp
Crayfish
Sea Catfish
Carp
Carp
Hylebos Waterway, Tacoma, WA
Niagara R., Niagara Falls, NY
Rouge R., River Rouge, MI
Niagara R., N. Tonawanda, NY
Bayou D'Inde, Sulfur, LA
Hylebos Waterway, Tacoma, WA
Brazos R., Freepott, TX
Eighteen Mile Cr., Olcott, NY
Niagara R., Niagara Falls, NY
Old Mormon Slough, Stockton, CA
Brazos R., Frecport, TX
Otter R., Baldwinville, MA
Mississippi R., Little Falls, MN
Wisconsin R., Brokaw, WI
Willamette R., Portland, OR
Medlins Pond. MorrisviUe, NC
Bernard Bayou, Gulfport, MS
Savannah R., Augusta, GA
James R., Glasgow, VA
Des Plaincs R., Lockport, IL
Medlins Pond, Morrisvilk, NC
Bernard Bayou, Gulfport, MS
Bayou D'Inde, Sulfur, LA
Old Mormon Slough, Stockton, CA
Chattahoochce R., Franklin, GA
Old Mormon Slough, Stockton, CA
Willamette R., Portland, OR
Brazos R., Freeport, TX
Ctaattaboochee R_ Franklin, GA
Chattaboochee R., Whitesburg, GA
* Number shown is total number of sites.
WB « whole-body bottom-feeding composite sample.
PF = predator fillet composite sample.
WP * whole-body predator composite sample.
-------
Concentration Comparison Between Site Categories
Description of Categories
The point and nonpoint source categories used for the dioxin/furan comparisons were
background sites (B); sites selected from the USGS NASQAN (NSQ); Superfund sites (NPL); sites
near pulp and paper mills that use chlorine for bleaching (PPC); sites near other types of pulp and
paper mills (PPNC); sites near former or existing wood preserving plants (WP); sites near industrial
or urban areas (IND/URB); sites near industrial areas that include refineries with catalytic reforming
operations (R/I); sites that could be influenced by runoff from agricultural areas (AGRI); and sites
near publicly owned treatment works (POTWs). The two broad categories, industry/urban and
refineries/other industry, resulted from a substantial number of sites having multiple point sources.
With the exception of background and NASQAN sites, categories were established based on
probable sources of various pollutants including dioxins, furans, and pesticides. Background sites
were selected to provide a comparison with areas relatively free of point and nonpoint source
pollution; however, some background sites do have other source categories present. NASQAN sites
were selected to evaluate the geographic extent and prevalence of fish contamination throughout
the country rather than to identify specific sources of this contamination.
Sites would, in general, be included in statistical tests (described below) only if a single
potential source of contamination existed at the site. The intent was to determine whether
concentrations would differ at sites with different sources. Multiple sources were excluded so as
not to infer a correlation with a given source when in fact the high contamination levels were due
to the contribution of another type of source. The number of sites per category varied for
dioxins/furans and other xenobiotics. Two categories (POTWs and agricultural areas) would not,
as data on these sites confirm, be expected to significantly impact overall dioxin/furan contamination
of fish. Accordingly, the presence of these categories would not preclude a site from being
designated as a single category site for purposes of statistical analysis for dioxins/furans. For
xenobiotics, no such "override" was included in the analysis of data.
Below is a listing of the number of sites included in each category for dioxins/furans. A
similar table is presented in Chapter 4 for xenobiotics. Category data were not available for each
site.
Number
Category Abbreviation of Sites
Background B 34
USGS NASQAN NSQ 40
Paper Mills using Chlorine PPC 78
Other Types of Pulp and Paper Mills PPNC 27
Wood Preserving Plants WP 11
Refineries/Other Industries R/I 20
NPL (Superfund Sites) NPL 7
Industry/Urban IND/URB 106
Agriculture AGRI 19
Publicly Owned Treatment Works (POTW) POTW 11
39
-------
Statistical Comparison Tests
To compare observed concentrations between site categories, box and whisker plots were
prepared for the te tra- and penta-dioxins individually and for total hexa-dioxins and total hexa-furans
and TEC values. A schematic box and whisker plot is shown in Figure 3-9. The box shows the
spread of the data between the 25th percentile and the 75th percentiie. The line inside the box
represents the median concentration. The "whiskers" or lines extend down to the 10th percentile
and up to the 90th percentile. The circles above or below the line represent the extreme upper and
lower 10 percent of the data. The maximum value of all samples at each site, including the
duplicates, was used. For dioxins/furans, values below detection have been replaced by one-half
the detection limit prior to determining the maximum value except for total HxCDDs and total
HxCDFs. For these plots the values below detection were assigned a value of zero because detection
limits were often high. The summary statistics for each category are shown beneath the plot.
Because the data sets consist of highly-skewed non-normal distributions, nonparametric
statistical methods were used to test the significance of the results. The Kruskal-Wallis test is a
one-way nonparametric analysis of variance used to determine whether concentrations from three
or more categories are from different populations or whether the observed differences could be due
to random variations of the parameters. The test is based on a comparison of ranks (order of the
observations, i.e., highest = 1, next highest = 2, etc.). The results are presented as an H statistic and
a probability (p) that the sets of samples are from the same population (null hypothesis). This value
p is then compared to a critical level. For this study a level of significance of 0.05 was used. If the
p values for a comparison of categories are less than 0.05, the two categories are considered to be
significantly different This test is analogous to the F test for parametric data, but less powerful.
The Kruskal-Wallis test is preferred over a test using only the median, because it considers the
distribution of the data as well as the median.
The Mann-Whitney U test is a nonparametric equivalent of the "t" test. The U test is also
based on ranks. This statistic was used to test for significant differences in concentrations between
two categories (e.g., background sites and agricultural sites). The U statistic is calculated and the
probability that the two sets of samples are from the same population is tabulated. A critical level
of 0.05 was used as the level of significance in this study. If the probability for a two-way
comparison was less than 0.05, the null hypothesis was rejected (i.e., the two categories being
compared are significantly different).
Site Category Comparisons
Tetra -Dioxins/Furans
Pulp and paper mills using chlorine appear to be the dominant source of 2,3,7,8 TCDD. The
paper mills using chlorine had the highest median concentration (5.66 pg/g) compared to 1.82 pg/g
for refinery/other industry sites and 1.27 pg/g for Superfund sites (Figure 3-10). Statistical com-
parisons based on the Mann-Whitney U tests (Table 3-5) showed that pulp and paper mills using
chlorine had significantly higher concentrations than other paper mills, wood preserving operations,
Superfund sites, industry/urban sites, or refineries/other industries. As would be expected, the box
40
-------
Box Plots for Column X,
300 '
w W v
280.
1 260-
§.
£ 240-
_ 220-
o
§ 200.
*
-------
I
Q
Q
O
00
r-T
co"
200
175
150
125
100
75
50
25
NSQ B PPC PPNC R/l NPL WP IND/URB POTW AGRI
Summary Table for 2,3,7,8 TCDD Box Plot
Site Category
Concentration
Range
n pg/g
Mean Stan. Dev. Median
NASQAN(NSQ) 40 0.17-4.73 1.02 1.02 0.65
Background (B) 34 0.06-2.26 0.56 0.38 0.50
Paper Mills Using Cl (PPC) 78 0.55-160.4 19.02 30.64 5.66
Other Paper Mills (PPNC) 27 0.48-7.15 2.17 2.21 1.09
Refinery/Other Industry (R/l) 20 0.50-21.55 4.38 5.88 1.82
Superfund Sites (NPL) 7 0.62-203.6 30.02 76.54 1.27
Wood Preservers (WP) 11 0.21-7.30 1.40 2.08 0.56
Industrial/Urban Sites (IND/URB) 105 0.10-56.34 4.04 8.05 1.40
POTW 8 0.18-2.24 0.90 0.76 0.63
Agricuttural (AGRI) 17 0.20-1.78 0.75 0.39 0.58
n - number of sites in category. Maximum value at each site was used. One-half the detection limit was
used for values below detection. Sites were assigned to only one category.
Figure 3-10. Box and whisker plot for 2,3,7,8 TCDD concentrations in fish tissue.
42
-------
Table 3.5
Mann-Whitney U Test Results for Dioxins Furan Comparing Selected Source Categories
Kruskal-Wallis
Mann-Whitney
Chemical
2,3,7.8-TCDD
2,3,7,8-TCDF
2,3,4,7,8-PeCDF
1,2,3,7,8-PeCDF
1,2,3,7,8-PeCDD
HxCDDs
HxCDFs
TEC
All Groups
Except NSQ
.0001
.0001
.0001
.0001
.0001
.0001
.0013
.0001
IND/URB.K/I,
NPL, PPC,
PPNC, WP
.0001
.0001
.0003
.0352
.0871
.34%
.4981
.0001
PPC, It
.
-------
plot for combined dioxins/furans based on TEC values (Figure 3-11) also shows that pulp and paper
mills using chlorine have the highest median concentration.
The highest median concentration of 2,3,7,8 TCDF was 14.0 pg/g at pulp and paper mills
using chlorine (Figure 3-12). The next highest median values were 3.6 pg/g for other pulp and paper
mill sites and 3.5 pg/g for Superfund sites. Pulp and paper mills using chlorine also had a
substantially higher mean concentration of 2,3,7,8 TCDF than any of the oiher categories, 39.2 pg/g,
compared to 7.2 pg/g for the next highest category, Superfund sites. The Mann-Whitney U tests
showed that with the exception of Superfund sites, pulp and paper mills using chlorine had
significantly higher concentrations of 2,3,7,8 TCDF than other categories. A Mann-Whitney U
comparison of pulp and paper mills using chlorine with Superfund sites results in a value that only
slightly exceeds the 0.05 critical value. The similarities between the categories are due in part to
the fact that there are only a few (i.e., 7) Superfund sites used in the analysis.
Penta-Dioxins/Furans
For 1,2,3,7,8 pentachlorodibenzodioxin (1,2,3,7,8 PeCDD), there were several significant
sources of contamination, including pulp and paper mills, Superfund sites, industry/urban sites, and
refinery/other industry sites (Figure 3-13). The highest median was for paper mills using chlorine
at 1.52 pg/g; refinery/other industry had the next highest at 1.35 pg/g followed by 1.09 pg/g for
industrial/urban. The highest concentration (27.5 pg/g) was found in the industrial/urban category
with the highest mean (3.3 pg/g) found in the refinery/other industry category. Mann-Whitney U
tests comparing pulp and paper mills using chlorine with Superfund sites, other paper mills,
refinery/other industry sites, and industry/urban sites showed no significant differences (Table 3-5).
For both 1,2,3,7,8 and 2,3,4,7,8 penta-furans, the highest median concentration was found
at Superfund sites (Figures 3-14 and 3-15). A review of the median values for other categories
indicates that there is no dominant source for either of these penta-furan congeners. This observation
is confirmed by the Kruskal-Wallis test for 1,2,3,7,8 PeCDF and by the Mann-Whitney U tests for
2,3,4,7,8 PeCDF (Table 3-5).
Hexa-Dioxins/Furans
For hexa-dioxins the highest median concentration, 3.19 pg/g, occurred at paper mills using
chlorine. Median values (Figure 3-16 ) for the next two highest source categories (refinery/other
industry and Superfund sites) were approximately the same at 1.97 and 1.94 pg/g, respectively. A
Kruskal-Wallis test (Table 3-5) for paper mills, refinery/other industry sties, industrial/urban sites,
Superfund sites, and wood preservers showed that none of the sources was significantly different
from the others with regard to fish contamination. Values below detection were set at zero for the
hexa-dioxin and hexa-furan box plots because the detection limits were often higher than the
measured concentrations.
For hexa-furans, the source category with the highest median concentration is refinery/other
industry (Figure 3-17). This category is followed by industrial/urban and Superfund sites. The
Kruskal-Wallis test (Table 3-5 ) shows that no single category is significantly different from all
others with regard to hexa-furan fish contamination.
44
-------
OJ
•
O
ULJ
225
200
175-
150
125'
100
75'
50
25'
0
o
8
NSQ
NPL WP IND/URB POTW AGRI
Summary Table for TEC Box Plot
Site Category
NASQAN (NSQ)
Background (B)
Paper Mills Using Cl (PPC)
Other Paper Mills (PPNC)
Refinery/Other lndustry(R/l)
Super-fund Sites (NPL)
Wood Preservers (WP)
Indjstrial/Urban Sites (IND/URB)
POTW
Agricultural (AGRI)
n
40
34
78
27
20
7
11
105
8
17
Concentration
Range
pg/g
ND-7.18
ND- 3.02
0.4-184.24
ND- 28.9
ND- 30.22
0.13-213.05
0.01-24.84
ND- 61 .07
0.03- 2.24
ND-4.44
Mean
1.12
0.59
25.84
5.70
8.89
33.86
4.34
7.79
0.70
1.02
Stan. Dev.
1.87
0.9
36.90
7.50
8.64
79.06
8.36
12.54
0.92
1.19
Median
0.16
0.21
10.62
2.39
6.81
4.36
0.43
3.26
0.12
0.79
ND = TEC value not determined because all values below detection. Maximum value at each site was used.
Sites were assigned to only one category.
Figure 3-11. Box and whisker plot for TEC concentrations in fish tissue.
45
-------
Q
O
00
r«."
CO
eg
350
300
250
200
150
100
50-
o
A-
o
8
o
WP IND/URB POTW AGRI
NSQ
B
PPC PPNC
PI
NPL
Summary Table for 2,3,7,8 TCDF Box Plot
Site Cateoorv
NASQAN (NSQ)
Background (B)
Paper Mills Using Cl (PPC)
Other Paper Mills (PPNC)
Refinery/Other Industry (R/l)
Superfund Sites (NPL)
Wood Preservers (WP)
Industrial/Urban Sites (IND/URB)
POTW
Agricultural (AGRI)
n
40
34
78
27
20
7
10
105
8
17
Concentration
Range
DO/CI
0.19- 16.61
0.10- 13.73
0.26 - 320.69
0.25 - 55.75
0.24 - 23.36
0.56 - 21 .23
0.18-8.84
0.24-61.58
0.24 - 2.00
0.19- 19.28
Mean
2.11
1.61
39.20
6.42
3.62
7.23
1.31
5.93
0.94
2.21
Stan. Dev.
3.66
2.51
66.18
10.72
5.16
8.62
2.54
9.49
0.72
4.52
Median
0.68
0.90
14.04
3.61
1.91
3.48
0.39
2.90
0.79
0.84
n 3 number of sites in category. Maximum value at each site was used. One-half the detection limit
was used for values below detection. Sites were assigned to only one category.
Figure 3-12. Box and whisker plot for 2,3,7,8 TCDF concentrations in fish tissue.
46
-------
30'
25
s
Q
Q
O
0>
CL
co
CM"
15
10
I
o
NSQ B
PPC PPNC R/l
NPL
WP IND/URB POTW AGRI
Summary Table for 1,2,3,7,8 PeCDD Box Plot
Site Category
NASQAN (NSQ)
Background (B)
Paper Mills Using Cl (PPC)
Other Paper Mills (PPNC)
Refinery/Other Industry (R/l)
Superfund Sites (NPL)
Wood Preservers (WP)
Industrial/Urban Sites (IND/URB)
POTW
Agricultural (AGRI)
n
39
33
78
27
20
7
11
105
8
17
Concentration
Range
pg/g
0.36-5.41
0.15-2.67
0.25-12.48
0.45-12.38
0.46-16.80
0.46-12.62
0.28-11.50
0.20-27.56
0.46-0.88
0.46-3.54
Mean
1.53
0.77
2.37
2.22
3.28
3.01
2.01
2.32
0.75
0.92
Stan. Dev.
1.24
0.54
2.72
3.19
4.17
4.34
3.51
3.93
0.18.
0.84
Median
0.90
0.54
1.52
0.68
1.35
1.00
0.52
1.09
0.84
0.62
n - number of sites in category. Maximum value at each site was used. One-half the detection limit was
used for values below detection. Sites were assigned to only one category.
Figure 3-13. Box and whisker plot for 1,2,3,7,8 PeCDD concentrations in fish tissue.
47
-------
u.
0
O
03
Q.
00
N."
m
CVJ
25-
20
15
543
NSQ
PPC PPNC
Rl
NPL
WP IND/URB POTW AGRI
Summary Table f
-------
I
fc
i
CO
NT
Tf
m
c\f
NSQ B
PPC PPNC Rl NPL WP IND/URB POTW AGRI
Summary Table for 2,3.4,7.8 PeCDF Box Plot
Site Cateoorv
NASQAN (NSQ)
Background (B)
Paper Mills Using Cl (PPC)
Other Paper Mills (PPNC)
Refinery/Other Industry (R/l)
Superfund Sites (NPL)
Wood Preservers (WP)
Industrial/Urban Sites (IND/URB)
POTW
Agricultural (AGRI)
n
40
34
78
27
20
7
10
104
8
17
Concentration
Range
DO/a
0.16-4.11
0.10- 1.39
0.25 - 20.14
0.40 • 10.21
0.42 - 33.25
0.48 - 7.53
0.42- 1.43
0.13 - 45.51
0.16-0.59
0.15- 1.02
Mean
0.78
0.50
2.92
1.71
5.44
2.93
0.63
4.09
0.42
0.53
Stan. Oev.
0.79
0.36
4.04
2.55
7.86
2.37
0.40
8.27
0.13
0.26
Median
0.46
0.42
1.37
0.59
2.32
2.73
0.42
0.98
0.44
0.42
n - number of sites in category. Maximum value at each site was used.
limit was used for values below detection.
One-half the detection
Figure 3-15. Box and whisker plot for 23,4,73 PeCDF concentrations in fish tissue.
49
-------
o>
_Q-
V)
Q
Q
O
x
I
15
o
70'
60
50-
40'
30
20
10
o
0
e
e
o
e
e
T •
=b JL.
o
o
0
t
«
0
o
o
o
a
" 0
t
NSQ
B
PPC PPNC R/l NPL WP IND/URB POTW AGRI
Summary Table for Total HxCOOs Box Plot
Site Category
NASQAN (NSQ)
Background (B)
Paper Mills Using Cl (PPC)
Other Paper Mills (PPNC)
Refinery/Other lndustry(R/l)
Superfund Sites (NPL)
Wood Preservers (WP)
Industrial/Urban Sites (IND/URB)
POTW
Agricultural (AGRI)
n
37
30
78
27
20
7
11
100
7
17
Concentration
Range
pg/g
ND -13.91
ND - 3.57
ND - 42.98
ND • 63.35
ND-35.17
ND - 9.07
ND -60.10
ND - 28.4
ND
ND -13.79
Mean
••••^••tt^H
1.73
0.39
4.68
9.23
5.54
2.96
7.04
3.60
ND
1.63
Stan. Dev.
2.94
0.80
6.66
16.77
9.75
2.99
17.90
5.49
ND
3.38
Median
0.51
ND
3.19
1.25
1.97
1.94
0.71
1.14
ND
0.44
n - number of sites in category. Maximum value at each site was used. Sites were assigned to only one
category. ND - limit of detection, here set at 0.0.
Figure 3-16. Box and whisker plot for total HxCDDs concentrations in fish tissue.
50
-------
60
50
B 40^
1
CO
u.
Q -5
O a
X
I
2
o
20
g
e
WP IND/URB POTW AGRI
Summary Table lor Total HxCDFs Box Plot
Site Category
Concentration
Range
n pg/g
Mean Stan. Dev. Median
NASQAN (NSQ) 39 NO-5.11 0.58
Background (B) 29 NO - 2.59 0.22
Paper Mills Using Cl (PPC) 78 ND -16.75 1.74
Other Paper Mills (PPNC) 27 ND-12.93 1.94
Refinery/Other lndustry(R/l) 20 ND • 22.46 3.69
Supertund Sites (NPL) 7 ND-6.08 1.22
Wood Preservers (WP) 11 ND-40.1 4.42
Industrial/Urban Sites (IND/URB) 103 ND-51.76 3.67
POTW 8 ND-0.35 0.04
Agricultural (AGRI) 17 ND-3.01 0.31
1.21
0.66
3.11
4.16
5.76
2.22
11.92
9.49
0.12
0.78
ND
ND
0.34
ND
1.05
0.41
ND
0.48
ND
ND
n = number of sites in category. Maximum value at each site was used. Sites were assigned to only one
category. ND - limit of detection, here set at 0.0.
Figure 3-17. Box and whisker plot for total HxCDFs concentrations in fish tissue.
-------
Chapter 4 - Other Xenobiotic Compound Results
and Analysis
This chapter presents results for all study compounds other than dioxins and furans. For
ease of presentation these other study compounds are referred to as "other xenobiotics" or simply
"xenobiotics." The term xenobiotic means a compound that does not naturally occur in living
organisms, in this case, fish. In addition to an overall summary, the discussion of results for
xenobiotic compounds is contained in three sections—xenobiotics detected in samples from greater
than 50 percent of the sites, between 10 and 50 percent of the sites, and less than 10 percent of the
sites. Within each of the three principal sections, information is provided, as appropriate, on high
concentration sources, geographical distribution, and source correlation analysis.
Chemical profile data and information for all of the 45 xenobiotics is presented in Appendix
C, Volume II. This information includes physical/chemical properties, standards and criteria,
chemical uses, and health effects. Concentration data for individual fish samples, as well as
information on where the samples were collected, can be found in Appendix D, Volume II. The
number of samples taken and analyzed by site can be determined by counting the samples for a
given site (episode number) in the data tables (Appendix D, Volume II). The number of fish in each
composite sample is provided in Appendix D-6 (Volume II). Other values for a given site can be
reviewed by identifying the episode number for the site from the site matrix (Table B-3, Appendix
B, in Volume I or Table D-l, Appendix D, in Volume II) and then looking at the data in the raw
data tables (Appendix D, Volume II).
PREVALENCE AND CONCENTRATION SUMMARY
A total of 45 compounds were measured in the fish tissue samples; these compounds include
34 organic compounds, PCBs with 1 to 10 substituted chlorines, and mercury. Summary data
regarding the prevalence and concentration of these compounds can be found on Table 4-1 and
Figure 4-1. Six pesticides, PCBs, three other industrial organic chemicals, and mercury were
detected at more than 50 percent of the sites. All the compounds were detected in samples from at
least one site. The compounds detected at more than 50 percent of the sites, at 10 to 50 percent of
the sites, and at less than 10 percent of the sites are as follows:
-------
TABLE 4-1
Summary of Xeaobiotic Compounds in Fish Tissue
Chemical
£'PDDE
Mercury
ToWtPCBs
Siphenyi
Nwiacfitor, Trans
CWorciarw, c«
Pentach(oro«nisote
Ofordarw. Trans
Owtdfin
Aiptw-aHC
724 rrtchiorobftrtzen*
H0xachtwoMnz«n«
Garrtma-BHC
123 TrichtofOto«nz«n«
Mirax
Nonacntor, ??o
12419?
131
477
3?a
647
3)0
450
444
2648
^3
W.^
69
225
127
243
344
125
63.2
7».S
76.65
•*5*
T4.9
t6Z
28.3
•J38
28.3
393
3?.5
f?,tf
164
76.2
5.12
155
3.24
Mean*
Standard
Qeviatkm
Median*
JUnits are ng/g )
29S.2S
260
1897.88
271
3!. £4
2«05
107T
16.68
2%A*
2.41
3.U)
5BO
2.ra
1.27
3.86
8.77
4.7S
4.t»
t. >S
2.19
0.98
0.47
598
&>2
*.«9
0.34
f.7J
0.33
1.35
0.46
a 17
0.57
0.35
003
0.09
0.02
97266
028
7S57JB
10.4
56.92
4276
[ 5206
36.74
58.37
4.53
19.41
A9.79
7.07
557
17.74
17.94
U.76
20.16
7.9
7.36
s.te
4.23
3201
0.95
11 22
2.1
9.9
209
20.68
2.96
t.42
872
4.2
035
t.l
0.22
5825
170
•joa?e
064
922
366 ~i
0.92
268
416
072
OH
ND
ND
V0
NO
So
NO j
ND
NO
WO
NO
NO
NO
HQ
NO
KO
NO
NO
NO
NO
NO
NO
ND
ND
ND
ND
Total Nurobet
of Sites
362
374
362
362
362
362
3e2
362 ^
362
362
362
362
362
362
362
362
362
362
362
362
362
362
362
3fi2
352
362
362
362
362
362
362
362
362
362
362
362
D
26
36
35
7
25
24
13
21
27
n
2
12
f4
3
34
31
22
18
9
21
33
8
10
}
29
6
20
S
32
1$
28
4
1?
30
15
16
.- D it designation of chwnical on histogram (f\gur* 4-1J
In cases wttero muftipla samples weca analy?«d fw »'», tfte vafue used f epr«se«4 th« highest concentration.
54
-------
Percent of Sites with Detected Levels
ro
01
01
o
-vl
01
o
o
FO
I
a
o
••*>
o
I
i:
o
1
a.
b«
o.
i
I
ff.
i
p,p DDE
Biphenyl
Mecury
Total PCBs
Nonachlor, trans
Pentachloroanisole
Chlordane, cis
Chlordane, trans
Dieldrin
Alpha-BHC
124 Trichlorobenzene
HCB
123 Trichlorobenzene
Gamma-BHC
Mirex
Nonachlor, cis
Oxychlordane
Chlorpyrifos
Pentachlorobenzene
Heptachlor Epoxide
Dicofol
1234 Tetrachlorobenzene
Trifluralin
'35 Trichlorobenzene
Endrin
1235 Tetrachlorobenzene
Octachlorostyrene
1245 Tetrachlorobenzene
Methoxychlor
Isopropalin
Nitrofen
Hexachlorobutadiene
Heptachlor
Perthane
PCNB
Diphenyl Disulfide
55
-------
More than 50 Percent
of the Sites
10 to 50 Percent
of the Sites
Less Than 10 Percent
of the Sites
Total PCBs
Biphenyl
Mercury
Pentachloroanisole
1,2,4 Trichlorobenzene
Pesticides:
DDE
trans-Nonachlor
cis-Chlordane
trans-Chlordane
Dieldrin
alpha-BHC1
Hexachlorobenzene
1,2,3 Trichlorobenzene
Pentachloro benzene
1,2,3,4 Telrachlorobenzene
1,3,5 Trichlorobenzene
Pesticides/Herbicides:
gamma-BHC1
Mirex
cis-Nonachlor
Oxychlordane
Chlorpyrifos
Heptachlor Epoxide
Trifluralin
Dicofol
Endrin
Octachlorostyrene
1,2,4,5 Tetrachlorobenzene
1,2,3,5 Tetrachlorobenzene
Hexachlorobutadiene
Diphenyl Disulfide
Pesticides/Herbicides:
Methoxychlor
Isopropalin
Nitrofen
Heptachlor
Perthane
Pentachloronitrobenzene
Mean fish tissue concentrations were highest for total PCBs and p,p'-DDE at 1890 and 295
ng/g, respectively (Table 4-1). These two compounds were also detected at over 90 percent of the
sampled sites. Mean concentrations of trans-nonachlor and dieldrin were the next highest at 31 and
28 ng/g, respectively. These compounds were also found at a large number of sites, 77 and 60
percent of the sampled sites, respectively. Biphenyl was detected at a large percentage of sites
(91 percent), but the levels at most sites were low. Only 12 percent of the sites had biphenyl
concentrations above the quantitation level (2.5 ng/gj.
As previously discussed in Chapter 3 for dioxins/furans, point and nonpoint sources were
divided into nine categories plus NASQAN sites for geographic coverage throughout the country.
Below is a listing of the number of sites included in each category for xenobiotics. The number of
sites for xenobiotics will be different from the number of sites for dioxins/furans for reasons
presented in Chapter 3, as well as the fact that not all xenobiotics were analyzed at all sites.
1 Alpba-BHC and gamma-BHC (or Lindane) are formally known as a-hexachlorocyclobexane and
y-bcxachJorocyclobexane, respectively. The former chemical designations are used in this document
56
-------
Number Number
Category Abbreviation of Sites
Background B 22
USGS NASQAN NSQ 40
Paper Mills using Chlorine PPC 42
Other types of Pulp and Paper Mills PPNC 17
Wood Preserving Plants WP 11
Refineries/Other Industries R/I 5
NPL (Superfund Sites) NPL 6
Industry/Urban IND/URB 35
Agriculture AGRI 19
POTW POTW 8
COMPOUNDS DETECTED AT MORE THAN 50 PERCENT OF THE SITES2
Total PCBs
Total PCBs were detected at over 91 percent of the sites sampled with the median value of
208.78 ng/g (Figure 4-2a). Twenty-six percent of the sites had fish tissue concentrations greater
than 1000 ng/g (Figure 4-2b). A major use of PCBs has been as dielectric fluids in transformers,
capacitors, and electromagnets. Prior to 1974, PCBs were also used as plasticizers, lubricants, ink
carriers, and gasket seals. PCB production in the United States stopped after 1977, and uses since
then have been limited mostly to small, totally enclosed electrical systems in restricted access areas.
PCBs can reach water bodies by runoff from PCB spills or electrical equipment fires, or runoff/seep-
age from disposal sites containing PCB-contaminated soils and equipment.
Summary statistics for the PCB congeners with 1 to 10 substituted chlorines show that the
median fish tissue concentration was highest for hexachlorobiphenyl followed by pentachloro-
biphenyl (Table 4-2). Total PCBs in this study refers to the sum of the concentrations of compounds
with 1 to 10 chlorines. Concentrations of specific Aroclor or mono-ortho substituted compounds
were not determined in this study. PCBs were detected in all parts of the country with the highest
levels detected in industrial regions. The prevalence of PCBs is consistent with their high
bioaccumulation potential and persistence in the environment. The sites with the five highest
concentrations are listed below:
Four chemicals found at less than 50 percent of the sites are presented in this section to facilitate their discussion.
These are gamma-BHC; 1,2,3 trichlorobenzene; cis-nonachlor; and oxychlordane.
57
-------
100
b)
TOTAL PCS
• . >1000 2S*
A - >6.2Sto1000 62
O - 0 to 6.25 12
•Parcart of s*aa in catagory cumulate
Total Sit**: 374
Rtot Only S*M: 28
Maximum waa Who)* Booy: 7
Figure 4-2. Total PCBs: a) cumulative frequency distribution and b) map of geographical
distribution of various concentration rmges in fish tissue.
-------
TABLE 4-2
Summary of PCBs in Fish Tissue
Chemical
Total Hexachlorobiphenyl
Total Pentachlorobiphenyt
Total Tetrachlorobiphenyl
Total Heptachlorobiphenyl
Total Trichlorobiphenyl
Total Oclachlorobiprtenyl
Total Dichlorobiphenyl
Total Monochlorobiphenyl
Total Decachtorobiphenyl
Total Nonachlorobiphenyl
Tola) PCBs
Percent of
Sites Where
Detected
88.7
86.7
72.4
69.1
57.5
34.8
30.7
13.8
3.3
9.7
91.4
Max'
8862
29578
60764
1850
18344
593
5072
235
29.5
413
Mean'
355.93
564.70
696.23
96.71
149.80
17.37
2143
1.22
0.44
3.04
1897.88
Standard
Deviation
867.13
1993.521
3647.97
209.98
1024.59
52
267.74
12.56
3.08
25
7557.8
Median*
76.85
72.4
23.09
16.85
2.09
NO
ND
NO
ND
ND
208.78
Total Number
ol Sites
362
362
362
362
362
362
362
362
362
362
362
'Concentrations are nanograms per gram (ng/g) or parts per billion (ppb) by wet weight. In cases where multiple samples were analyzed per site, the value used represents the
highest concentration.
-------
PCBs
Cone. Episode
ng/g Number Type of Fish Location
124192 3259 WB Sucker Hudson R., Fort Miller, NY
29130 2429 WB Carp Fox R., Depere Dam, WI
25240 3134 WB Sucker Manitowoc R., Chilton, WI
24118 3182 WBCarp Mud R., Russellville, KY
23809 3142 WBCarp Sheboygan R., Kohler, WI
PCB contamination from past spills occurred in the vicinity of the first two sites and the last
site. Fish samples with the next three highest PCB concentrations were collected at locations near
various industrial and other source categories. It is not apparent from available information which,
if any, of these sources can be identified as the cause of each of the next three highest PCB
concentrations. Sources in the vicinity of these samples include a metal plating shop, a rendering
plant, an incinerator, a water softening plant, a window manufacturing facility with wood treatment
operations, and agriculture croplands.
The top 10 percentile sites (36 out of 362) included three additional sites on the Fox River
and one additional site on the Hudson River. Historical PCB contamination was present at 12 of
the top 10 percentile sites including five Superfund sites. The remaining top 10 percentile sites
were located near industrial facilities including chemical and automobile manufacturing plants,
foundries, refineries, and paper mills. Two of the sites in the top 10 percentile were located near
plants with PCB discharge limits in their NPDES permits (one on the Grass River in New York and
one on the Raquette River in New York). The box plot confirms that high concentrations of PCBs
were associated with paper mills, refinery/other industry sites, Superfund sites, and industrial/urban
areas (Figure 4-3). The two highest median concentrations were 525 ng/g for Superfund sites and
349 ng/g for refinery/other industry sites. The Kruskal-Wallis test (Table 4-3) showed that no
dominant source existed.
Biphenyl
Biphenyl was detected at a large percentage of the sites (91.4 percent), but the concentrations
at most sites were low. Eighty-eight percent of the sites had concentrations below 2.5 ng/g (Figure
4-4a). Biphenyl is used in the manufacture of PCBs and is also a breakdown product of PCBs.
Biphenyl is also produced during the manufacturing of benzene and has other industrial uses as
well. The sites with the five highest concentrations are listed below:
-------
£UWJir
18CKXH
16000
14000
3>
1) 12000-
£ 10000-
(2 8000-
6000-
4000-
2000-
n.
o
0
0
e
o
• o
0
o " e
i _L • A ,
e — i — j a
NSQ
PPC PPNC Rl NPL WP IND/URB POTW AGRI
Summary Table for Total PCBs Box Plot
Site Category
NASQAN (NSQ)
Background (B)
Paper Mills Using Cl (PPC)
Other Paper Mills (PPNC)
Refinery/Other Industry (R/l)
Superfund Sites (NPL)
Wood Preservers (WP)
Industrial/Urban Sites (IND/URB)
POTW
Agricultural (AGRI)
n
39
20
39
17
5
6
10
31
6
15
Concentration
Range
DO/Q
ND • 7977
NO -480
ND - 17723
ND-6061
ND - 2974
2.51 • 1075
ND-1804
2.54- 12027
ND - 1677
ND- 1064
Mean
449.1
46.9
1247.0
1225.1
B33.5
491.0
260.6
1277.9
302.4
97.4
Stan. Dev.
1408.9
108.7
3147.5
1739.5
1230.5
390.5
561.4
2374.9
674.3
274.1
Median
24.8
ND
293.2
483.7
349.3
525.2
38.6
213.2
22.2
8.6
n = number of sites in category. ND's set at zero. Maximum concentrations at sites were used.
Figure 4-3. Box and whisker plot for total PCBs in fish tissue.
61
-------
TABLE 4.3
Results of Statistical Tests for Selected Xenobiotics and Mercury
Chemical
Pentachloobenzene
1.2,3,4-Tetrachlcxob
1,3,5-Trichlorobenzene
Total PCBs
Biphenyl
Mercury
1,2,4-Trichlorobenzene
Hexachlorobenzene
1,2,3-Trichlorobenzene
Pentachloranlsole
Kruskal-Wallis
All Groups
Except
NSQ
.7614
izene.8587
e .9600
.0001
.6338
.0222
e .0645
.0970
e .3530
.0473
AN Groups
Except
NSQ, B
.6393
.7880
.9283
.0012
.8390
.0203
.0550
.1176
.2811
.1979
NPL,
IND
.8529
.7417
.9180
.8368
.7417
.3706
.9016
.4836
.3127
.6356
Mann-Whitney
PPC,
IND
.1954
.8872
.3206
.3848
.8685
.5909
.0228
.0164
.4214
.4079
PPNC,
IND
.6821
.3214
.8886
.9914
.8716
.8297
.7876
.1996
.0511
.1036
WP,
IND
2246
.9516
.3624
.0099
.3164
.0177
.0709
.0210
.4038
.2486
B,
IND
.1995
.7723
.5243
.0001
.0842
.0489
.1590
.0167
.8094
.0613
AG,
IND
.4121
.5980
.2917
.0001
.2275
.0975
.2759
.4968
.8697
.2321
POTW,
IND
3227
7108
4583
0210
.5640
.0017
7262
0580
.2840
.7262
RI.B
.2088
.2923
.6836
.0324
.9458
.6256
.2623
.0832
.6836
.1968
Rl,
AG
.2949
.1904
.5127
.0887
.8273
.5705
.3827
.4581
.7600
.2752
R/l,
POTW
2733
.2733
.5839
2012
.6481
.0828
.7150
.1207
2733
.8551
R/l
IND
.4368
.2254
.9818
.9453
.2723
.0470
.8369
.8014
.7837
.6974
Kruskal-Wallis
Mann-Whitney
Chemical
PPC, PPNC
R/I.NPL.IND
WP,
PPC
WP,
PPNC
PPC,
PPNC
POTW,
PPC
POTW,
NPL
POTW,
R/l
Total PCBs .9058
Pentachloranisole —
Mercury —
.1181
.0350
.2256
POTW,
WP
.0158
.1093
.0828
.0562
Values shown are two-tail probabilities that groups are different. The critical level was set at 0.05. If p<0.05, the categories were considered to be significantly different.
Site Categories
INDVURB = Industry and/or Urban
NSQ =
AG = Agriculture
B x Background WP =
NPL = National Priority List (Superfund site) PPC =
POTW = Publicly Owned Treatment Works (sewage) PPNC =
R/l = Refineries using catalytic reforming process and other industry
National ambient stream quality monitoring network. (This designation is
independent of source categories )
Wood preserving related activities
Paper and pulp mills using chlorine for bleaching
Other paper and pulp mills including deinking plants
62
-------
20 40 60
Percentile of Sites
100
Biphenyl (ng/g):
• - >50 1*
A - > 2.5 to 50 11
O - 0 to 2.5 88
'Percent of sites in category
Fillet Only Sites: 28
Maximum was Fillet: 13
Figure 4-4. Biphenyl: a) cumulative frequency distribution and b) map of geographical
distribution of various concentration ranges in fish tissue.
63
-------
Biphenyl
Cone. Episode
ng/g Number Type of Sample Location
131.7 2654 WBCarp Toms River, NJ
75.6 3042 WBCarp Missouri R.,Omaha, ME
70.6 3403 WB River Carpsucker Holston R., S. Fork, Kingsport, TN
70.2 3038 WBCarp DesMoines R., Des Moines, LA
53.8 3115 PF Catfish Mississippi R., E. St. Louis
(Sauget), IL
These five sites are near chemical manufacturing plants as were 24 of the top 36 sites
representing the highest 10 percentile. The remaining sites were near Superfund sites or paper mills.
The overall geographic distribution of biphenyl concentrations and the cumulative frequency
distribution show that high concentrations (>50 ng/g) were detected mostly in the Midwest and
Northeast (Figure 4-4b).
A comparison of source categories for biphenyl (Figure 4-5) shows that Superfund sites had
the highest median concentration, 0.76 ng/g. A Kruskal-Wallis test for all categories except
NASQAN and background showed that no significant differences between categories existed (Table
4-3).
Mercury
Mercury was detected in at least one sample from 92 percent of the sites. Mercury has been
used in making batteries, lamps, thermostats, and other electrical devices and as a fungicide in latex
and exterior water-based paints. Effective August 1990, mercury was banned from interior paint.
Mercury is present in soil as a component of a number of minerals (e.g., cinnabar, HgS). It is also
discharged to the atmosphere from natural degassing processes and from the burning of fossil fuels.
Mercury compounds occur in both organic and inorganic forms. In fish tissue it is nearly all in the
organic form, methylmercury. The measured mercury concentrations were usually higher in the
fillet samples than in the whole-body samples. This is because, unlike the other organic chemicals
studied, organic mercury compounds are taken up and stored in muscle tissue rather than the lipid.
There were, however, 15 sites where the concentration in a whole-body sample was higher than that
in a fillet sample from the same site. This disparity may have been due to a number of factors,
including species variability, stomach content (which may include significant quantities of con-
taminated sediment ingested during feeding), and other variables.
The measured concentrations ranged up to 1.77 \Lglg with 2 percent of the sites greater than
1 ng/g (Figure 4-6a); most of the higher concentrations were in the Northeast (Figure 4-6b). The
highest concentration was on the Wisconsin River near Boom Bay at Rhinelander, Wisconsin. The
sites with the five highest concentrations are given below:
64
-------
40
35
30
55 25
03
Q.
co
20
15
10
75.6
t
70.6
t
NSQ
B PPC PPNC R/l NPL WP IND/URB POTW AGRI
Summary Table for Biphenyi Box Plot
Site Category
Concentration
Range
n ng/g
Mean Stan. Dev. Median
NASQAN (NSQ) 39 ND-75.6
Background (B) 20 ND-1.04
Paper Mills Using Cl (PPC) 39 ND-70.6
Other Paper Mills (PPNC) 17 ND-3.35
Refineries/Other industry (R/l) 5 ND-0.98
Superfund Sites (NPL) 6 ND-2.7
Wood Preservers (WP) 10 ND-1.5
Industrial/Urban Sites (IND/URB) 31 ND-32.8
POTW 6 0.1 -0.79
Agricultural (AGRI) 15 ND-1.11
2.51
0.42
3.18
0.87
0.44
0.97
0.60
2.56
0.55
0.48
12.04
0.30
11.36
0.87
0.40
1.09
0.60
6.38
0.24
0.31
0.49
0.38
0.54
0.61
0.43
0.76
0.45
0.68
0.63
0.53
n > number of sites in category. NO's set at 0.
Maximum concentrations at sites were used.
Figure 4-5. Box and whisker plot for biphenyl in fish tissue.
65
-------
20
40 60
Percentile of Sites
•percent of sites in category cumulative
Total Sites: 374
Fillet Only Sites: 128
Maximum was Whole Body: 15
Figure 4-6.
Mercury: a) cumulative frequency distribution and b) map of geographical
distribution of various concentration ranges in fish tissue.
66
-------
Mercury
Cone. Episode
ug/gfpprrO Number Type of Sample Location
1.77 2397 PF Walleye Wise. R/Boom Bay, Rhinelander, WI
1.66 3259 PFLmBass Hudson R., Fort Miller, NY
1.63 2027 PFLmBass Kiamichi R., Big Cedar, OK
1.40 3122 WB Carp Menominee R., Quinnesac, MI
1.13 2290 PFLmBass Savannah R., Augusta, GA
The fish sample with the highest concentration was found at a site designated as background.
The site with the third highest concentration was designated as background and agriculture.
Additional investigation at these sites is needed to determine sources of mercury contamination.
Industrial facilities located in the vicinity of the other three top five sites include pulp and paper
mills, a pesticide manufacturing plant, and a textiles facility.
Ten of the sites with the highest 10 percentile concentrations were near paper mills. Four
were near Superfund sites, and most of the remaining were from industrial areas. Sources could
not be identified at all of these sites. Five sites considered to represent background conditions and
six NASQAN sites were included in the top 10 percentile sites.
The box plot for mercury shows that the highest median concentration (0.61 |ig/g) was for
POTWs (Figure 4-7). The remaining median values had a relatively small range with the lowest
being background at 0.09 u.g/g and the highest being refinery/other industry at 0.24 Hg/g.
Pentachloranisole
Pentachloroanisole was detected in at least one sample from 65 percent of the sites with the
median concentration of the sites at 0.9 ng/g (Figure 4-8a). The majority of the higher concentration
sites (greater than 2.5 ng/g) are in the eastern part of the country (Figure 4-8b). This compound is
a metabolic breakdown product of pentachlorophenol (PCP). PCA is retained in the fish and is
therefore easier to measure. The primary uses of PCP are for treating telephone poles, fence posts,
and railroad ties. This compound is also used as an antimicrobial agent in pulp and paper
manufacturing, to control slimes in cooling towers, and to make anti-fouling paint. Prior to 1984,
it was used in the production of the pesticide sodium pentachlorophenate and as a herbicide. The
sites with the five highest concentrations out of 362 are listed below.
67
-------
.OJ
~o>
u
CD
NSQ
PPC PPNC R/l
NPL
WP IND/URB POTW AGRI
Summary Table tor Mercury Box Plot
Site Category
NASQAN (NSQ)
Background (B)
Paper Mills Using Cl (PPC)
Other Paper Mills (PPNC)
Refinery/Other Industry (R/l)
Superfund Sites (NPL)
Wood Preservers (WP)
Industrial/Urban Sites (IND/URB)
POTW
Agricultural (AGRI)
n
39
21
40
17
5
6
11
33
6
15
Concentration
Range
ND-
ND-
ND-
ND-
0.08-
ND-
0.06-
ND-
0.12
ND-
0.98
1.77
1.4
0.46
0.49
0.89
0.88
0.72
- 0.98
0.82
Mean
••^•l^HBMI^BI
0.29
0.34
0.26
0.16
0.29
0.28
0.31
0.15
0.59
0.27
Stan. Dev.
0.25
0.40
0.33
0.15
0.16
0.32
0.24
0.14
0.30
0.24
Median
0.23
0.16
0.12
0.09
0.24
0.22
0.21
0.12
0.61
0.17
n - number of sites in category. NO'S set at 0.
Maximum concentrations at sites were used.
Figure 4-7. Box and whisker plot for mercury in fish tissue.
68
-------
lOOOr-
Pentachloroanisole
WWW
Percantife of Sites
100
Pentaehloroanisole (ng/g):
• - >100 2*
A - > 2.5 to 100 34
O - 0 to 2.5 64
'Percent of sites in category
Total Sites: 362
Fillet Only Sites: 30
Maximum was Fillet: 8
Figure 4-8. Pentachloroanisole: a) cumulative frequency distribution and b) map of
geographical distribution of various concentration ranges in fish tissue.
69
-------
Pentachloroanisole
Cone. Episode
ng/g Number Type of Fish Location
647 3375 WBCarp Chattahoochee R., Austell, GA
570 3185 WB Channel Catfish Bernard Bayou, Gulfport, MS
334 3376 WBCarp Chattahoochee R., Whitesburg, GA
240 2618 WBQuillback Hamilton Canal, Hamilton, OH
187 3377 WBCarp Chattahoochee R., Franklin,GA
A wood treatment plant and Superfund site with solvents present are located near the Bernard
Bayou site. The Hamilton Canal site is near a paper mill and Superfund site. The other three top
five sites are located near paper mill operations. Eight of the top 36 sites (highest 10 percentile)
were located near Superfund sites of which four were related to wood preserving. Paper mills were
located near 17 of the top 36 sites.
The box plot for pentachloroanisole shows that the highest median concentration was 1.7
ng/g for nonchlorine paper mills (Figure 4-9). The second highest median concentration was for
sites near pulp and paper mills that use chlorine in the bleaching process (0.8 ng/g).
1.2,3 and l,2t4Trichlorobenzene
The compounds 1,2,3 trichlorobenzene and 1,2,4 trichlorobenzene (TCB) were detected in
at least one sample at 42 percent and 53 percent of the sites, respectively. The median concentra-
tions, however, were low (below detection for 1,2,3 TCB and 0.14 ng/g for 1,2,4 TCB) (Figure 4-
lOa.b). The two compounds are used in a variety of industrial applications including 1,2,4 TCB as
a solvent and dielectric fluid and 1,2,3 TCB as a coolant in electrical installations, in the production
of dyes, and in products to control termites. The sites with concentrations above 2.5 ng/g are located
for the most part near industrial organic chemical manufacturing plants. The five sites with the
highest concentrations out of 362 sites are as follows:
1,2,3 TCB
Cone. Episode
ng/g Number Type of Fish Location
69.0 2056 WBCarp Ohio R., West Point, KY
54.9 3097 PF Brown Bullhead Red Lion Cr., Tybouts Corner, DE
30.2 3164 WBCarp Haw R., Saxapahaw, NC
26.8 3376 WBCarp Chattahoochee R., Whitesburg,GA
24.8 2341 WBCarpsucker Ohio R., Markland, KY
70
-------
225
200
175-
150'
125'
c
ra
o 100-
o
n
75-
50'
25
334
I
,-L.
NSQ
O
JL
B
PPC PPNC R/l
NPL
WP IND/URB POTW AGRI
Summary Table for Pentachloroanisole Box Plot
Concentration
Range
Site Category
NASQAN (NSQ)
Background (B)
Paper Mills Using Cl (PPC)
Other Paper Mills (PPNC)
Refinery/Other Industry (R/l)
Superfund Sites (NPL)
Wood Preservers (WP)
Industrial/Urban Sites (IND/URB)
POTW
Agricultural (AGRI)
n
39
20
39
17
5
6
10
31
6
15
ng/g
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
- 46.8
- 3.33
- 85.1
- 334
- 13.2
- 2.99
- 4.47
-13
- 24.20
- 7.31
Mean
3.75
0.59
5.46
33.10
4.21
1.00
0.86
2.44
4.42
1.18
Stan. Dev.
8.48
1.14
14.32
89.53
5.97
1.39
1.46
3.88
9.72
2.34
Median
0.33
ND
0.77
1.67
0.32
0.22
ND
0.42
0.16
ND
n = number of sites in category. ND's set at 0.
Maximum concentrations at sites were used.
Figure 4-9. Box and whisker plot for pentachloroanisole in fish tissue.
71
-------
a) 123 Trichlorobenzene
1
124 Trichlorobenzene
Figure 4-10. Cumulative frequency distributions of a) 1,2,3 trichlorobenzene and b) 1,2,4
trichlorobenzene in fish tissue. (Maximum concentration at each site was used.
The bar along the x-axis indicated values below the detection.)
72
-------
1,2,4 TCB
Cone.
Episode
Number
Tvoejjl Fish
Location
264.8
191
104
103.8
80.4
2654 WB Carp
2056 WB Carp
2290 WB Spotted Sucker
3097 PF Brown Bullhead
3411 WB Redhorse Sucker
Toms R., NJ
Ohio R., West Point, KY
Savannah R., Augusta, GA
Red Lion Cr., Tybouts Corner, DE
Rochester Embayment, Rochester, NY
Two of the sites are the same for both 1,2,3, TCB and 1,2,4 TCB. Of the other eight sites
shown above, three are near Superfund sites with chlorobenzene contamination (3181,3097,2654).
Two sites are near paper mills (3376,2290), one is near a chemical manufacturing plant (3411), and
the remaining two are near agricultural/rural areas. For 1,2,4 TCB, nine of the highest 36 sites were
near Superfund sites. Chemical manufacturing facilities are near 12 of the sites and paper mills near
another six sites. Distribution of 1,2,3 TCB and 1,2,4 TCB is shown in Figures 4-11 a,b. The
highest mean concentration for 1,2,3 TCB is 2.2 ng/g from nonchlorine paper mills and for 1,2,4
TCB is 3.2 ng/g for sites in the industrial/urban category (Figures 4-12 and 4-13).
Pe sticides/Herbicides
DDE
The most frequently detected xenobiotic compound was p,p' -DDE at 98.6 percent of the
sampled sites (Figure 4-14a). DDE is a metabolic breakdown product of the widely-used pesticide
DDT. The geographic distribution of fish tissue concentrations (Figure 4-14b) shows the
widespread occurrence of DDE, which is consistent with historic pesticide use patterns of DDT (see
profile in Appendix C). The prevalence of DDE at a large number of sites, even though use of DDT
was banned in 1972, is consistent with its persistence in the aquatic environment and its high
bioaccumulation potential. The concentrations of DDE found at the top 5 out of 362 sites sampled
are listed below:
Cone.
ne/g
Episode
Number
p,p' -DDE
Type of Fish
Location
14028
8708
3221
3214
2493
3315 WBCarp
3282 WB Carp
3084 WB Channel Catfish
3212 WBCarp
3231 WBCarp
Union Canal, Lebanon, PA
Alamo R., Calipatria, CA
Arroyo Colorado, Harlingen, TX
Owyhee R., Owyhee, OR
Yakima R., Richland, WA
73
-------
1,23 TCB (ng/g):
• - >5 4*
A - 2.5 to 5 4
O - 0 to 2.5 92
'Percent of sites in category
Total Sites:
Fillet Only:
Maximum was Fillet:
362
30
32
124 TCB (ng/g):
• - >5
A - >2.5 to 5
O « 0 to 2.5
•percent of sites in category
Fillet Only: 30
Maximum was Fillet: 21
Figure 4-11. Map of geographical distribution of various concentration ranges for a) 1,2,3
trichlorobenzene and b) 1,2,4 trichlorobenzene in fish tissue.
74
-------
s
-------
30
2S
§
-------
10000r
b)
1000
I
w
P,P DDE
90th percentite
75th percenbie
SOtd percenbie
25lh percontile
10th percent) le
1 site > 10000
362 Sites
20 40 60
Percentile of Sites
so 100
DDE (ng/g):
• - >320
A - > 2.5 to 320
O - 0 to 2.5
•Percent of sites in category
Figure 4-14. p,p'-DDE: a) cumulative frequency distribution and b) map of geographical
distribution of various concentration ranges in fish tissue.
77
-------
The maximum DDE concentration was found in a whole-body carp sample from Union
Canal at Lebanon. Pennsylvania, near pesticide manufacturing plants. The other four sites are
located in agricultural areas.
Six of the highest 10 percentile sites (36 out of 362 sites) were also located in agricultural
areas without industrial activities. Five of the sites were near Superfund sites. Most of the remaining
sites were located in industrial areas. The box plot (Figure 4-15) shows that the highest median
concentration was 201 ng/g for agricultural areas. Kruskal-Wallis tests (Table 4-4) comparing
agricultural sites with Superfund and industrial/urban sites showed no significant differences with
regard to fish contamination levels.
Chlordane and Related Compounds (Nonachlor and Oxychlordane)
The next most frequently detected pesticides were chlordane and the compounds related to
chlordane. Chlordane, itself, is a chlorinated hydrocarbon that occurs in two forms—cis and trans.
The cis-isomer was detected at about 3 percent more sites than the trans-isomer (Figure 4-16 a,b,
c). Prior to 1987, this compound was widely used for termite and ant control and for agricultural
uses such as dipping nonfood roots and tops. Also, prior to 1980 it was used to control insects on
a variety of crops including corn, grapes, and strawberries. At present, it can be used only for
subsurface termite control. Related compounds are cis- and trans-nonachlor and oxychlordane.
Nonachlor is a component of chlordane (trans can be 7 to 10 percent in technical-grade chlordane
(Takamiya, 1987)) as well as an impurity of heptachlor. Trans-nonachlor was detected at 77 percent
of the sites, whereas cis-nonachlor was detected at only 35 percent of the sites (Figure 4-17 a,b, c).
Oxychlordane is a metabolic breakdown product of chlordane. Oxychlordane was detected at 27
percent of the sites (Figure 4- 16d). Nonachlor and chlordane have a high potential for bioaccumula-
tion, while oxychlordane has a lower potential. The total chlordane and total nonachlor concentra-
tions were compared for the same sample and found to be correlated based on a linear function (i~
= 0.7) but not as strongly as cis- versus trans-chlordane (r* = 0.89). Total chlordane is the sum of
the cis- and trans-chlordane isomer concentrations measured in the same sample. Total nonachlor
is the sum of the cis- and trans-nonachlor isomers. The correlations are consistent with the multiple
sources of nonachior. Comparing the geographic distribution of the two compounds (Figure
4-18a,b) shows that most of the sites with high levels of total nonachlor (greater than 100 ng/g) also
have a high level of chlordane.
The maximum concentrations at the top five sites for each of these compounds were detected
near industrial areas and Superfund sites (Table 4-5). The Monongahela River at Clairton,
Pennsylvania, an industrial area with manufacturing plants of inorganic chemicals and pesticides,
had the highest concentrations of total, cis-, and trans-chlordane and total and trans- nonachlor.
This site also had high concentrations of oxychlordane and cis-nonachlor. The highest concentra-
tions of cis-nonachlor and oxychlordane were also in industrial areas. Lake Michigan at Waukegan,
Illinois, and Peshtigo River Harbor, Peshtigo, Wisconsin, respectively. The remaining sites were
located near various industrial areas involving the production of inorganic and organic chemicals,
and pesticides. Sources for the top 10 percentile sites were predominantly industrial areas near
chemical manufacturing plants (17 out of 36). Superfund sites were near 10 of the 36 sites. All of
these sites were located in areas with nearby industrial activities. The highest median concentrations
for chlordane were near Superfund sites and industry/urban areas (Figure 4-19). For total nonachlor
78
-------
400Q
350O
3000-
250O
1
01 200O
Q
Q
q
e£ 15004
100O
500-
14028
8708
NSQ
B PPC PPNC Rl
NPL WP IND/URB POTW AGRI
Summary Table for p.p'DDE Box Plot
Site Category
NASQAN (NSQ)
Background (B)
Paper Mills Using Cl (PPC)
Other Paper Mills (PPNC)
Refinery/Other Industry (R/l)
Superfund Sites (NPL)
Wood Preservers (WP)
Industrial/Urban Sites (IND/URB)
POTW
Agricultural (AGRI)
n
39
20
39
17
5
6
10
31
6
15
Concentration
Range
PQ/q
1.09- 1223
ND-384
1 .0 - 895
0.9 - 1157
5.9 - 2329
1 .5 - 805
1.65-91.5
7.23 - 14028
2.49 - 516
13.1 • 8708
Mean
136.18
56.28
87.27
161.94
586.87
200.17
33.13
602.34
98.16
1526.89
Stan. Dev.
226.21
93.42
167.67
306.58
1000.14
300.35
32.7
2499.49
204.84
2313.13
Median
46.90
11.68
22.20
42.50
41.50
97.95
16.85
78.80
17.40
201.00
n = number of sites in category. ND's set at 0. Maximum concentrations at sites were used.
Figure 4-15. Box and whisker plot for p,p'-DDE in fish tissue.
79
-------
Table 4.4
Results of Statistical Tests for Selected Xenobiotics
(Pesticides/Herbicides)
Kruskat-Walfis
Mann-Whitney
Chemical
All Groups Ind/URB B.PPC.PPNC AG
Except NSQ NPL.AG WP.POTW IND, URB
AG.NPL
AG.B
IND, B
Total Nonachlor
TrifluraMn
Mirex
Heptachlor Epoxide
Dieldrin
Endrin
Chtorpyrifos
Alpha-BHC
IsopropaKn
Total Chlordane
p,p' DDE
Gamma BHC
Dicofol
Oxychtordane
.0071
.4822
.6451
.9599
.0891
.8983
.4019
.0905
.9951
.0047
.0001
.0417
.6233
.2994
.7565
.1363
.8643
.7704
.6856
.5777
.5426
.4388
.7358
.6774
.1074
.3614
.2085
.7081
.1946
9870
.3180
9899
.4053
.7063
.4757
.1437
9920
.2289
.5430
.0184
.8068
.9567
.5346
.0809
.6477
.6144
.5269
.6732
.6990
.3989
.4821
.6144
.0403
.2657
.0893
.4748
.5593
.1021
.6128
.8153
.4835
.5858
.4835
.2129
1.000
.3115
.1857
.6404
.2429
1.000
.0113
.0956
.4334
.8415
.3861
.8415
.5938
.1880
1.000
.0164
.0002
.1615
.2861
.6892
.0013
.8926
.7212
.7576
.0176
.8020
.2242
.0087
.4403
.0036
.0017
.0056
.4635
.1708
Values shown are two-tail probabilities that groups are different The critical level was set at 0 05 If p<0 05, the categories were considered to be significantly different
Site Categories:.
IND/URB = Industry and/or urban
AG = Agriculture
B = Background
NPL = National Priority List (Superfund site)
POTW = Publicly Owned Treatment Works (sewage)
R/l = Refines using catalytic reforming process and
other industry
NSQ = National Ambient Stream Quality monitoring network. (This designation is independent
of source categories.)
WP = Wood preserving related activities
PPC - Paper and pulp mills using chlorine for bleaching
PPNC = Other paper and pulp mills including deinking plants
80
-------
1000r
10O
OJ
3
a> Total-CHLORDANE
90tfi p»rcent>to
50th percennla
20 40 60
Percentile of Sites
3<2SilM
M 100
1000,
100
I
10
b)
cis-CHLORDANE
S0thp*«»fttl«
30 40 60
Percentile of Sites
362SHM
80 100
100Qi
100
I
trans-CHLORDANE
WMhperoentta
7
362Si«M
20 40 60 N
Percentile of Sites
too
100
2 10
I
8
Oxychlordane
9 » 40 tO » 100
P«rc*ntito of Srta»
Figure 4-16. Cumulative frequency distribution of a) total chlordane, b) cis-chlordane, c)
trans-chlordane and d) oxychlordane. (Maximum concentration at each site was
used. The bar along the x-axis indicated values below the detection.)
u
-------
10001
trans-NONACHLOR
20
40 60
Percentile of Sites
ao
100
1000
100
I
8
8
2 10
b)
cis-NONACHLOR
90th p»rc»n«l»
75tti p*rc*nll*
20 40 60 80
Percent) le of Sites
100
1000r
100
£ 10
c) Total-NONACHLOR
90»i pcnwnH*
362SJIM
20 40 60 80
Percentile of Sites
100
Figure 4-17. Cumulative frequency distribution of a) trans-nonachlor b) cis-nonachlor, and c)
total nonachlor. (Maximum concentration at each site was used. Bar at x-axis
represents sites with levels below detection.)
82
-------
Total Chlordane (ng/g):
• - >100 11*
A - > 2.5 to 100 52
O . Oto1 37
'Percent of sites in category
29
Maximum was Fillet: 15
Total Nonachlor (ng/g):
• - >100 13*
A - > 2.5 to 100 60
O - 0 to 2.5 27
'Percent of sites in category
Maximum was Fillet: 11
Figure 4-18. Map of geographical distribution of various concentration ranges for a) total
chlordane and b) total nonachlor in fish tissue.
83
-------
TABLE 4-5
Sites With Highest Concentrations Of
Chlordane Related Compounds
Maximum
Concentration Episode
Chemical ng/g Number
Total Chlordane
cis-Chlordane
trans-Chlordane
Oxychlordane
Total Nonachlor
cis-Nonachlor
trans- Nonachlor
688
384
379
376
369
378
200
1%
185
179
310
206
191
188
182
243
96.2
91.4
87.2
77
601
521
477
340.9
299
127
124
123
83.2
65.7
477
398
350
279
242
2215
3045
3435
3376
3048
2215
3048
3045
3376
2383
2215
3435
3376
3045
2190
2427
2618
2215
3117
2439
2215
3377
3117
2394
3181
3117
2215
3377
3285
2383
2215
3377
3117
2394
3181
Type of Fish
WBCarp
WBCarp
WBBigmouth Buffalo
WBCarp
WBCarp
WBCarp
WBCarp
WBCarp
WBCarp
WBCarp
WBCarp
WB Bigmouth Buffalo
WBCarp
WBCarp
WBCarp
WBCarp
WBCarp
WBCarp
PF Lake Trout
WBCarp
WBCarp
WBCarp
PF Lake Trout
WBCarp
WBCarp
PF Lake Trout
WBCarp
WBCarp
Stingray
WBCarp
WBCarp
WBCarp
PF Lake Trout
WBCarp
WBCarp
Location
Monongahela, Clairton, PA
Missouri R., Kansas City, MO
Mississippi R., Natchez, MS
Chattahoochee R., Whitesburg, GA
Mississippi R., West Alton, MO
Monongahela R., Clairton, PA
Mississippi R., West Alton, MO
Missouri R., Kansas City, MO
Chattahoochee R., Whitesburg, GA
Des Plaines R., Lockport, IL
Monongahela R., Clairton, PA
Mississippi R., Natchez, MS
Chattahoochee R., Whitesburg, GA
Missouri R., Kansas City, MO
Nishnabotna R., Hamburg, LA
Peshtigo R. Harbor, Peshtigo, WI
Hamilton Canal, Hamilton, OH
Monongahela R., Clairton, PA
Lake Michigan, Waukegan, IL
Great Miami R., New Baltimore, OH
Monongahela R., Clairton, PA
Chattahoochee R., Franklin, GA
Lake Michigan, Waukegan, IL
Great Miami R., Franklin, OH
Ohio R., West Point, KY
Lake Michigan, Waukegan, IL
Monongahcla R., Clairton, PA
Chattahoochee R., Franklin,GA
Colorado Lagoon, Long Beach, CA
DCS Moines R., Lockport, IL
Monongahela R., Clairton, PA
Chattahoochee R., Franklin, GA
Lake Michigan, Waukegan, IL
Great Miami R., Franklin, OH
Ohio R., West Point, KY
Total number of sites for each chemical was 362.
84
-------
400
350
300
'35
S 250
0)
C
| 200
O
1 150
100
50
8
o
o
o
s
i
NSQ
B
PPC PPNC Rl
NPL WP IND/URB POTW AGRI
Summary Table for Total Chlordane Box Plot
Concentration
Range
Site Category
NASQAN (NSQ)
Background (B)
Paper Mills Using Cl (PPC)
Other Paper Mills (PPNC)
Refinery/Other Industry (R/l)
Superfund Sites (NPL)
Wood Preservers (WP)
Industrial/Urban Sites (IND/URB)
POTW
Agricultural (AGRI)
n
39
20
39
17
5
6
10
31
6
15
B
ND
ND
NO
ND
ND
ND
ND
ND
ND
ND
>o/a
-251.7
-38.3
-379
-376
- 131.5
-76.60
- 14.23
-384
-4.86
- 120.4
Mean
31.80
5.20
20.54
48.73
35.45
23.25
3.0
32.80
1.42
17.20
Stan. Dev.
64.97
10.30
63.90
116.27
55.00
27.53
4.69
73.25
1.95
30.68
Median
3.66
ND
ND
4.52
11.2
13.42
0.62
11.29
0.63
7.85
n = number of sites in category. ND's set at 0. Maximum concentrations at sites were used.
Figure 4-19. Box and whisker plot for total chlordane in fish tissue.
85
-------
(Figure 4-20) the highest median concentrations were near refinery/other industry sites and
industry/urban sites. The only median concentration above the detection limit for oxychlordane
was near refinery/other industry sites (Figure 4-21). A single dominant source was not observed
for either compound based on Kruskal-Wallis tests (Table 4-4).
Dieldrin
Dieldrin, an organochlorine pesticide widely used prior to 1974, was detected at 60 percent
of the 362 sites, (Figure 4-22a). The cumulative frequency distribution shows 9 percent of the sites
with a concentration above 100 ng/g (Figure 4-22b). The top 5 out of 362 sites for dieldrin are listed
below:
Dieldrin
Cone. Episode
ng/g Number Type of Fish Location
450 3161 WB Sucker CobbsCr., Philadelphia, PA
405 3117 PF Lake Trout Lake Michigan, Waukegan, IL
323 3036 WBCarp Nishnabotna R., Hamburg, IA
312 2199 WB Bigmouth Buffalo Missouri R., Lexington, MO
260 3272 WB White Surfperch Lauritzen Canal, Richmond, CA
The first two sites are near Superfund sites in industrial areas. The next two sites are located
in agricultural areas. The fifth site is located at a former pesticide packaging plant.
The highest median for dieldrin (13.0 ng/g) was for locations near Superfund sites and the
next highest for sites near industrial/urban areas (9.9 ng/g) (Figure 4-23).
alpha/gam ma-BHC
Prior to 1977, alpha-BHC was a component of technical grade gamma-BHC, or lindane.
Lindane is an insecticide/acaricide which has been used to treat seeds, hardwood lumber, and
livestock and also to control soil pests for tobacco, fruit, and vegetable crops. The five sites with
the highest concentrations of 362 sites for alpha- and gamma-BHC are listed below.
86
-------
o>
300
250
200
03 150
O
S.
o
100
50-
521
o
O.
3-
NSQ B PPC PPNC Rl NPL WP IND/URB POTW AGRI
Summary Table for Total Nonachtor Box Plot
Site Category
NASQAN (NSQ)
Background (B)
Paper Mills Using Cl (PPC)
Other Paper Mills (PPNC)
Refinery/Other Industry (R/l)
Superfund Sites (NPL)
Wood Preservers (WP)
Industrial/Urban Sites (IND/URB)
POTW
Agricultural (AGRI)
n
39
20
39
17
5
6
10
31
6
15
Concentration
Range
Pd/q
ND- 221.3
ND - 30.4
ND - 159.3
ND - 521
ND- 166.6
ND- 132.9
ND - 22.52
ND-245
ND - 78.2
ND- 105.0
Mean
26.26
5.68
17.70
54.00
46.48
32.35
5.07
32.45
16.49
19.88
Stan. Dev.
49.28
9.84
36.10
130.03
68.47
49.92
7.15
50.08
30.77
27.75
Median
7.07
ND
2.29
6.59
28.76
14.7
2.01
11.3
2.72
7.87
n = number of sites in category. ND's set at 0. Maximum concentrations at sites were used.
Figure 4-20. Box and whisker plot for total nonachlor in fish tissue.
87
-------
I
CD
ra
•g
_o
o
>»
X
O
80
70
60
50
40
30
20
10
NSQ
e
9
f f J3
B
1
PPC PPNC R/l NPL WP IND/URB POTW AGRI
Summary Table for Oxychlordane Box Plot
Site Category
NASQAN (NSQ)
Background (B)
Paper Mills Using Cl (PPC)
Other Paper Mills (PPNC)
Refinery/Other Industry (R/l)
Superfund Sites (NPL)
Wood Preservers (WP)
Industrial/Urban Sites (IND/URB)
POTW
Agricultural (AGRI)
n
39
20
39
17
5
6
10
31
6
15
Concentration
Range
ng/g
ND - 77.0
ND- 4.64
ND- 14.4
ND - 3.48
ND- 11.7
ND- 14.3
ND
ND - 42.3
ND-17.9
ND- 6.75
Mean
4.67
0.50
0.73
0.34
3.87
2.38
ND
3.34
2.98
2.62
Stan. Dev.
14.11
1.34
2.59
0.92
4.52
5.84
ND
8.25
7.31
0.68
Median
ND
ND
ND
ND
2.62
ND
ND
ND
ND
ND
n * number ol sites in category. ND's set at 0.
Maximum concentrations at sites were used.
Figure 4-21. Box and whisker plot for oxychlordane in fish tissue.
88
-------
lOOQi
100
a) DIELDRIN
90ti p»rc«ntil*
362S4IM
20 40 60
Percentile of Sites
80 100
Dieldrin (ng/g):
• > > 100 9*
A - > 2.5 to 100 46
O - 0 to 2.5 45
'Percent of sites in category
Fillet Only: 30
Maximum was Fillet: 11
Figure 4-22. Dieldrin: a) cumulative frequency distribution and b) map of geographical
distribution of various concentrations in fish tissue.
89
-------
o>
Oj
b
350
300
250
200
150
100
a
9
*
I ' I
NSQ B
PPC PPNC
NPL
WP IND/URB POTW AGRI
Summary Table for Dieldrin Box Plot
Site Cateqory
NASQAN (NSQ)
Background (B)
Paper Mills Using Cl (PPC)
Other Paper Mills (PPNC)
Refinery/Other Industry (R/l)
Superfund Sites (NPL)
Wood Preservers (WP)
Industrial/Urban Sites (INDAJRB)
POTW
Agricultural (AGRI)
n
39
20
39
17
5
6
10
31
6
15
Concentration
Range
PO/q
ND - 323
ND- 136
ND-236
ND-41.5
ND - 64.9
ND- 260
ND • 7.73
ND- 116
ND • 38.2
ND- 188
Mean
35.46
14 .31
14.86
4.90
16.64
54.55
0.97
18.48
7.86
43.94
Stan. Dev.
71.16
35.45
41.18
9.94
27.40
101.77
2.45
29.71
15.16
69.37
Median
ND
ND
1.40
1.84
4.18
13.05
ND
9.96
0.64
ND
n a number of sites in category. ND's set at 0. Maximum concentrations at sites were used.
Figure 4-23. Box and whisker plot for dieldrin in flsh tissue.
90
-------
alpha-BHC
Cone.
ng/g
Episode
Number
Tvoe of Fish
Location
44.4
29.0
20.8
19.3
18.6
3098 WB White Sucker
2427 WB Carp
2410 WBCarp
2383 WBCarp
2056 WXCarp
Red Clay Cr., Ashland, DE
Peshtigo R. Harbor, Peshtigo, WI
Rouge R., River Rouge, MI
Des Plaines R., Lockport, 1L
Ohio R., West Point, KY
Cone.
ns/2
Episode
Number
gamma-BHC (Lindane)
Type of Fish Location
83.3
44.5
38.8
27.4
25.7
3042 WB Carp
2416 WBCarp
3098 PF American Eel
2439 WB Carp
3342 WB Spotted Sucker
Missouri R., Omaha, NE
Cuyahoga R., Cleveland, OH
Red Clay Cr., Ashland, DE
Great Miami R., New Baltimore, OH
Lumber R., Lumberton, NC
Five of these sites are near chemical manufacturing plants (2383, 2410, 2416, 3042, and
3181). Paper mills were located near three of the sites (2427, 2439, and 3342). The remaining site
is in an agricultural area where mushroom farming is done, which uses large quantities of pesticides.
Fifty-five percent of these sites were above detection for alpha-BHC, while only 42 percent
of the sites were above detection for gamma-BHC (Figure 4-24a,b). The box plots for alpha-BHC
and gamma-BHC are shown in Figures 4-25 and 4-26, respectively. A geographical distribution of
various concentration ranges of alpha- and gamma-BHC is shown in Figure 4-27a,b.
COMPOUNDS DETECTED AT BETWEEN 10 AND 50 PERCENT OF THE SITES3
Hexachlorobenzene
Hexachlorobenzene (HCB) was one of the original targeted compounds because it may
contain dioxin and is toxic itself. HCB can be produced in a number of ways: as a by-product of
chlorinated solvent manufacturing; from incineration of municipal waste; from chlorination of
wastewater; and as a breakdown product of lindane. It is also an impurity in other currently
registered pesticides, (e.g., pentachloronitrobenzene (PCNB)) and in pentachlorophenol (see profile
Five chemicals found at less than 10 percent of the sites are presented here for ease of discussion. These are
1,2,3,5 and 1,2,4,5 trichlorobenzene; methoxycblor; isopropalin; and perthane. One chemical, heptachlor epoxide,
found at 16 percent of the sites, is presented in the next section with heptachlor.
91
-------
100Qr
40 60 80 100
Percentile of Sites
1000
100
10
b) GAMMA-BHC (LINDANE)
362 S*M
20 40 SO SO
Percentile of Sites
100
Figure 4-24. Cumulative frequency distribution of a) alpha-BHC and b) gamma-BHC (lindane)
in fish tissue.
92
-------
I
o
CD
CO
d.
30
25
20
15-
10
o
«
i
o
o
NSQ
B
1
1
PPC PPNC Rl
NPL
WP IND/URB POTW AGRI
Summary Table for Alpha-BHC Box Plot
Site Category
NASQAN (NSQ)
Background (B)
Paper Mills Using Cl (PPC)
Other Paper Mills (PPNC)
Refinery/Other Industry (R/l)
Superfund Sites (NPL)
Wood Preservers (WP)
Industrial/Urban Sites (IND/URB)
POTW
Agricultural (AGRI)
n
39
20
39
17
5
6
10
31
6
15
Concentration
Range
pq/q
ND - 12.30
ND - 9.08
ND- 11.30
ND - 2.77
ND - 4.97
ND - 8.43
ND- 1.08
ND - 17.48
ND - 3.98
ND • 7.56
Mean
1.98
0.72
1.74
0.99
1.92
2.49
0.21
2.20
1.41
1.32
Stan. Oev.
2.98
2.09
2.75
0.99
2.11
3.18
0.44
4.11
1.82
2.19
Median
0.93
ND
ND
0.85
0.96
1.26
ND
0.91
0.56
ND
n = number of sites in category. ND's set at zero. Maximum concentrations at sites were used.
Figure 4-25. Box and whisker plot for alpha-BHC in fish tissue.
93
-------
30
25
O
CO
O
15-
10
83.3
1
o
o
o
T
NSQ
B
PPC PPNC R/l
NPL WP IND/URB POTW AGRI
Summary Table for Gamma-BHC Box Plot
Site Category
Concentration
Range
n ng/g
Mean Stan. Dev. Median
NASQAN(NSQ) 39 ND - 83.3 3.25
Background (B) 20 ND-2.97 0.15
Paper Mills Using Cl (PPC) 39 ND-25.7 2.66
Other Paper Mills (PPNC) 17 ND-21.9 3.33
Re»inery/Other Industry (R/l) 5 ND- 3.1 1.49
Superfund Sites (NPL) 6 ND- 7.8 1.30
Wood Preservers (WP) 10 ND- 3.3 0.57
Industrial/Urban Sites (IND/URB) 31 ND-10.5 1.99
POTW 6 ND-0.58 0.10
Agricultural (AGRI) 15 ND- 9.6 1.15
13.91
0.66
5.85
6.60
1.21
3.18
1.09
2.97
0.24
2.52
ND
ND
ND
0.63
1.41
ND
ND
0.37
ND
ND
n > number of sites in category. ND's set at 0.
Maximum concentrations at sites were used.
Figure 4-26. Box and whisker plot for gamma-BHC in fish tissue.
94
-------
Gamma-BHC
Lindana (ng/g):
• - >5
A - > 2.5 to 5
O - 0 to 2.5
'Percent of sites in category
Fillet Only Sites: 30
Maximum was Fillet: 7
A - > 2.5 to 10
O - 0 to 2.5
•Percent of sites in category
Fillet Only Sites: 30
Maximum was Fillet: 12
Figure 4-27. Map of geographical distribution of various concentration ranges for a)
gamma-BHC (lindane) and b) alpha-BHC in fish tissue.
-------
in Appendix C). The compound is not readily affected by transformation processes (e.g., hydrolysis)
and has a high potential for bioaccumulation. Given this variety of sources, it is not surprising that
the compound was found at sites located in nearly aU parts of the country (Figure 4-28a). HCB was
detected at 46 percent of the sites (Figure 4-28b). though the median concentration was below the
detection limit. Pentachlorobenzene is also an impurity in PCNB and was found in detectable
quantities at some of the same locations as discussed later in this chapter. Sites with the five highest
concentrations out of 362 sites are listed below:
Hexachlorobenzene
Cone. Episode
ng/g Number Type of Sample Location
913 3085 WB Sea Catfish Brazos R., Freeport, TX
202 3086 WB Catfish Bayou D'Inde, Sulfur, LA
93.7 2532 WB Carp Mississippi R., St. Francisville. LA
85.5 2376 WB White Sucker Quinipiac R., North Haven, CT
75 3063 WB Sea Catfish Calcasieu R., Moss Lake, LA
The first two sites are near pesticide manufacturing plants and the remaining sites are near
manufacturing plants for other types of chemicals. At the Quinipiac River site, there is also a
Superfund site known to have solvent contamination. The predominant sources for the top 10
percentile sites (36 out of 362) were pesticide/chemical manufacturing plants and Superfund sites.
Six sites originally selected because of organic chemical manufacturing plants were included in the
top 10 percentile sites. Two agricultural sites where pesticides are extensively used were included
in the top 10 percentile sites (one at Calipatria, California, and one at Gila Bend, Arizona). A
statistical comparison (Kruskal-Wallis test. Table 4-3) of all the various source categories (Figure
4-29) shows that no significant differences exist between any of the categories regarding fish
contamination levels.
Pentachlorobenzene
Pentachlorobenzene is an impurity in pentachloronitrobenzene and the sites with the highest
concentrations of pentachlorobenzene are mostly in Texas and Louisiana (Figure 4-30a). It was
detected at 22 percent of the sites (Figure 4-30b). The top five sites are listed below.
96
-------
Hexachlorobenzene (ng/g):
• - >50 1*
A - > 2.5 to 50 20
O - 0 to 2.5 79
'Percent of sites in category
Total Sites: 362
Fillet Only: 27
Maximum was Fillet: 8
I
100
10
b) Hexachlorobenzene
30 40 «o n
Parcwnto of Situ
Figure 4-28. Hexachlorobenzene: a) map of geographical distribution of various concentration
ranges and b) cumulative frequency distribution in fish tissue.
97
-------
D)
1
OJ
-------
Pentachlorobenzene (ng/g):
A - > 2.5 to 10
O - 0 to 2.5
•Percent of sites in category
Total Sites: 362
Fillet Only: 30
Maximum was Fillet: 6
•oo
i1
i
1 "
3
i
b) Pentachlorobenzene
*
/
I
KMi pram* jf
* MZliM
0 JO 40 «0 M 100
P«rc*ntilt of SilM
$• 10
1
3
1 i
c) 135 Trichlorobenzene
a
4
.
A
J
3CSiM '
t
0 20 40 » 10 '00
P«rto*ntil« of Srt •»
Figure 4-30. Pentachlorobenzene: a) map of geographical distribution of various concentration
ranges and b) cumulative frequency distribution in fish tissue, c) Cumulative
frequency distribution of 1,3,5 trichlorobenzene in fish tissue.
99
-------
Pentachlorobenzene
Cone. Episode
ng/g Number Type of Sample Location
125 3086 WB Catfish Bayou D'Inde. Sulfur, LA
51.4 3063 PF Spotted Sea Trout Calcasieu R., Moss Lake, LA
46.3 3097 WBCarp Red Lion Cr., Tybouts Corner, DE
42.6 3085 WB Sea Catfish Brazos R., Freeport, TX
9.6 2532 WB Carp Mississippi R., St. Francisville, LA
Four of these sites are near chemical manufacturing plants and the other site (3097) is a
Superfund site with HCB contamination. In the top 10 percentile of the sites, 22 of the 36 sites out
of 362 were near chemical manufacturing plants and nine were near Superfund sites of which four
had HCB contamination. The box plot (Figure 4-31) shows that none of the source categories have
median concentrations above detection.
1,3.5 Trichlorobenzene
The compound 1,3,5 trichlorobenzene (TCB) is used as a solvent for dyes and in the
manufacturing of other organic compounds. Though detected at 11 percent of the sites, the
compound 1,3,5 trichlorobenzene was detected above the quantitation limit at only three sites
(Figure 4-30c). These sites are listed below:
1,3,5 TCB
Cone. Episode
ng/g Number Type of Sample Location
14.9 3403 WB River Carpsucker So. Fork of Holston R., Kingsport, TN
9.2 2290 WB Spotted Sucker Savannah River, Augusta, GA
2.77 2056 WBCarp Ohio River, West Point, KY
Sites 3403 and 2290 are near paper mills. The latter site also has other industrial/urban
sources nearby. Site 2056 is near a Superfund site known to be contaminated with PCBs, dioxins,
furans, and solvents. The median concentration of all source categories was below detection (Figure
4-32).
Tetrachlorobenzenes
Cumulative frequency distributions of the tetrachlorobenzenes (TECB) show that these
compounds were detected at less than 15 percent of the sites (Figure 4-33a,b,c). The tetrachloroben-
zenes are moderately to highly volatile and, as a result, may be higher than reported because the
analytical procedures for this study included an evaporation step. The chemical 1,2,4,5
tetrachlorobenzene is used in the manufacturing of 2,4,5 T (2,4,5 trichlorophenoxyacetic acid), a
100
-------
OJ
tu
N
c
_O
c
-------
CT
I
¥
0)
N
I
O
o
in
CO
14-
12-
10
NSQ
B
J
PPC PPNC R/l
NPL
WP IND/URB POTW AGRI
Summary Table tor 1,3,5-Trichtorobenzene Box Plot
Site Category
NASQAN (NSQ)
Background (B)
Paper Mills Using Cl (PPC)
Other Paper Mills (PPNC)
Refineries (RFNY)
Supertund Sites (NPL)
Wood Preservers (WP)
Industrial/Urban Sites (IND/URB)
POTW
Agricultural (AGRI)
n
39
20
39
17
5
6
10
31
6
15
Concentration
Range
ng/g
ND - 0.06
ND - 0.24
ND- 14.9
ND - 2.35
ND - 0.54
ND - 0.55
ND
ND- 1.20
ND
ND
Mean
0.002
0.02
0.40
0.16
0.11
0.09
ND
0.13
ND
ND
Stan. Dev.
0.01
0.06
2.38
0.57
0.24
0.22
ND
0.32
ND
ND
Median
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
n a number of sites in category. ND's set at 0.
Maximum concentrations at sites were used.
Figure 4-32. Box and whisker plot for 1,3,5 trichlorobenzene in fish tissue.
102
-------
1000
100
g 101
a) 1234-TETRACHLOROBENZENE
362 Sites
*
/
»
20 40 60
Percemile of Sites
80 100
1000r
100
to
§
10
b) 1235-TETRACHLOROBENZENE
362SMM
20
60 SO
100
Percentile of Sites
1000i
100
S 10j
c) 1245-TETRACHLOROBENZENE
M2SMM
20 40 60
Percentile of Sites
80 100
Figure 4-33. Cumulative frequency distribution of a) 1,2,3,4 tetrachlorobenzene, b) 1,2,3,5
tetrachlorobenzene and c) 1,2,4,5 tetrachlorobenzene in fish tissue.
103
-------
primary component of the defoliant Agent Orange used in Vietnam. It has also been used as a
precursor for the manufacture of other organic chemicals and in the dye industry. The 1,2,3,4 isomer
is a component of dielectric fluids, and was the most commonly detected of the three isomers (13
percent of the sites versus 9.4 percent for 1,2,3.5 TECB and 9.1 percent for 1,2,4,5 TECB). Median
concentrations were below detection for all three of these compounds. Geographic distributions of
TECB concentrations are shown in Figure 4-34a,b,c.
The sites with the top five concentrations out of 362 were the same for 1,2,3,5 and 1,2,4,5
TECB as follows:
Cone.
ng/g
Episode
Number Type of Sample
1,2,3,5 and 1,2,4,5 TECB
Location
28.3 3097 PF Brown Bullhead
15.3 2056 WBCarp
12.9 2341 WBCarpsucker
12.0 2290 WB Spotted Sucker
10.7 3086 PF Red Drum
Red Lion Creek, Tybouts Corner, DE
Ohio River, West Point, KY
Ohio River, Markland, KY
Savannah River, Augusta, GA
Bayou D'Inde, Sulfur, LA
The first two sampling locations are near Superfund sites, and the others are near chemical
plants (2341 and 3086) and paper mills (2290).
The top five sites for 1,2,3,4 TECB are shown below. The first three are the same as
described above for 1,2,3,5 and 1,2,4,5 TECB. Site 3096 is located near a refinery, industrial
chemical facilities, and a POTW. Site 3094 is near chemical manufacturing plants and a POTW.
Median values from all source categories were below detection (Figure 4-35).
Cone.
ng/g
1,2,3,4 TECB
Episode
Number
Type of Sample
Location
76.65
11.50
11.3
10.6
10.4
3097
2056
2341
3096
3094
PF Brown Bullhead
WBCarp
WB Carpsucker
WB Channel Catfish
BF Channel Catfish
Red Lion Creek, Tybouts Comer, DE
Ohio River, West Point, KY
Ohio River, Markland, KY
Delaware River, Eddystone, PA
Delaware River, Torresdale, PA
104
-------
a)
1234TECB(ng/g):
• - >5 2-
A. « 2.5 to 5 1
O « 0 to 2.5 97
Total Sites: 362
Fillet Only: 30
Maximum was Fillet: 9
'Percent of sites in category
b)
1235TECB(ng/g):
• = >5 2'
A -2.5 to 5 1
O » 0 to 2.5 97
Total Sites:
Fillet Only:
Maximum was Fillet:
•Percent of sites in category
C)
1245TECB(ng/g):
• « >5 2'
A « 2.5 to 5 1
O « 0 to 2.5 97
362
30
3
Total Sites: 362
Fillet Only. 30
Maximum was Fillet: 2
•Percent of sites in category
Figure 4-34. Map of geographical distribution of various concentration ranges for a) 1,2,3,4
tetrachlorobenzene, b) 1,2,3,5 tetrachlorobenzene, and c) 1,2,4,5
tetrachlorobenzene in fish tissue.
105
-------
Q)
N
0)
.a
o
CO
CJ
22.5-
20
17.5'
15'
12.5
10
7.5
T
2.5
NSQ
8
PPC PPNC R/l
NPL
WP IND/URB POTW AGRI
Summary Table for 1,2,3,4-Tetrachlorobenzene Box Plot
Site Category
Concentration
Range
n ng/g
Mean Stan. Dev. Median
NASQAN(NSQ) 39 ND ND
Background (B) 20 ND - 0.25 0.03
Paper Mills Using Cl(PPC) 39 ND-0.88 0.03
Other Paper Mills (PPNC) 17 ND-0.11 0.02
Refinery/Other Industry (R/l) 5 ND-5.21 1.74
Supertund Sites (NPL) 6 NO-20.92 3.49
Wood Preservers (WP) 10 ND-1.01 0.10
Industrial/Urban Sites (IND/URB) 31 ND - 0.76 0.04
POTW 6 ND ND
Agricultural (AGRI) 15 ND ND
ND
0.08
0.14
0.03
2.46
8.54
0.32
0.14
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
n • number of sites in category. ND's set at 0.
Maximum concentrations at sites were used.
Figure 4-35. Box and whisker plot for 1,2,3,4 tetrachlorobenzene in fish tissue.
106
-------
Pesticides/Herbicides
Mirex, Chlorpyrifos, Dicofol, Methoxychlor, and Perthane
Mirex was used primarily to control fire ants in the Southeast between 1962 and 1975 (NAS,
1978). Mirex has also been used on pineapple mealy bugs in Hawaii and as a fire retardant in plastics
and other products. Mirex was detected at 38 percent of the sites primarily in the Southeast and the
Great Lakes region (Figure 4-36a). The chemical was produced at plants located along the Niagara
River, and it occurred at high levels in this area as shown below:
Mirex
Cone. Episode
ng/g Number Type of Sample Location
225 2328 PF Chinook Salmon Lake Ontario, Olcott, NY
137 3305 WB Channel Catfish Racquette R., Massena, NY
131 2329 PF Brown Trout Lake Ontario, Rochester, NY
85.4 3412 WBCarp Oswego Harbor, Oswego, NY
73.7 3301 WBCarp Eighteen Mile Cr., Olcott, NY
The box and whisker plot (Figure 4-37) shows that the highest concentration was found in
the industrial/urban category. The only median value above detection was for sites in the
refinery/other industry category.
Chlorpyrifos, an organophosphate insecticide, was originally developed in the 1960's to
replace organochlorine pesticides such as DDT. It is used on cotton, peanuts, sorghum, and a variety
of fruits and vegetables, as well as for control of termites and household pests. For Chlorpyrifos,
over 70 percent of fish concentrations at all sites were below detection (Figure 4-36b). The
geographic distribution map shows that the few sites with relatively high concentrations (above 50
ng/g) are scattered throughout the East and Midwest and in California (Figure 4-38). The highest
concentrations were observed at sites near agricultural facilities. The top 5 out of 362 sites are listed
below:
707
-------
a .<
a)
Mirex
o 20 40 n «o 100
P«c«ntil« of Situ
1000)
100
10
b)
75*
CHLORPYRIFOS
362SIIW
20 40 «0
Percentile of Sites
ao 100
Figure 4-36. Cumulative frequency distribution of a) mirex and b) chlorpyrifos in fish tissue.
108
-------
X
o
100y
90
80
70
60
50
40
30
20
10'
0
9
O
w
41
NSQ B
PPC PPNC R/l
NPL
J.
1
WP INDAJRB POTW AGRI
Summaty Table for Mirex Box Plot
Site Category
NASQAN (NSQ)
Background (B)
Paper Mills Using Cl (PPC)
Other Paper Mills (PPNC)
Refineries/Other Industry (R/l)
Superfund Sites (NPL)
Wood Preservers (WP)
Industrial/Urban Sites (IND/URB)
POTW
Agricultural (AGRI)
n
39
20
39
17
5
6
10
31
6
15
Concentration
Range
ng/g
ND-23.1
ND-11.3
ND-21.6
ND-35.5
ND-2.0
ND-0.8
ND-0.5
ND-85.4
ND-2.6
ND-10.4
Mean
1.6
0.7
1.6
4.9
0.8
0.2
0.1
3.9
0.6
1.3
Stan. Dev.
5.0
2.5
4.0
9.6
0.9
0.3
0.2
15.6
1.1
3.0
Median
ND
ND
ND
ND
0.7
ND
ND
ND
ND
ND
n = number ot sites in category. ND's set at 0. Maximum concentrations at each site were used.
Figure 4-37. Box and whisker plot for mirex in fish tissue.
109
-------
*P«re»nt of sfttt in category
Total Sites: 362
Fillet Only: 30
Maximum was Fillet: 8
Figure 4-38. Map of geographical distribution of various concentration ranges for chlorpyrifos
in fish tissue.
-------
Chlorpyrifos
Cone.
ng/g
Episode
Number
Tvoe of Sample
Location
344 3282 WB Carp
645 3375 WB Carp
63.7 3071 WB Carp
62.7 3141 PF Northern Pike
61.7 3283 WB Carp
Alamo R., Calipatna, CA
Chattahoochee R, Austell, GA
San Antonio R., Elmendorf, TX
Milwaukee R., Milwaukee, WI
New R., Westmoreland, CA
Three of the sites are located in agricultural areas, while the remaining sites (3071 and 3141)
are located in urban areas with a variety of nearby industrial sources. The box and whisker plot
also shows that the highest mean concentration was for sites in the agricultural category (Figure
4-39).
Dicofol, methoxychlor, and perthane are pesticides similar in structure to DDT, but less
persistent Dicofol and methoxychlor are active ingredients of currently registered pesticides.
These three pesticides were detected at less than 16 percent of the sites versus 99 percent of the sites
for DDE, the metabolic breakdown product of DDT ( Figure 4-40a,b,c). Dicofol is primarily used
to control mites on cotton and citrus crops. Other crops to which it has been applied include apples,
pears, apricots, cherries, and vegetables. It is also used on turf and shade trees. Methoxychlor, also
similar to DDT, has not been widely used since 1982. Prior to that time, it had been applied to a
wide variety of fruit, vegetable, and forage crops and had been used to control mosquitos and flies
in homes and businesses Methoxychlor has a lower bioaccumulation factor than dicofol and was
detected at fewer sites (7 percent versus 155 percent). Dicofol and methoxychlor concentrations
were greater than the quantification limit of 2.5 ng/g in samples from 7 and 5 percent of the sites,
respectively (see Figure 4-41a,b) Most of the sites appear to be in agricultural areas where citrus
and other fruits and vegetables are grown. The box plot for dicofol is shown in Figure 4-42. The
highest mean concentration of all the categories was for sites near agricultural areas (27 ng/g).
The highest five concentrations of dicofol and methoxychlor are listed below:
Dicofol
Cone.
ne/e
Episode
Number
Tvoe of Samnle
Location
74.3 3355 WB Carp
36 0 3252 WB Sucker
21.1 3198 WB Sucker
18.4 3208 WB Sucker
14.9 3117 PF Lake Trout
Old Mormon Slough, Stockton, CA
Boise River, Parma, ED
South Platte River, Denver, CO
Malheur River, Ontario, OR
Lake Michigan, Waukegan, EL
-------
60-
344
t
50-
O)
O)
V)
o
40
Q.
£
JC
O
30'
20
10'
NSQ
o
o
B
v
I
PPC PPNC R/l
NPL
-4=—Ur-l ,
WP IND/URB POTW AGRI
Summary Table for Chlorpyrifos Box Plot
Site Category
NASQAN (NSQ)
Background (B)
Paper Mills Using Cl (PPC)
Other Paper Mills (PPNC)
Refineries/Other Industry (R/l)
Superfund Sites (NPL)
Wood Preservers (WP)
Industrial/Urban Sites (IND/URB)
POTW
Agricultural (AGRI)
n
39
20
39
17
5
6
10
31
6
15
Concentration
Range
ng/g
ND-40.8
ND-5.13
ND-22.6
ND-45.6
ND-19.4
ND
ND-2.51
ND-61.7
ND
ND-344
Mean
2.34
0.40
1.15
4.71
4.40
ND
0.25
3.89
ND
24.46
Stan. Dev.
7.43
1.29
5.02
11.98
8.43
ND
0.79
11.50
ND
88.56
Median
ND
ND
ND
ND
0.48
ND
ND
ND
ND
ND
n = number of sites in category. ND's set at 0.
Maximum value at each site was used.
Figure 4-39. Box and whisker plot for chlorpyrifos in fish tissue.
112
-------
1000,
100
a) DICOFOL (KELTHANE)
90th percanoie
r
*
362 SUM
20 40 60
Percentile of Sites
so 100
100Q
100
I
I 10
1
b) METHOXYCHLOR
t
A
f
4
362SitM *
1000
100
f 10
3
i
c) PERTHANE
A
*
362SilM
0 20
40 60
Percentile of Sites
80 100
20 40 60 80
Percentile of Sites
100
Figure 4-40. Cumulative frequency distribution of a) dicofol (kelthane), b) methoxychlor, and
c) perthane in fish tissue.
in
-------
A - > 2.5 to 10
O - 0 to 2.5
'Percent of sites in category
Fillet Only:
Maximum was Fillet:
Methoxychlor (ng/g):
• - >20
A - > 2.5 to 20
O - Oto2.5
1
4
95
'Percent of sites in category
Fillet Only:
Maximum was Fillet:
Figure 4-41. Map of geographical distribution of various concentration ranges for a) dicofol
and b) methoxychlor in fish tissue.
114
-------
I
o
o
18-
16
14.
12.
10
8
6
4
p.
t
o
—
o
• 0
e
• °
1 • T
1
o
o
NSQ
B
PPC PPNC R/l NPL WP IND/URB POTW AGRI
Summary Table for Dicofol Box Plot
Site Category
NASQAN (NSQ)
Background (B)
Paper Mills Using Cl (PPC)
Other Paper Mills (PPNC)
Refineries/Other Industry (R/l)
Superfund Sites (NPL)
Wood Preservers (WP)
Industrial/Urban Sites (IND/URB)
POTW
Agricultural (AGRI)
n
39
20
39
17
5
6
10
31
6
15
Concentration
Range
ng/g
ND-5.37
ND-2.29
ND-4.53
ND-2.44
ND-3.69
ND
NO
ND-0.50
ND-4.09
ND-18.40
Mean
0.54
0.27
0.14
0.28
1.02
ND
ND
0.02
0.68
2.66
Stan. Dev.
1.44
0.70
0.74
0.65
1.61
ND
ND
0.09
1.67
5.41
Median
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
n = number of sites in category. ND's set at 0.
Maximum concentrations at sites were used.
Figure 4-42. Box and whisker plot for dicofol in fish tissue.
115
-------
Methoxychlor
Cone.
H2/2
Episode
Number
Tvne of Samole
Location
393.
17.9
8.22
8.15
7.71
3195
3375
2056
3172
3144
WB Chub
WBCarp
WBCarp
WBCarp
WBCarp
Jordan River, Salt Lake City, UT
Chattahoochee River, Austell, GA
Ohio River, West Point, KY
Coosa River, AL/GA State Line
Fox River, Portage, WI
The two highest concentrations (3355 and 3195) were found near Superfimd sites. The
Stockton, California, site is also influenced by agricultural runoff. Two additional locations were
near Superfund sources which could be identified as the cause for the high concentrations.
Agricultural areas and pesticide manufacturing plants were also near sites in the top 10 percentile.
Perthane was detected above the quantitation limit in only one sample—a whole body catfish
from the Delaware River at Torresdale, Pennsylvania (3094) where this compound was manufac-
tured. Prior to 1980, perthane was used as an insecticide on fruit and vegetable crops and to protect
woolens against moths and beetles.
Trifluralin and Isopropalin
Trifluralin and isopropalin, both currently registered dinitroaniline herbicides, were found
above the quantitation limit at 11 and 3 percent of the sites, respectively (Figure 4-43a,b). The
largest quantities of trifluralin are used primarily on soybeans, cotton, peanuts, wheat, and barley.
The States with the highest uses are Arkansas, Illinois, Iowa, Minnesota, Missouri, North Dakota,
South Carolina, Tennessee, and Texas (Resources for the Future, 1986). With a few exceptions,
the sites with the highest concentrations were located in these States. Three of the sites on the
Missouri River in Nebraska and Kansas were located near pesticide manufacturing plants (Figure
4-44a,b). Trifluralin has a low leaching potential from soils due to its strong capacity for sorption.
Isopropalin is less persistent in the aquatic environment due to its greater volatility. Isopropalin
was also used on fewer crops, primarily tobacco, peppers, and tomatoes, and therefore would be
expected to be less prevalent. At present, the only currently registered use is for tobacco. Box plots
for trifluralin and isopropalin show that all median values for the categories were below detection
(Figures 4-45 and 4-46, respectively).
Endrin
Endrin is an organochlorine pesticide and a contaminant of dieldrin. Endrin was detected
in at least one sample from 10.5 percent of the sites (Figure 4-47a). Endrin is less persistent in the
environment than dieldrin and has a lower bioconcentration factor. Endrin was used on tobacco
crops prior to cancellation of this use in 1964. Until 1979 it was used mostly to control bollworms
on cotton in the Southeast. Other past uses included controlling termites, mice, and rodents, and
treatment for a variety of grains and other crops. In 1984, all registered uses of endrin were
116
-------
100Qi
100
!
TRIFLURALIN
90* p*fc*nbl«
361 SiM*
20 40 60
Percentile of Sites
80 100
1000i
100
ISOPROPALIN
362 Si to*
20 40 60 80
Percentile of Sites
100
Figure 4-43. Cumulative frequency distribution of a) trifluralin and b) isopropalin in fish tissue.
777
-------
Trifluralin(ng/g):
• . >100 2*
A - > 2.5 to 100 9
O - 0 to 2.5 89
•percent of sites in category
Fillet Only:
Maximum was Fillet:
29
teopropafrn (ng/g):
• • >10 2"
A - > 2.5 to 10 1
O « 0 to 2.5 97
'Parctm of srt»» in category
F«tatOnly:
Maximum was Fillet:
30
0
Figure 4-44. Map of geographical distribution of various concentration ranges for a) trifluralin
and b) isopropalui in fish tissue.
1J8
-------
c
1
•'c
180
160
140
120
100
80'
60
40-
20
ff\J
458
t
o
s
I
o
o
f
1
<
I
& o
e
_ •
e
e
•
NSQ B PPC PPNC R/l NPL WP IND/URB POTW AGRI
Summary Table for Trifluralin Box Plot
Site Category
NASQAN (NSQ)
Background (B)
Paper Mills Using Cl (PPC)
Other Paper Mills (PPNC)
Refineries (RFNY)
Superfund Sites (NPL)
Wood Preservers (WP)
Industrial/Urban Sites (IND/URB)
POTW
Agricultural (AGRI)
n
39
20
39
17
5
6
10
31
6
15
Concentration
Range
ng/g
ND-458
ND-163
ND-23.1
ND-3.4
ND - 2.9
NO
NO
ND-82.8
NO
ND-153
Mean
20.92
10.80
0.59
0.20
0.58
ND
ND
6.37
NO
23.35
Stan. Dev.
77.01
37.73
3.70
0.82
1.30
ND
ND
18.83
ND
46.52
Median
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
n - number of sites in category. ND's set at 0.
Maximum concentrations at sites were used.
Figure 4-45. Box and whisker plot for trifluralin in fish tissue.
119
-------
35'
30'
O)
25
ra
CL
20
10
1
NSQ B PPC PPNC R/l NPL WP IND/URB POTW AGRI
Summary Table for Isopropalin Box Plot
Site Category
NASQAN (NSQ)
Background (B)
Paper Mills Using Cl (PPC)
Other Paper Mills (PPNC)
Refinery/Other lndustry(R/l)
Superiund Sites (NPL)
Wood Preservers (WP)
Industrial/Urban Sites (IND/URB)
POTW
Agricultural (AGRI)
n
39
20
39
17
5
6
10
31
6
15
Concentration
Range
ng/g
ND-25.9
NO
NO
NO
NO
NO
ND-10.2
ND-37.5
NO
NO
Mean
1.27
ND
ND
ND
ND
ND
1.02
1.83
ND
ND
Stan. Dev.
4.89
ND
ND
ND
ND
ND
3.23
6.98
ND
ND
Median
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
n - number of sites in category. ND's set at 0.
Maximum concentrations at sites were used.
720
Figure 4-46. Box and whisker plot for isopropalin in fish tissue.
-------
1000,
100
03
•g 10
a)
ENDRIN
90(1 p*rc*nbl*
362 SiH*
20 40 60
Percentile of Sites
ao
f
/
100
Endrin (ng/g):
• - >50
A - >2.5 to 50
O - 0 to 2.5
'Percent of sites in category
Fillet Only:
Maximum was Fillet:
30
1
Figure 4-47. Endrin: a) cumulative frequency distribution and b) map of geographical
distribution of various concentration ranges in fish tissue.
121
-------
voluntarily canceled. The geographic distribution of sites is shown in Figure 4-47b. The box plot
(Figure 4-48) shows that median concentrations for all source categories were below detection.
COMPOUNDS DETECTED AT LESS THAN 10 PERCENT OF THE SITES4
Octachlorostyrene
Octachlorostyrene is not intentionally produced. It can be formed as a by-product of the
electrolytic production of chlorine using graphite anodes and coal tar pitch and the electrolytic
production of magnesium. The sites where it occurred at levels above quantification {2.5 ng/g) are
located in areas where industrial organic chemicals are manufactured. It was detected at only
9 percent of the sites (Figure 4-49a).
Hexachlorobutadiene
Hexachlorobutadiene is a by-product of the carbon disulfide process for the manufacture of
the solvent carbon tetrachloride. It was detected in at least one sample from three percent of the
sites (Figure 4-49b). Concentrations were above 2.5 ng/g at only four sites. The top five sites (all
of which are near organic chemical manufacturing plants) are listed below:
Hexachlorobutadiene
Cone. Episode
ng/g Number Type of Sample Location
164.00 3063 WB Sea Catfish Calcasieu R., Moss Lake, LA
23.00 3085 WB Sea Catfish Brazos R., Freeport, TX
10.50 3115 PF Catfish Mississippi R., E. St. Louis (Sauget), IL
2.54 3065 WB Flathead Catfish Mississippi R., Baton Rouge, LA
2.37 3086 WB Catfish Bayou D'Inde, Sulfur, LA
Diphenyl Disulfide
Diphenyl disulfide was detected at only two sites (Figure 4-49c). This compound is used in
small amounts in the pharmaceutical industry, in the vulcanizing of rubber, and as a flavoring agent.
Some chemicals found at less than 10 percent were presented elsewhere for ease of discussion. See footnotes 2,
page 57, and 3, page 91.
122
-------
100i
90'
162
t
I
T3
LU
70'
60-
50-
40-
30-
20
10
0
o
I
NSQ
LJ.
B PPC
o
o
PPC PPNC R/l
NPL
WP IND/URB POTW AGRI
Summary Table for Endrin Box Plot
Site Category
Concentration
Range
n ng/g
Mean Stan. Dev. Median
NASQAN (NSQ) 39 ND-7.5
Background (B) 20 ND-26.5
Paper Mills Using Cl (PPC) 39 ND-162
aher Paper Mills (PPNC) 17 NO
Refinery/Other lndustry(R/l) 5 ND
Superfund Sites (NPL) 6 ND-16.2
Wood Preservers (WP) 10 ND
Industrial/Urban Sites (IND/URB) 31 ND-7.37
POTW 6 ND
Agricultural (AGRI) 15 ND-45.4
0.53
2.00
5.22
ND
ND
3.64
ND
0.32
ND
4.23
1.65
6.50
25.90
ND
ND
6.55
ND
1.38
ND
12.30
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
n = number of sites in category. ND's set at 0.
Maximum concentrations at sites were used.
Figure 4-48. Box and whisker plot for endrin in fish tissue.
123
-------
a j
Octachlorostyrene
363 S4M
20 «o ao ao
Pcrcantila of Silas
100
I
To
Hexachlorobutadiene
20
P*rc«ntil« of Sites
5 ,
c) Diphenyl Oisulfide
JO « «0 10 '00
Ptrontito of Sitat
I "
Nitrofen
3(2 Sta
100
Parcantila of SitM
Figure 4-49. Cumulative frequency distribution of a) octachlorostyrene,
b) hexachlorobutadiene, c) diphenyl disulfide, and d) nitrofen in fish tissue.
124
-------
Pesticides/Herbicides
Nitrofen
Nitrofen is a selective herbicide that has not been used in the United States since 1984. Prior
to that time it was used to control weeds in vegetables including sugar beets, rice, and on cereal
grains. It can biodegrade and undergo photolysis so this chemical is less persistent than a compound
such as DDT, and was detected at only 2.8 percent of the sites (Figure 4-49d). This compound was
above the quantitation limit at the following sites:
Nitrofen
Cone. Episode
ng/g Number Type of Sample Location
17.9 3354 WBCarp New Mormon Slough, Stockton, CA
12.8 3300 WB White Sucker Niagara River Delta, Porter, NY
10.4 2654 WBCarp Toms River, NJ
10.6 3302 WB White Sucker Niagara River, Lewiston, NY
3.95 3288 PFSquawfish Blanco Drain, Salinas, CA
The site with the highest concentration is located near a Superfund site, as is the Toms River,
New Jersey, site. The Stockton, California, site is also influenced by agricultural runoff. The
Niagara River sites are near chemical manufacturing facilities and agricultural areas. The Blanco
Drain is located in an agricultural irrigated area where pesticides are used extensively.
Heptachlor and Heptachlor Epoxide
Heptachlor is an insecticide that has been used to control fire ants in southern States and soil
insects on com. Its uses were limited in 1983 to subsurface termite control and dipping of nonfood
roots and tops. Massachusetts, Minnesota, and New York allow no uses. It is also a contaminant
of chlordane, which is widely used for termite control, especially in urban areas. Heptachlor is
moderately volatile and can also be transformed by other environmental processes including
hydrolysis and photolysis. It is metabolically converted to heptachlor epoxide, which bioaccumu-
lates to a greater extent than heptachlor and is less affected by transformation processes. Heptachlor
epoxide was detected in samples from more sites and, in general, at higher concentrations than
heptachlor (Figure 4-50a,b). Thirteen percent of the sites had maximum concentrations over
2.5 ng/g for heptachlor epoxide, but only 3 percent for heptachlor. Heptachlor epoxide was found
at higher concentrations in the Midwest, particularly in the Mississippi River system (Figure 4-51).
The box plot for heptachlor epoxide shows that median concentrations for all categories were below
detection (Figure 4-52).
725
-------
1000r
100
I
HEPTACHLOR
362 Site*
20 40 60 BO
Percentile of Sites
100
lOOOl
100
~ 10
b) HEPTACHLOR EPOXIDE
90th peroentil*
362 Sites
20 40 60
Percentile of Sites
BO 100
Figure 4-50. Cumulative frequency distribution of a) heptachlor and b) heptachlor epoxide in
fish tissue. (Maximum concentration at each site was used. Bar on x-axis
represents sites below detection.)
126
-------
Heptachlor (ng/g):
• . >25 1*
A - > 2.5 to 25 2
O - 0 to 2.5 97
'Percent of sites in category
Total Sites:
Fillet Only.
Maximum was Fillet:
\
362 \ ^
30 XJ
0
Heptachlor EpoxkJe (ng/g):
• . >25 3*
A - > 2.5 to 25 10
O - 0 to 2.5 87
'Percent ot sites in category
Maximum was Fillet:
Figure 4-51. Map of geographical distribution of various concentration ranges for a) heptachlor
and b) heptachlor epoxide in fish tissue.
127
-------
70i
I
-------
Pentachloronitrobenzene
Pentachloronitrobenzene (PCNB) is used as a soil fungicide, a seed dressing agent for
peanuts, to control stem and root rot on flowers and vegetables, and to minimize mold growth on
cotton and turf. PCNB was detected at four sites (Figure 4-53a,b). The highest concentration of
PCNB was found in a whole-body carp sample from the Missouri River at St. Joseph (3044) located
near an agricultural chemical manufacturing plant, and the next highest was a whole-body carp
sample from the Scioto River at Chillicothe, Ohio (3132) near pesticide and inorganic chemical
manufacturing plants and a Superfund site.
COMPARISON WITH NATIONAL CONTAMINANT BIOMONITORING PROGRAM
The National Contaminant Biomonitoring Program (NCBP), formerly part of the National
Pesticide Monitoring Program, is an ongoing study begun in 1964 to determine how organochlorine
pollutant levels vary over geographic regions and change over time. Fish have been monitored
since 1967 and the latest analyses were performed in 1984 for 19 organochlorine compounds and
7 metals (cadmium, lead, mercury, arsenic, copper, selenium, and zinc). Fifteen of the or-
ganochlorine compounds and mercury were also analyzed in the NSCRF.
The 1984 NCBP sampled 112 sites for organic chemicals and 109 sites for metals. The
monitoring sites were selected to represent watersheds, and included all of the major river basins in
the continental United States. Only 11 sites were common to both the NCBP and NSCRF studies.
Composite samples consisted of five fish and were collected at each site for three fish species-two
bottom feeder species and one predator species.
A total of 15 organic compounds and mercury were measured in both studies. In the NSCRF,
11 compounds were found at greater than 50 percent of the sites. Eight of these compounds were
analyzed in the NCBP: p.p'-DDE, PCBs, dieldrin, cis- and trans-chlordane, pentachloroanisole,
trans-nonachlor and alpha-BHC. All of these compounds, except alpha-BHC, were found at greater
than 50 percent of the sites in the NCBP. Several other pesticides were found at higher concentra-
tions in the NCBP including dieldrin, endrin, gamma-BHC, and chlordane-related compounds. This
is consistent with the larger proportion of sites near agricultural areas in the NCBP. Additionally,
the percent occurrence forp,p'-DDE and PCBs in both studies is very close. The percent occurrences
for DDE were 99 in the NSCRF and 98 in the NCBP, and 91 for PCBs in both studies. Mercury
was similar, found in samples from 92 percent of the sites in the NSCRF and 100 percent of the
sites in the NCBP. These results highlight the ubiquitous extent of these three compounds.
129
-------
f
2
a
a) Pentachloronitrobenzene
Pentachloronitrobenzene (ng/g):
• =>2.5 0.5*
O = 0 to 2.5 99.5
362
Fillet Only: 30
Maximum was Fillet: 0
'Percent of sites in category
Figure 4-53. Pentachloronitrobenzene: a) cumulative frequency distribution and b) map of
geographical distribution of various concentration ranges in fish tissue.
130
-------
Chapter 5 - Fish Species Summary and Analysis
This chapter provides biological information on the various fish species sampled as well as
a summary of average fish tissue concentration data by type of fish species. At most of the sampled
sites, few, if any, different types of species were collected. As a consequence, only limited
bioaccumulation or other comparions can be made between fish species for a given sampling site.
Nevertheless, the tables showing the concentration of chemicals by fish species may provide a good
basis for follow-up studies or as a supplement to other fish contamination studies. Additionally,
the information on fish feeding strategies may prove useful in developing future source correlation
studies.
SUMMARY OF FISH SPECIES SAMPLED
Though protocols were established to minimize fish sample variables among sites, over 119
different species representing 33 taxonomic families of fish were collected for this study. Fresh-
water, estuarine, and marine samples were included. Table 5-1 lists the species by scientific and
common name and shows the number of sites at which they were sampled. This table also shows
feeding strategy and indicates whether the fish is found in a freshwater and/or marine environment.
Sampling locations were shown earlier in Figure 2-4. Tissue concentrations have been measured
in catadromous species (e.g., American eel, Anguilla rostrata): anadromous species (e.g., salmon,
Onchorhynchus): and freshwater, estuarine, and marine species, in addition to exotic introduced
species such as Tilapia. In addition, 17 samples of shellfish were collected, which are described at
the end of this section.
The 14 most frequently sampled species were as follows:
Bottom Feeder Species Number of Sites Where Sampled
Carp 135
White Sucker 32
Channel Catfish 30
Redhorse Sucker 16
Spotted Sucker 10
Game Species Number of Sites Where Sampled
Largemouth Bass 83
Smallmouth Bass 26
Walleye 22
Brown Trout 10
White Bass 10
Northern Pike 8
Flathead Catfish 8
White Crappie 7
Bluefish 5
131
-------
TABLE 5-1
Distribution and Feeding Strategy for Fish Spedes Collected
Scientific Name
Common Name
Range
i
Feeding
Strategy2
No. of
Sites3
Class - Chondrichthyes
Order - Squalifonnes
Family - Carcbarbinidae
Talri
Order - Rajifonnes
Family - Rajidae
Raa
Family - Dasyatidae
Dasvatis (species unknown)
Order - Chimaehformes
Family - Chimaeridae
Hvdrolagus cnlliei
Class • Osteicfatbyes
Order - Acipenseriformes
Family - Acipensendae
Acinenser tfan.
-------
TABLE 5-1 (CONT.)
Scientific Name
Order - Osteoglossitbnnes
Family - Hiodonudae
Hiodon alosoides
Order - Salmoniformes
Family - Salmomdae
Coregonus clupeaformis
Oncorfavnchus gorbuscha
Oncorhvncfaus kisutch
Oncorfavnchus mvkiss
OncQrhvnchii<; tshawvtscba
Prosopium wj|]iarns,9nj
.Salmn rlarlci
Salmn salaf
.Salmn rni|ta
Salvelinus fontmalis
Salvelinus malma
Salvelinus namavcush
Family - Osmeridae
Hypomesus pretiosus
Family - Esocidae
Esox lucius
Hsox niger
Esox spp.
Order - Cypriniformes
Family - Cyprinidae
Acrocheilus ahitacens
f arassius auratus
Ctenopharyngodon idella
Cypnnus carpio
Gila spp.
Orthodon microlepidotus
Ptvchocbeilus
Family - Catostomidae
Carpiodes carpio
Carpiodes cvprinus
Catmtnmns carnstnmns
Catnstnmns columhianns
Catnstnmiis commersoni
Catostntnus macrncheilus
Catostomus occide.ntalis
Common Name
Goldeye
Lake Whitefish
Pink Salmon
Coho Salmon
Rainbow Trout
Chinook Salmon
Mountain Whitefish
Cutthroat Trout
Atlantic Salmon
Brown Trout
Brook Trout
Dolly Varden
Lake Trout
Surf Smelt
Northern Pike
Chain Pickerel
Pickerel; Pike
Chiselmouth
Goldfish
Grass Carp
Common Carp
Chub
Sacramento Blacklist)
Squawfish
River Carpsucker
Quillback
Longnose Sucker
Bridgelip Sucker
White Sucker
Largescale Sucker
Sacramento Sucker
Sucker (unspecified)
Range l
F
Both
Both
Both
Both
Both
F
Both
Both
Bothfl]
Both
Both
F
Both
F
F
F
F
F[T]
F[T]
F[I]
F
F
F
F
F
F
F
F
F
F
-
Feeding
Strategy "
P
P
P
P (Pise.)
P (Fish. Insects. Algae)
P(Pisc.)
P (Aq. Insects)
P
P (Pise.)
PfPisc.)
P
P
P(Pisc.)
B
PCPisc.)
P
P
B
B
B
B (Omni.)
B
B
B (Pise.)
B
B
B
B
B (Omni.)
B
B
-
No. of
Sites3
1
7
2
10
2
2
1
1
8
4
1
1
1
1
135
1
1
9
4
1
2
3
32
2
3
32
' Estuarioe/Muine: M = Mahoe: F 3 Freshwater; [1] = Introduced
2 P = Predator: B = Bottom Feeder
Number of sites where fish were collected and analyzed
SOURCE: AFS. 1980
Puc. = Piscivorous: Omni. = Omnivorous
133
-------
TABLE 5-1 (CONT.)
Scientific Name
F.rimv7nn nblongus
Frimv7nn sucetta
Hypentehum nigricans
[ctiobus huhalus
Ictiobus cvpnneilus
Ictiobus niger
Vf invtrema rf|filat10p.]S
Moxostoma anisurum
Moxostoma congestum
Moxostoma duquesnei
Moxostoma ervthnmim
Moxostoma marml^piflntnm
\foxostoma rtner;||n]-||rn
Moxostoma
Order - Silunformes
Family - Ictaluridae
T^alnms ram*
Ictalurus furcatus
Ictalurus melas
\f taliir^ pyalis
Ictalurus nehulosns
ItitfllimiS nimctatm
Pylodictis nlivam
Common Name
Creek Chubsucker
Lake Chubsucker
Northern Hog Sucker
Smailmouth Buffalo
Bigmouth Buffalo
Black Buffalo
Spotted Sucker
Silver Redhorse
Gray Redhorse
Black Redhorse
Golden Redhorse
S nonhead Redhorse
Black tail Redhorse
Redhorse Sucker
White Catfish
Blue Catfish
Black Bullhead
Yellow Bullhead
Brown Bullhead
Channel Catfish
Flatnead Catfish
Catfish (unspecified)
Range
F
F
F
F
F
F
F
F
F
F
F
F
F
F
F
F
F
F
F
F
F
-
Feeding No. of
Strategy 2 Sites 3
B
B
B
B
B
(Zooplankton & Crust)
B
B (Zooplankton
Insect Larvae/Plants )
B (Aq. Insects)
B (Aq. Insects)
B (Aq. Insects)
B (Aq. Insects)
B (Aq. Insects)
B (Aq. Insects)
B (Aq. Insects)
B
B (Omni.)
B (Omni.)
B (Omni.)
B (Omni.)
B (Omni.)
P(Pisc.)
-
1
I
1
5
4
1
10
1
1
1
1
1
1
16
4
6
2
1
4
30
8
11
Family - Ariidae
Atius fells
Order - Gadifonnes
Family - Gadidae
Gadus morfaua
Order - Perciformes
Family - Percichthyidae
Mnmne
\
-------
TABLE 5-1 (CONT.)
Scientific Name
Family - Centrarchidae
Ambloplites rupestris
Lepomis aunrus
Lepomis cvanellus
.epomis gihhosus
^epomis gulosus
.epornis marmrhirus
.epomis megalotis
^epornis microlophus
Microptenis coosae
Micropterus dQlonueui
Microptems notius
Micropterus punctuiatus
Microptenis ^alrr|ojf|<^
Pomoxis anmiians
Pomoxis nigrnmaciilatm
Family - Percidae
Perca flavescens
Stizostedion canadense
Stizostedion vitreum
vitiemn
Family - Pomatomidae
Pomatnmiis saltarrix
Family - Carangidae
Caranx barthnlnmaei
Taranx hippos
Taranx ignohlis
Family - Lutjanidae
Lutianus camnechanus
Family - Sparidae
Archosargus prabato
-rephalns
Family - Sciaenidae
Aplodinotus grunniens
Cynoscion nebulosus
Pynnscirm regalis
Equetus punctatus
Leiostomus xanthums
Common Name
Rock Bass
Redbreast Sunfish
Green Sunfish
Pumpkinseed
Warmouth
Bluegill
Longear Sunfish
Redear Sunfish
Redeye Bass
Smallmoutb Bass
Suwannee Bass
Spotted Bass
Largemouth Bass
White Crappie
Black Crappie
Crappie (unspecified)
Yellow Perch
S auger
Walleye
Bluefish
Yellow Jack
Crevalle Jack
Papio
Red Snapper
Sheepshead
Freshwater Drum
Spotted Seatrout
Weakfish
Spotted Drum
Spot
Range '
F
F
F
F
F
F
F
F
F
F
F
F
F
F
F
-
F
F
F
M
M
M
M
M
M
F
Both
M
M
Both
Feeding^
Strategy "
p
P
p
p
p
P (Insects)
P
P (Mollusks)
P
P(Pisc.)
P
P
P
P(Pisc.)
P(Pisc.)
-
P
P
P (Pise.)
P (Pise.)
P
P
P
P
P
P (Mollusks & Fish)
P
P
P
P
No. of
Sites3
4
2
2
1
1
4
1
1
1
26
1
3
83
7
4
3
1
3
22
5
1
1
1
2
2
3
3
3
1
3
^ EiQuhDe/Mahne: M x Marine: F ^ Freshwiter: [I] = Introduced
: P = Predator: B = Booom Feeder
3 Number of sites where fish were collected and analyzed
SOURCE: AFS. 1980
Pise. = Piscivorous: Omni. = Omnivorous
135
-------
TABLE 5-1 (CONT.)
Scientific Name
Micropogontaij ifnfliilanis
Pogomas cromjs
^f jan^fjns ocellatus
Family - Cichlidae
Tilapia (species uncertain)
Tilapia 7iHi
Family - Embiotocidae
Phapertylnp fnrt^m^
Family - Mugilidae
Mu£il ccrhfllufi
Family - Scorpaenidae
Sehastes aunculatus
Sehastes caurinits
S chaste* maiigcf
Sehastes paucispinis
Sebastes pronger
Family - Cottidae
Cottus (species unknown)
Order - Pleuronecufonnes
Family - Bothidae
Paralichthys dentatm
Paralichthys lethnstigma
Family - Pleuronectidae
HippoglQssnidg^ ela.tsndnn
Hvpsopsetta giumlata
Pla^chthys stellafiis
Pletimnichthvs yprticalis
Pseudopleuronectes
americanus
Common Name
Atlantic Croaker
Black Drum
Red Drum
Redbelly Tilapia
White Surijperch
Striped Mullet
Brown Rockfisb
Copper Rockfish
Quillback Rockfisb
Bocaccio
Redstripe Rockfisb
Sculpin
Coastrange Sculpin
Summer Flounder
Southern Flounder
Flatbead Sole
Diamond Turbot
Starry Flounder
Homybead Turbot
Winter Flounder
Range
Both
M
Both
m
M
Both
M
M
M
M
M
Both
M
Both
M
M
Both
M
M
Feeding
Strategy 2
p
p
p
B
B
B
P
P
P
P
P
P
B
B (Plants & Insects)
P
P
P
P
P
P
P
No. of
Sites3
3
3
3
1
1
1
3
4
1
2
2
1
5
1
4
^ Esttunne/Minoe: M = Marine: F = Frahwtier; (I) = Introduced
- P = Prediior B = Bottom Feeder
Number of litei where fish were collected and analyzed
SOURCE: AFS. 1980
Pise. = Piscivorous: Omni. = Omnivorous
136
-------
PREVALENCE AND AVERAGE CONCENTRATION OF CHEMICALS BY SPECIES
Table 5-2 shows average fish tissue concentrations for each of the dioxin/furan compounds
in the 14 most commonly sampled fish species at targeted sites. With the exception of four
congeners (1,2,3,4,7,8,9 HpCDF; 1,2,3,4,7,8 HxCDD; 1,2,3,6,7,8, HxCDF; 1,2,3,7,8,9 HxCDF),
whole-body samples from bottom-feeding species have higher dioxin/furan concentrations than
fillet samples from game fish. Average concentrations were the highest in carp for four of the six
dioxins, and three of the nine furans. The highest concentrations of the other congeners were found
in spotted and redhorse suckers and channel catfish for the bottom-feeding species. For game fish
species, the highest concentrations were found in white crappie for two of the six dioxins, four of
nine furans, and TEC. Brown trout had the highest average concentration for one dioxin and two
furans. The highest concentrations of the other congeners were found in largemouth bass, white
bass, northern pike, and bluefish. The occurrence of pollutants in the most frequently sampled fish
species varied by chemical. Some pollutants (i.e., 2,3,7,8 TCDF and 1,2,3,4,6,7,8 HpCDD) were
found in the majority of samples (Table 5-3). Two furans, 1,2,3,7,8,9 HxCDF and 1,2,3,4,7,8,9
HpCDF, were not found in quantities above detection in any of the game fish fillets, but were
detected in a small number of the bottom feeder whole-body samples.
Table 5-4 shows the average fish tissue concentration of selected xenobiotics for the 14 most
commonly sampled species at targeted sites. Average mercury concentrations are higher in game
fish analyzed as fillets than bottom feeders analyzed as whole-body samples. As discussed in
Chapter 4, this result would be expected because mercury is stored in the muscle tissue rather than
the lipid and would, therefore, exhibit higher concentrations in fillets than in whole-body samples.
Ten xenobiotics are detected in whole-body samples of bottom feeders and in fillet samples of game
fish at roughly the same average concentrations. These compounds are biphenyl, chlorpyrifos,
dicofol, dieldrin, endrin, mirex, oxychlordane, PCBs, DDE, and trifluralin. Twelve compounds
have higher average concentrations in whole-body samples of bottom feeders than in fillet samples
of game fish: alpha and gamma-BHC; heptachlor epoxide; pentachloroanisole; pentachloroben-
zene; chlordane; nonachlor; three trichlorobenzenes; 1,2,3,4 tetrachlorobenzene; and
hexachlorobenzene. Biphenyl, mercury, PCBs, and DDE were found in a majority of both
whole-body and fillet samples with concentrations above detection (Table 5-5). Endrin, 1,3,5
trichlorobenzene and trifluralin were found in quantities above detection in only a few of the game
fish fillet samples collected.
HABITAT AND FEEDING STRATEGY OF MOST FREQUENTLY SAMPLED
SPECIES
Common Carp
The common carp (Cyprinus carpio) is distributed widely throughout most parts of the
country. It prefers the shallows of warm streams, lakes, and ponds containing an abundance of
vegetation. It is not normally found in clear, cold waters or streams of high gradients.
The spawning period for this species can last from April to August, but generally spawning
occurs in late May and June. Shallow and weedy areas of lakes, ponds, tributaries, streams, swamps,
floodplains, and marshes are suitable spawning grounds. The young carp consume zooplankton as
137
-------
TABLE 5-2
Average Fish Tissue Concentrations of Dioxins and Furans for Major Species
Fish Species
Bottom Feeders
Carp
White Sucker
Channel Catfish
Redhorse Sucker
Spotted Sucker
Gam* Fish
Largemouth Bass
Smallmouth Bass
Walleye
Brown Trout
White Bass
Northern Pike
Flathead Catfish
White Grapple
Bluefish
2378
TCDD
7.76
8.08
11.56
4.65
1.73
1.73
0.72
0.88
2.52
3.00
0.77
0.78
2.13
0.85
12378
PeCDD
3.63
2.05
2.37
1.50
2.34
0.59
0.50'
0.54*
1.01
0.66
0.46*
0.43
0.60
0.56
123478
HxCDD
2.16
1.03
1.61
1.40
1.70
1.12
1.13*
0.99*
1.07*
1.05*
1.23*
0.90
1.29*
1.23*
123678
HxCDD
6.81
1.96
5.62
2.36
12.08
1.28
0.79
0.73
0.98
0.78
0.91
1.06
1.03*
0.98*
123789
HxCDD
1.54
0.88
1.29
0.84
1.14
0.64
0.64*
0.62*
0.68*
0.61*
0.69*
0.50
0.83*
0.69*
1234678
HpCDD
22.29
3.72
9.40
4.94
17.48
2.48
0.67
0.88
1.18
1.01
0.73
1.67
1.33
0.65
2378
TCDF
10.15
22.89
2.22
30.09
7.49
2.18
1.93
1.83
3.74
5.07
1.01
1.63
10.46
2.11
12378
PeCDF
1.31
1.10
0.52
0.75
2.12
0.37
0.36*
0.35*
0.60
0.40
0.44
0.40
0.54
0.41
23478
PeCDF
4.01
2.64
2.91
1.28
2.06
0.47
0.51
0.38
1.36
0.49
0.66
0.56
0.67
0.59
123478
HxCDF
2.54
2.21
2.41
2.10
2.22
1.24
1.28
1.04
1.47
1.04
1.41*
1.05
1.33*
1.42*
123678
HxCDF
1.91
1.29
1.41
1.16
1.79
1.23
1.23
1.09*
1.12*
1.16*
1.42*
1.20*
1.33*
1.42*
123789
HxCDF
1.16
1.06
1.38*
1.19*
1.28*
1.21*
1.26*
1.07*
1.09*
1.13*
1.38*
1.17*
1.30*
1.39*
234678
HxCDF
1.20
1.09
1.62
1.50
1.78
0.88
0.89*
0.75
0.94*
0.81*
0.98*
0.61*
0.95*
0.98*
1234678
HpCDF
2.49
1.23
2.55
1.57
1.77
0.82'
0.69
0.74
0.67*
0.63
0.56
0.56
0.96*
0.72*
1234789
HpCDF
1.22
1.13
1.26
1.36*
1.08
1.21*
1.30*
1.21*
1.16*
1.17*
1.30*
1.10*
1.34*
LSI-
TEC
13.06
12.79
14.80
9.22
6.23
1.91
0.65*
0.79*
3.31
3.44
0.66
0.99
3.80
1.41
Values calculated using wtiole body samples (or bottom feeding species and fillet samples for Game Fish (predators).
Values below detection have been replaced by one-half detection limit for the given sample. Asterisk indicates all values below detection.
Units » pg/g.
138
-------
TABLE 5-3
Detailed Summary of Occurrence of Prevalent Dioxins/Furans by Fish Species
Fish Species
Bottom Feeders
Carp
White Sucker
Channel Cattish
Redhorse Sucker
Spotted Sucker
Game Fish
Largemouth Bass
Smallmouth Bass
Walleye
Brown Trout
White Bass
Northern Pike
Flathead Catfish
White Crappie
Bluefish
2378
TCDD
106/135
28/37
12/19
9/15
6/10
34/75
9/22
5/18
2/8
5/10
4/7
3/6
1/8
3/4
12378
PeCDD
89/133
20/36
13/17
7/15
5/10
10/73
0/21
0/18
3/7
2/10
0/6
3/6
1 /8
1 /4
123478
HxCDD
73/125
7/34
6/18
1 /14
4/10
2/72
0/20
0/16
0/7
0/10
0/7
1 /6
0/7
0/4
123678
HxCDD
102/125
20/34
16/18
9/14
7/10
18/72
2/19
1/16
1 11
2/10
6/7
4/6
0/7
0/4
123789
HxCDD
71/125
7/34
12/18
3/14
6/10
5/72
0/20
0/16
0/7
0/10
0/7
1/6
0/7
0/4
1234678
HpCDD
103/108
28/31
18/18
12/13
10/10
37/67
10/18
9/16
2/6
8/9
2/7
5/6
2/7
1 /4
2378
TCDF
124/135
35/37
16/19
14/15
9/10
42/75
16/22
12/18
6/8
10/10
4/6
2/6
3/8
4/4
12378
PeCDF
83/134
19/37
9/19
6/15
2/10
6/74
0/22
0/18
2/8
4/10
1 17
1/6
1 /8
1 /4
23478
PeCDF
96/134
27/37
15/19
11 /15
6/10
12/74
5/22
3/18
4/8
4/10
1 17
2/6
1 /8
4/4
123478
HxCDF
79/126
14/34
9/18
5/ 15
2/10
10/73
1 /20
1/16
2/7
1 / 10
0/7
2/6
0/6
0/4
123678
HxCDF
45/126
4/34
5/18
1/15
1 /10
2/73
1 /20
0/16
0/7
0/10
0/7
0/6
0/7
0/4
123789
HxCDF
2/126
1/34
0/18
0/15
0/10
0/73
0/20
0/16
0/7
0/10
0/7
0/6
0/7
0/4
234678
HxCDF
63/126
8/34
8/ 18
3/15
1 /10
6/73
0/20
1/16
0/7
0/10
0/7
2/6
0/7
0/4
1234678
HpCDF
84/109
16/31
10/18
5/13
5/10
13/67
1 /18
2/16
0/6
1 /9
1 /7
3/6
0 17
0/4
1234789
HpCDF
6/109
2/31
1 / 18
0/13
1 / 10
0/67
0/18
0/16
0/6
0/9
0/7
0/6
0/7
0/4
Values were determined using whole body samples for bottom-feeding species and tillet samples for game species.
First number indicates number of samples where delected; second number indicates total number of samples at different sites for given species analyzed.
It more than one fillet or whole body sample ot the same species at a site was analyzed, only the highest value was used.
139
-------
TABLE 5-4
Average Fish Tissue Concentrations of Xenobiotics for Miyor Species
Fish Species
Bottom Feeder*
Carp
White Sucker
Channel Cat
Redhorse Sucker
Spotted Sucker
Game Fl»h
Largemouth Bass
Smallmouth Bass
Walleye
Brown Trout
White Bass
Northern Pike
Flathead Cat
White Crappie
Bluefish
Alprta-BHC
3.10
3.31
2.87
0.82
145
0.15
0.36
ND
1 59
0.34
055
0.92
023
038
Gamma BHC
434
1.66
317
0.41
2.63
0.07
0.15
ND
ND
0.79
ND
058
ND
012
Biphenyl
438
128
1.24
125
3.35
0.38
033
040
081
0.62
059
060
021
0.20
Chlor pyrites
823
1 75
697
0.35
056
023
008
004
ND
1 32
11.43
2257
ND
ND
Dicofol
088
048
059
ND
005
020
ND
ND
0.94
ND
031
1 28
ND
ND
Dieldnn
44.75
2275
15.44
535
552
501
234
3.73
20.13
935
9.04
37.38
ND
2.87
Endrin
1 40
024
907
097
ND
ND
ND
ND
ND
ND
ND
3.45
ND
ND
Heptachlor
Epoxide
400
1 09
050
ND
ND
0.30
007
0.21
208
1 40
ND
057
ND
ND
Mercury
(ug/g)
0 11
0.11
009
027
0.12
046
034
051
0 14
035
034
027
022
022
Mirex
3 70
435
1459
057
1 79
021
1 99
008
4398
0.11
239
ND
ND
0.13
Oxycrilordane
820
3 10
641
237
005
047
054
111
538
084
400
063
ND
ND
PCBs
2941 13
169781
130052
487.72
13390
23226
49622
36865
243407
28835
78840
52119
2234
36806
Fish Species
Bottom Feeders
Carp
White Sucker
Channel Cat
Redhorse Sucker
Spotted Sucker
Game Fi»h
Largemouth Bass
SmaXmouth Bass
Walleye
Brown Trout
White Bass
Northern Pike
Flathead Cat
White Crappie
Btuefish
Pentacriloro-
anisote
1650
906
39.60
2.87
17.68
057
023
076
009
093
1 51
031
0.33
0.05
Pentachloro-
benzene
1.04
0.39
1.32
002
0.02
0.02
0.02
ND
060
ND
009
ND
ND
ND
DDE
41543
7839
627.77
87.25
7531
5572
33.63
3400
158.90
17.44
5950
755.18
1004
29.13
Total
Chlordane
67.15
1842
5439
16.48
1233
289
401
362
725
1067
545
1607
0.34
7.74
Total
Nonachlor
63.15
2083
6628
3073
15.00
4.21
782
804
3260
16.00
1388
14.04
028
7.56
123TCB
1.54
0.16
0.14
055
334
022
070
029
».»0
021
030
0.10
008
6.25
124TCB
4.77
030
0.37
6.48
1200
0.19
059
038
098
0.10
023
0.18
0.08
466
135TCB
008
0.14
ND
008
1 00
0.03
004
ND
ND
ND
ND
ND
ND
057
1234TECB
0.30
015
088
009
009
001
004
0004
009
001
001
ND
ND
ND
Tnfluralin
1255
NO
1.00
ND
ND
ND
ND
ND
ND
ND
ND
4437
ND
ND
Hexachloro-
benzene
358
362
236
058
002
020
036
0.11
306
083
020
085
ND
ND
Values calculated using whole body sample) for bottom feeding species and fillet samples for Game Fish (predators). Values below detection have been set at zero.
Units - ng/g. unless noted.
140
-------
TABLE 5-5
Detailed Summary of Occurrence of Prevalent Xenobiotics by Fish Species
Fish Species
Bottom Feeder*
Carp
White Sucker
Channel Cat
Redhorse Sucker
Spotted Sucker
Gam* Fish
Largemouft Bass
SmaHmouth Bass
Waleye
Brown Trout
White Bass
Northern Pike
Flathead Cat
White Crappie
Bluefish
Alpna-BHC
77/128
24/35
7/16
6/14
3/10
5/31
4/15
078
1/3
3/5
1/6
2/4
1/4
1/3
Gamma-BHC
57/128
18/35
7/16
4/14
2/10
3/31
2/15
078
0/3
4/5
0/6
1/4
0/4
1/3
Biphenyt
124/128
33/35
16/16
14/14
10/10
29/31
15/15
8/8
3/3
5/5
6/6
4/4
4/4
2ft
Chlorpyritos
46/128
7/35
9/16
3/14
1/10
4/31
1/15
1/8
0/3
3/5
3/6
3/4
0/4
0/3
Dtcotot
12/128
7/35
4/16
0/14
1/10
7/31
0/15
0/8
1/3
0/5
2/6
1/4
0/4
0/3
Dieldrin
91/128
24/35
11/16
8/14
5/10
9/31
8/15
3/8
2/3
5/5
3/6
4/4
0/4
2/3
Endrin
16/128
3/35
2/16
2/14
0/10
0/31
0/15
0/8
0/3
1/5
0/6
1/4
0/4
0/3
Heptachkv
Epoxkte
33/128
2/35
2/16
0/14
0/10
2/31
1/15
2/8
2/3
2«
cue
1/4
0/4
0/3
Mercury
111/133
29/34
16/17
14/15
9/10
65/66
20/20
19/19
7/8
6/6
7/7
6/6
5/7
3/3
Mirex
55/128
9/35
7/16
6/14
6/10
6/31
6/15
2/8
2/3
3/5
3/6
0/4
0/4
1/3
Oxychlordane
36/128
9/35
6/16
5/14
1/10
4/31
3/15
2/8
2/3
2/5
1/6
1/4
0/4
0/2
PCBs
122/128
32/35
15/16
14/14
9/10
26/31
14/15
8/8
3/3
5/5
5/6
4/4
3/4
3/3
Fish Species
Bottom Feeders
Carp
White Sucker
Channel Cat
Redhorse Sucker
Spotted Sucker
Game Fish
Largemouth Bass
SmaHmouth Bass
WaReye
Brown Trout
White Bass
Northern Pike
Rathead Cat
White Crappie
Bluefish
Pentachkxo-
anisote
103/128
25/35
11/16
11/14
7/10
6/31
4/15
6/8
1/3
5/5
2/6
2/4
1/4
1/3
Pentachloro-
benzene
42/128
7/35
4/16
1/14
1/10
1/31
1/15
0/8
2/3
0/5
1/6
0/4
0/4
0/3
ODE
126/128
34/35
16/16
14/14
9/10
31/31
15/15
8/8
3/3
5/5
6/6
4/4
4/4
2/3
Total
Chbrdane
109/128
24/35
12/16
7/14
7/10
12/31
8/15
4/8
2/3
4/5
3/6
3/4
1/4
3/3
Total
Nonachlor
114/128
24/35
14/16
10/14
8/10 '
18/31
9/15
3/8
2/3
5/5
4/6
4/4
1/4
3/3
123TCB
35/128
9/35
3/16
6/14
7/10
17/31
9/15
3ft
3/3
4/5
3/6
1/4
1/4
3/3
124 TCB
60/128
18/35
7/16
6/14
8/10
17/31
8/15
3/8
3/3
3/5
2/6
2/4
2/4
3/3
135 TCB
14/128
2/35
0/16
2/14
2/10
3/31
1/15
0/8
0/3
0/5
0/6
0/4
0/4
1/3
1234 TECB
16/128
5/35
2/16
2/14
1/10
1/31
3/15
1/8
1/3
1/5
1/6
0/4
0/4
0/3
TriHuralin
31/128
0/35
1/16
0/14
0/10
0/31
0/15
0/8
0/3
1/5
0/6
3/4
0/4
0/3
HexacWoro-
benzene
72/128
16/35
6/16
4/14
2/10
6/31
5/14
2/8
2/3
3/5
1/6
2/4
0/4
0/3
Values were determined using whole body samples for bottom-feeding species and Mlel samples lor predator species.
First number indicates number ol samples where detected; second number indicates total number of samples at different sites tor given species analyzed.
If more than one Fillet or whole body sample of the same species at a site was analyzed. only the highest value was used.
141
-------
their major food source. Adults consume fish, snails, plants, bottom ooze, insect larvae, insects,
crustaceans, mollusks, and fish eggs.
White Sucker
The white sucker (Catostomuscommersoni) is found in the northeastern, central, and eastern
regions of the country. It is a common inhabitant of the most highly polluted and turbid waters. It
tolerates a wide range of environments and stream gradients. However, it is found most often in
lakes or reservoirs with clear to slightly turbid waters and a bottom consisting of gravel or sand with
sparse vegetation.
Spawning generally occurs in mid-April to early May in swift water or rapids over gravel
bottoms. The young feed on algae, zooplankton. and blood worms, and the adults consume fish,
fish eggs, mud, plants, algae, insects, mollusks, and zooplankton.
Channel Catfish
The channel catfish (Ictalurus punctatus) is found throughout the central pan of the country
and into parts of the western and eastern United Slates. It prefers clear, rocky, well-oxygenated
streams, lakes, and reservoirs, but can adapt to slow-moving, silty streams.
The spawning period generally occurs from May to July in inlet streams or tributaries. The
spawning nest is located in a crevice, under a bank, rock, or log, and can be constructed on several
types of bottom substrate. The young consume aquatic insects and zooplankton, while the adults
take any food available to them. This can include fish, plants, frogs, crayfish, clams, worms, algae,
and decaying or dead matter.
Spotted Sucker
The spotted sucker (Minytrema melanops) is found in the central and southeastern regions
of the United States. It prefers large rivers and their sloughs and reservoirs that are slow moving
with a soft bottom of muck or sand with vegetation. It is intolerant of turbid waters, various
industrial pollutants, and bottoms covered with flocculent clay silts.
Spawning occurs throughout the month of May in pool-like areas near riffle over a rubble
bottom. The young and adult spotted suckers both feed on zooplankton, insect larvae, crustaceans,
algae, and higher plant material.
Redhorse Sucker
Redhorse suckers are most commonly found in the central and eastern parts of the country.
Redhorse suckers generally prefer swiftly flowing sections of small to medium-sized streams with
clear water and a gravel, bedrock, or sand bottom. They are intolerant of siltation and pollution in
their habitat.
142
-------
Spawning generally occurs during the month of April in shallower areas with a proper bottom
substrate. Redhorse suckers are highly selective when it comes to choosing a spawning area. The
water depth (0.5-2.0 ft) and the bottom substrate (approximately 70 percent fine rubble. 10 percent
coarse rubble, and 20 percent sand and gravel) are the most important factors for a proper spawn.
The young feed principally on phytoplankton, and the adults feed primarily on aquatic insects. For
the data analyses in this report, all species of redhorse sampled were grouped under the name
redhorse sucker.
Largemouth Bass
The largemouth bass (Micropterussalmoides) is found in most parts of the country. It prefers
medium to large rivers, lakes, sloughs, ponds, and backwaters with clear to slightly turbid waters.
It is usually found in shallower areas with dense to sparse vegetation.
The spawning period generally occurs from late April to early June. They tend to spawn a
little earlier than the smallmouth bass. The fish spawn in quiet bays with emergent vegetation on
a sand, gravel, or, occasionally, mud bottom. The young feed on algae, zooplankton, and insect
larvae, while the adults feed on fish, crayfish, mammals, large insects, and amphibians.
Smallmouth Bass
The smallmouth bass (Micropterus dolomieui) is found mostly in the northeastern and
central parts of the country, but can be found in limited areas of other parts of the country. It prefers
medium to large streams, rivers .and lakes with clear water, rocky or sandy bottoms, aquatic
vegetation, and clean gravel shores.
Spawning generally occurs during late May and throughout June. The spawning nest is built
on a gravel bottom beside a large boulder, log, stump, or foreign object in the shallows. The young
consume insect larvae, zooplankton, and small insects, and the adults consume mostly fish but will
also eat crayfish, insects, mammals, and amphibians.
Walleye
The walleye (Stizostedion vitreum vitreum) is found in most parts of the country except for
the most western and southern areas. It prefers large clearwater rivers and lakes with sand and
gravel bottoms. It is usually found in quiet backwaters and sloughs of these rivers and lakes.
Spawning generally occurs between mid-April and early May in wave-washed shallows or
up inlet streams with gravel bottoms. This species prepares no spawning nest so the eggs are
scattered over the gravel bottom of the area. The young consume zooplankton, insect larvae, and
fry of other fish species, and the adults consume mostly fish, but will also eat insects, crayfish, and
lamprey eels.
143
-------
White Bass
The white bass (Morone chrvsops) is found throughout the country, but is most heavily
concentrated in the central United States. It prefers large, open rivers and lakes with clear to turbid
waters and moderate currents.
The spawning period runs from late April into early June over most of its range. The
spawning grounds consist of a firm bottom of sand, gravel, rubble, or rock in the shallows. This
species builds no spawning nest, so the eggs are scattered over the bottom of the spawning area.
The young white bass consume algae and zooplankton, and the adults consume fish, insect larvae,
insects, and zooplankton.
Brown Trout
The brown trout (Salmo trutta) is most heavily concentrated in the northeastern and western
parts of the country. It prefers coldwater streams and lakes, but can tolerate warmer water than
other species of trout. In streams, it can be found in deeper and slower moving pools, and in the
Great Lakes, it is found close to the shore.
The spawning period generally occurs from October to December in waters ranging in size
from large streams to small spring-fed tributaries. The spawning nest is made on a gravel bottom
in the shallower sections of the stream. The young feed primarily on zooplankton and insect larvae,
and the adults eat mostly fish but will also consume larval insects, insects, leeches, snails, crayfish,
freshwater shrimp, and worms. The brown trout is known to eat more fish than the other species
of trout.
Flathead Catfish
The flathead catfish (Pylodictisolivaris) is generally found in the central parts of the country.
It prefers large, rocky rivers with deep pools, plenty of cover, and swiftly moving waters.
The spawning period generally occurs in the months of June and July. The spawning nest
is built in a secluded dark shelter over a gravel bottom. The young consume aquatic insect larvae,
and the adults consume mostly fish but will occasionally feed on crayfish.
Northern Pike
The northern pike (Esox lucius) is found in the northeastern and north central parts of the
country. It prefers cool to moderately warm weedy lakes, ponds, and slow-moving rivers. It can
be found in areas of light to dense aquatic vegetation with clear to slightly turbid waters.
The spawning period generally occurs in late March or early April in shallow flooded
marshes or inlet streams. Grasses, sedges, or rushes with fine leaves are most suitable for egg
deposition. The young feed on phytoplankton, zooplankton, and insects, and the adults consume
mainly fish but will also consume crayfish, mammals, and frogs.
144
-------
White Grapple
The white crappie (Pomoxis annularis) is found mostly in the central part of the country,
but can be found in limited areas in other regions. It prefers sloughs, backwaters, landlocked pools
and lakes, and pools in moderate-sized to large streams with slightly turbid to turbid waters. It is
found in the shallow and warm areas with sparse vegetation over a variety of substrates.
The spawning period generally occurs in the months of May and June. The spawning nests
are made in colonies near vegetation over a hard clay or gravel bottom in the shallows. The young
consume zooplankton and small insects, and the adults consume mostly fish but will occasionally
feed on insects.
Blue Fish
The bluefish (Pnmatnmus saltatrix^ is an ocean predator found in the tropical and temperate
waters of the world with the exception of the central and eastern Pacific. It lives around large shoals
in open water and moves in toward coastal waters to feed. This movement inward, as well as other
migrations, is correlated with the movement of prey species of fish. It will attack fish almost as
long as itself and will kill prey that it does not eat. The bluefish is the only ocean fish included in
the 14 most frequently sampled species for this study.
Shellfish
There were 17 shellfish samples analyzed in the study. These included 4 dungeness crabs,
2 hepatopancreas organs of crabs, 3 crayfish, 3 soft shell clams, 2 pacific oysters, 1 unidentified
oyster, 1 unidentified mussel, and 1 unidentified shellfish. The different species of shellfish
exhibited a wide range of chemical concentrations. This could be attributed to differences in habitat
and food sources between species. Varying chemical concentrations within each type of species
are most likely related to the location of capture.
The dungeness crabs, on average, were found to have the highest chemical concentrations
of all the shellfish analyzed. The chemicals accumulate in the hepatopancreas organ of the crab in
very high concentrations. The high concentrations of chemicals in these crabs may relate to the
large amount of fish consumed as part of their diet The crayfish consumes a smaller proportion of
fish in its diet than the dungeness crabs. It also consumes other types of food including some plant
material. This may account for the differences in chemical concentrations between the two species.
The oysters, mussels, and clams analyzed for some of the study sites are filler feeders and
consume similar types of food. The soft shell clams show higher chemical concentrations than the
other species of filter feeders. This may be explained by differences in habitat among these species.
The clams prefer a muddy or sandy bottom, and the oysters and mussels prefer a rocky bottom. A
muddy and soft bottom will tend to accumulate more contaminants than a rocky bottom, so this
would most likely have a direct effect on the clams. Overall, the filter feeders showed lower
chemical concentrations than the crabs and crayfish.
145
-------
Chapter 6 - Estimate of Potential Human Health Risks
This chapter presents risk estimates to human health based on fillet concentration data shown
in Appendix D. Most of the fillets were from game fish, but a few were from bottom feeders likely
to be consumed by humans. Carcinogenic risks were estimated for 14 of the xenobiotic compounds
for which cancer potency factors were available. Noncarcinogenic risks were estimated for the 21
compounds for which risk values (i.e., reference doses) were available. Human health risks were
not calculated for dioxins/furans due to the current review of the potency of these chemicals. The
estimated risks presented in the report are intended as a screening assessment. A detailed site-
specific risk assessment would require additional samples and would incorporate local consumption
rates and patterns, and the actual number of people exposed. Information on the specific health
effects of the study compounds and aquatic or wildlife effects, where available, are included in the
chemical profiles. Appendix C.
Potential upper-bound human cancer risks from consumption of fish were estimated using
fillet samples for selected analytes. Fillet data were available at 182 sites for mercury and 106 sites
for the xenobiotic compounds, excluding dioxins and furans. Risks were calculated using the
average fillet concentration at each site for the few places where more than one fillet concentration
sample was available. The calculations were based on standard EPA risk assessment procedures
for lifetime exposure with upper-bound cancer potency factors and three fish consumption rates of
6.5,30, and 140 g/day. The reasons for setting these rates are discussed in the section on Exposure
Assessment.
The compounds evaluated were those for which cancer potency factors and/or reference
doses have been established. These compounds are listed below:
Biphenyl • Hexachlorobutadiene
• alpha-BHC • Isopropalin
gamma-BHC (Lindane) • Mercury
Chlordane • Mirex
Chlorpyrifos • Pentachloroanisole
p.p'-DDE • Pentachlorobenzene
Dicofol • Pentachloronitrobenzene
Dieldrin • Polychlorinated biphenyls (PCBs)
Endrin • 1,2,4,5 Tetrachlorobenzene
Heptachlor • l,2,4Trichlorobenzene
Heptachlor epoxide • Trifluralin
Hexachlorobenzene
147
-------
METHOD OF ESTIMATING RISKS
Dose-Response Assessment
In developing risk assessment methods, EPA has recognized that fundamental differences
exist between carcinogenic dose-response variables and noncarcinogenic dose-response variables
that could be used to estimate risks. Because of these differences, human health risk characterization
is conducted separately for potential carcinogenic and noncarcinogenic effects. However, car-
cinogenic chemicals may also cause noncarcinogenic effects (i.e., a variety of toxic endpoints other
than cancer may be associated with exposure to carcinogens). Consequently, reference dose (RfD)
values have been established for many carcinogens and are used in the evaluation of potential
noncarcinogenic effects.
Key dose-response variables used in quantitative risk estimates are cancer potency factors
(CPFs) for carcinogens and RfD values for noncarcinogens. The carcinogenic potency factor
(expressed in units of (mg/kg/day)" ) is typically determined by the upper 95 percent confidence
limit of the slope of the linearized multistage model that expresses excess cancer risk as a function
of dose. The RfD (expressed in units of mg/kg/day) is an estimated single daily chemical intake
rate that appears to be without risk if ingested over a lifetime.
Available dose-response information for quantitative risk assessment is summarized in
Table 6-1 for the chemicals investigated. Potency factors and reference dose values were collated
primarily from the Integrated Risk Information System database (IRIS, 1989), and supplemented
where necessary by information from other sources such as the Public Health Risk Evaluation
Database (PHRED, 1988). As shown in Table 6-1, substances with the highest carcinogenic potency
(i.e.. those with the highest carcinogenic potency factors) are dieldrin, heptachlor epoxide, and
PCBs. Substances with the highest noncarcinogenic potency toxicity (i.e., those with the lowest
RfD values) are mirex, heptachlor epoxide, and dieldrin.
Human health risks due to PCBs were estimated based on the total of all the congeners
present. EPA has developed a CPF only for total PCBs. While recent research (Smith et al., 1990)
indicates that toxicity varies depending on the number of chlorines present and their position, EPA
has not adopted this type of approach. Smith's research also indicates that certain PCBs can induce
similar changes in enzymatic activity as dioxins and furans. At present the approved EPA approach
is to estimate risks due to PCBs and dioxins/furans separately. The specific PCBs thought to induce
enzyme changes (coplanar PCBs and mono-ortho analogues) were not quantified separately in this
study. The risks due to chlordane were estimated using the CPF for chlordane and the sum of the
concentrations of cis- and trans- chlordane, cis- and trans-nonachlor, and oxychlordane measured
in the same fillet sample. This sum is referred to as combined chlordane. Heptachlor and heptachlor
epoxide have separate CPF and RfD values that are different from chlordane.
Exposure Assessment
The exposure assessment for consumption of chemically contaminated fish and shellfish
consisted of:
148
-------
TABLE 6-1
Dose-Response Variables Used in Risk Assessment
Analyte
Biphenyl
Chlordane
Chlorpyrifos
DDE (p,p-)
Dicofol (Kelthane)
Dieldrin
Endrin
Heptachlor
Heptachlor epoxide
Hexachlorobenzene
Hexachlorobutadiene
Isopropalin
a-Hexachlorocyclohexane
y-Hexachlorocyclohexane
Mercury
Mirex
Pentachloroanisole
Pentachlorobenzene
Pentachloronitrobenzene
Polychlorinated biphenyls
1 ,2,4,5 Tetrachlorobenzene
1 ,2,4 Trichlorobenzene
Trifluralin
Cancer Potency
Factor (CPF)
(mg/kg/day)"
IJOxlO00
1 _ j
3.40xlO'lc'd
4.40xlO'lb
1.60xlOlc
4.50xl00c
9.10x10*
1.70xlOut
7.8xlO"2c
—
6.30x10°*
1.30xl00f
—
1.80x10°;
1.60xlO'2g
7.70x1 0**
—
—
7.70xlO'3c
EPA
Cancer
Evidence
Rating a
NA
B2
NA
B2
C
B2
D
B2
B2
B2
C
NA
B2
B2
D
R
D,R
D
pending
B2
D
D
C
Reference
(RfD)
(mg/kg/day)
5.00xlO'2b
6.00x10,
3.00xlO"3c
S.OOxlO"4^
—
5.00xlO'5c
3.00x10
s'oOxlO'f
Sr1
1.30xlO'5c
_Af\
s.ooxio":0
2.00xlO'3c
1.50xlO'2c
Aa
3.00x10^
3.00x1 0"4*
fLff
2.00x1 0'f
3.00xlO'2e
-------
Defining chemical concentrations to be used,
Selecting consumption rates for various segments of the population, and
Estimating chemical doses.
The detected fillet concentration at each site was used to estimate risks, [f more than one
fillet sample, excluding duplicates, was available, the average concentration was used, even if the
fish species were different. Multiple fillets were available at four sites that represented 4 percent
of the sites with xenobiotic data. Fillet composite samples consisting of fewer than three fish were
not used for the risk assessment Three consumption rates were used to estimate exposure:
• 6.5 g/day, which is the average fish consumption rate of freshwater and estuanne fish
across the United States (U.S. EPA, 1980a),
• 30 g/day, which is representative of the average fish consumption rate by average sport
fishermen (U.S. EPA, 1989b); and
• 140 g/day, which is representative of the consumption rate for the 95th percentile of
sport fishermen and is appropriate for subsistence consumers (U.S. EPA, 1989b).
Risks for consumption rates of 6. 5 g/day, 30 g/day, and 140 g/day can be read directly from
the nomographs in Appendix B. The nomographs can be used to estimate risks at consumption
rates between 1 and 1000 g/day.
The consumption rate was combined with the chemical concentration data to estimate a
range of daily doses over a lifetime associated with each chemical and location. For xenobiotics,
a concentration of zero was used for individual samples in which the analyte was not detected.
(Specific sample detection limits for xenobiotics were not available.)
Standard EPA methods were used to estimate exposure and risk due to ingestion of fish
(US EPA, 1986b, 1989d). Exposure doses were determined using an equation that assumes a
constant daily fish ingestion rate over a lifetime (70 years).
where:
Dy = estimated dose (mg/kg/day) for chemical i at ingestion rate j
Ci = concentration of chemical i in fish or shellfish
Ij = ingestion rate for the jth percentile of the population
W = assumed human body weight (70 kg).
Risk Characterization
Potential upper-bound risks associated with each carcinogen were estimated as the prob-
ability of excess cancer using the equation.
150
-------
Rij = 1 - exp (- Djj x Pi)
where:
Rij = Risk associated with chemical i at consumption rate j
Pi = Carcinogenic potency factor for chemical i (mg/kg/day
Dij = Dose of chemical i at consumption rate j (mg/kg/day).
The carcinogenic potency factors used and methods of dose estimation are as described
above (see Dose Response Assessment and Exposure Assessment sections).
Potential hazards associated with noncarcinogenic toxic effects of the various chemicals
were expressed as a ratio:
Hij = Dij/R/Di
where:
Hij = Hazard index of chemical i at consumption rate j
Dij = Dose of chemical i at consumption rate j (mg/kg/day)
RfDj = Reference dose for chemical i (mg/kg/day).
The hazard index is a ratio of a dose of a chemical to the level at which noncarcinogenic
effects are not expected to occur (i.e., reference dose, RiD). If the value of the hazard index is less
than 1.0, it follows that toxic effects are not expected to occur. The methods of dose estimation are
as described above.
CARCINOGENIC RISK ESTIMATES
Potential upper-bound human carcinogenic risks were estimated for targeted and back-
ground sites using the maximum, mean, and median concentrations for all chemicals with CPF
values (Tables 6-2 and 6-3). The fish tissue concentrations associated with these estimated cancer
risks are given in Table 6-4. Table 6-5 presents a summary of the fish samples that exceed risk
levels of 10"6 to 10"3 for each of the chemicals with CPF values. The highest lifetime risk levels are
associated with total PCBs. The cancer risk exceeded 10"4 at 42 of 106 sites for total PCBs, for a
fish consumption rate of 6.5 g/day. PCBs also exceeded 10 risks at 10 sites. A complete list of
sites is presented in Appendix D-10.
Risks for chlordane were estimated for the sum of the cis- and trans-chlordane isomers, cis-
and trans-nonachlor isomers, and oxychlordane (referred to as combined chlordane). The CPF
factor for chlordane is used since separate cancer potency factors are not available for nonachlor
and oxychlordane. This method is consistent with the EPA's Office of Pesticide Programs, which
also combines the concentrations of the cis- and trans- isomers of chlordane and nonachlor with
oxychlordane and the four chlordene isomers (referred to as TTR-Total Toxic Residue). The four
chlordene isomers were not measured for this study. Heptachlor and heptachlor epoxide have
different CPF and RfD values from those for chlordane, so were not added.
151
-------
TABLE 6-2
Estimates of Potential Upper-Bound Cancer Risks
at Targeted Sites Based on Fillet Samples3'1"
Chemical
PCBs
DDE
Combined Chlordane
Dieldrin
a-Hexachlorocyclohexane
Y-Hexachlorocyclohexane
Hexachlorobenzene
Heptachlor
Heptachlor Epoxide
Mirex
Trifluralin
Dicofol
Hexachlorobutadiene
Pentachloroanisole
aConsumpiion rate of fish set at 6.
Maximum0
3.7xlO'3
8.9xlO'5
9.3xlO'5
6-OxlO"4
l.OxlO'5
S.lxlO"6
8.0xlO'6
1.2xlO'7
3.4xlO"5
3.8xlO"5
8.3xlO"8
6.1xlO"7
6.4xlO'7
7.2xlO'8
5g/day.
Mean
3.4X10"4
4.1xlO'6
3.6xlO'6
2.2xlO"5
4.4xl(T7
3.6xlO~8
2.5xlO"7
l.lxlO'7
8.7xlO'6
7.4xlO'7
1.7xlO"9
2.8xlO"8
7.1xlO'9
2.0xlO'9
No. of
Sites with
Median6 Fillet Data
6.0xlO'5 106
4.6xlO'7 106
5.5xlO"7 106
1.2xlO"6 106
— 106
— 106
— 106
— 106
— 106
— 106
— 106
— 106
— 106
— 106
Cancer Potency Factors used are given in Table 6-1.
c'cU Risk shown is associated with maximum, mean, and median fillet concentration at targeted sites.
Values below quantification set at zero.
Combined chlordane is the sum of cis- and trans-chlordane isomers, cis- and trans-nonchlor isomers, and
oxychlordane.
8Dash indicates median fillet concentration was below detection.
752
-------
TABLE 6-3
Estimates of Potential Upper-Bound Cancer Risks at Background*1 Sites
Based on Fillet Samples
Chemical
PCBs
DDE
Maximum3
3.2xlO"5
1.4xl(T6
Mean
8.0xlO'6
4.1xlO'7
Median0
—
1.4xlO"7
No. of
Sites with
Fillet Data
4
4
Consumption rate of fish set at 6.5 g/day.
CPF values used are given in Table 6-1.
Dash indicates median fillel concentration was below detection.
a blCRisk shown is associated with maximum, mean, and median fillet concentration at background sites.
Values below quantification were set at zero.
It is important to note that background risks are estimated from a small number of samples. Also, as
indicated in Chapter 2, the background samples were, in some cases, selected for purposes of comparison
and do not necessarily represent areas completely free from point and nonpoim sources of pollution.
Note:
All fillet concentrations at background sites were below detection for dieldrin, chlordane, alpha-BHC, gamma-BHC,
hexachlorobenzene, heptachlor, heptachJor epoxide, rnirex, trifluralin, dicofol, hexachlorobutadiene, and
pentachloroanisole.
153
-------
TABLE 6-4
Fish Tissue Concentrations Used to Estimate Cancer Risks
TARGETED SITES
Chemical
PCBs
DDE
Combined Chlordane
Dieldrin
a-Hexachlorocyclohexane
y-Hexachlorocyclohexane
Hexachlorobenzene
Heptachlor
Heptachlor Epoxide
Mirex
Trifluralin
Dicofol
Hexachloro butadiene
Pentachloroanisole
Maximum
5148.1
2820
770
405
17.5
6.68
50.7
0.28
40.7
225
116.0
14.9
88.3
48.6
Mean
477.4
130.6
29.6
15.1
0.75
0.30
1.6
0.003
1.0
4.42
2.35
0.68
0.98
1.3
Median
84.5
14.6
4.6
0.8
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
No. of
Sites with
Fillet Data
106
106
106
106
106
106
106
106
106
106
106
106
106
106
Units are ng/g unless noted.
BACKGROUND SITES
Chemical
PCBs
DDE
Maximum
44.8
43.0
Mean
11.2
13.0
Median
ND
4.4
No. of
Sites with
Fillet Data
4
4
All fillet concentrations at background sites were below detection for dieldrin, chlordane, alpha-BHC, gamma-BHC,
Hexachlorobenzene, heptachlor. beptachlor epoxide, mirex, tnfluralin, dicofol, hexachlorobutadiene, and
pentachloranisole.
Combined chlordane is the sum of cis- and trans-chlordane isomers, cis- and tram-nonachlor isomers, and
oxychlordane.
154
-------
TABLE 6-S
Number of Sites with Estimated Upper-Bound Risks
TARGETED SITES
RISK LEVEL (Cumulative)
Chemical
No. of Sites
with Fillet
Data (>lin 1.000,000)
-3
in 100,00)
10
in 10,000) (>1 in 1,000)
PCBs
Dieldrin
Combined Chlordane
DDE
Heptacblor Epoxide
Alpha- BHC
Mirex
HCB
Gamma-BHC
Heptachlor
Dicofol
Hexachlorobuladiene
Pentachloroanisole
Trifluralin
106
106
106
106
106
106
106
106
106
106
106
106
106
106
89
53
44
40
9
11
8
5
0
0
0
0
0
0
79
31
10
10
2
1
2
0
0
0
0
0
0
0
42
6
0
0
0
0
0
0
0
0
0
0
0
0
10
0
0
0
0
0
0
0
0
0
0
0
0
0
BACKGROUND SITES
Chemical
RISK LEVEL (Cumulative)
No. of Sites
with Fillet >106 >10'5 >10'4
Data (>1 in 1.000,000) (>1 in 100,000) (>l in 10,000) (>1 in 1,000)
PCBs
DDE
4
4
1
0
0
0
0
0
Basis: 1) Used EPA (i.e., upper bound) cancer potency factors.
2) Used consumption rate of 6.5 grams/day.
3) Used average fillet concentrations at the few sites with multiple samples.
Combined chlordane is the sum of cis- and trans-chlordane isomers, cis- and trans-nonachlor isomers, and
oxychlordane.
755
-------
The mean, median, and maximum risks using 30 g/day and 140 g/day are compared to the
risks using 6.5 g/day in Table 6-6. For the median fillet concentrations at targeted sites, estimated
risks equal or exceed 10"5 for PCBs at 6.5 g/day and 30 g/day. At the higher consumption rate of
140 g/day, estimated risks due to combined chlordane and dieldrin were also above 10' .
As a final step in the risk characterization, a graphical tool was developed for estimating
potential health risks at consumption rates from 1 to 1,000 g/day for all chemicals that exceeded a
10'6 risk level. These nomographs are included in Appendix B. As an example, the graph for
estimating the carcinogenic risks from p,p'-DDE is shown in Figure 6-1. In each graph, the methods
and assumptions outlined above were used to plot potential health risks for three consumption rates
(i.e., 6.5 g/day, 30 g/day, and 140 g/day). In addition to the consumption rates shown, a scale is
provided on each graph so that health risks can be estimated for any consumption rate in the range
of 1 to 1,000 g/day. This is an important feature because potential health risks may vary with
regional, cultural, or ethnic differences in species of fish eaten and consumption rates. Hence, using
the nomographs provided herein, it is possible to evaluate potential health risks associated with
specific consumption rates at a given site.
NONCARCINOGENIC RISKS
Noncarcinogenic hazard indices were summarized for targeted and background sites for the
chemicals with reference dose values available (Table 6-7). Based on a fish consumption rate of
6.5 g/day, the hazard index, defined previously, exceeded 1 (meaning adverse effects may occur)
at only a few targeted sites for PCBs, mirex, and combined chlordane. The hazard indices associated
with the mean and median concentrations for these same chemicals were less than 1.0. The hazard
indices for all chemicals at background sites were also less than 1.0.
Graphs for estimating noncarcinogenic hazard index values at various consumption rates
were prepared for most of the compounds evaluated. Using these graphs, one can determine whether
the hazard index would exceed a value of 1 at consumption rates between 1 and 1, 000 g/day. For
example, using the maximum DDE concentration at targeted sites (2,819 ng/g), a hazard index value
of 0.52 was estimated for a 6.5-g/day consumption rate, whiJe for a 30-g/day rate it was about 2
(Figure 6-2). The graphs for the other compounds are included in Appendix B following those for
estimating carcinogenic risks.
156
-------
TABLE 6-6
Estimated Upper-Bound Risks at Three Fish Consumption Rates Based on Fillet Samples
Maximum
Background 6.5 30 140
PCBs 3.2xl05 1.5xlcT4 6.9xl04
DDE UxlO"6 6.4xl06 3.0xl05
Targeted 6.5 30 140
PCBs 3.7xlO"3 1.7x1 1)"2 7.6xlO"2
DDE 8.9xlOS 4.lxl04 1.9xI03
Combined 9.3x10 5 4.3xl04 2.0xlO'3
Chlordane
Dicofol 6.lxllV7 2.8xl()"6 1.3xlO'5
Dieldrin 6.0xlO~4 2.8xl03 1.3xlO'2
a-Hexachloro- l.OxlO5 4.6xl()5 2.2xl04
cyclohexane
y-Hexachloro- 8.1xiO"7 3.7xl06 1.7xlO"5
cyclohexane
Hexachloro- 8.0x10 6 3.7xl05 1.7xlO~4
benzene
Hexachloro- 6.4xlO"7 3.0xl06 I.4xl05
butadiene
Heptachlor 1.2xlO"7 5.4xl06 2.5xlO"5
lleptachlor
Epoxide 3.4x1 0"5 1.6xlO"4 7.3xl04
Mirex 3.8xlO"5 l.SxlO"4 8.2xlO"4
Pentachloro- 7.2xlOK 3.3xlO"7 1.6xl06
anisole
Trifluralin 8.3xl08 3.8xl()'7 1.8xlO"6
Mean
Background 6.5 30 140
PTBs 8.0xl06 3.7xlO"5 17xl()'4
DDE 4.1xl07 1.9xlO"6 8.8xl06
Targeted 6.5 30 140
PCBs 3.4xlO"4 .6xlO~3 7.3xlO'3
DDE 41xlO'6 .9xl05 8.9xlO'5
Combined 3.6xl06 .6xl05 7.7xl05
Chlordane
Dicofol 2.8xIO"8 .3xlO'7 6.0xl()'7
Dieldrin 2.2xlO"5 .OxlO4 48xl()4
a-Hexachloro- 4.4xlO"7 2.0x1 0'6 9.4x1 0'6
cyclohexane
Y-Hexachloro- 3.6xlO'8 1.7xl07 7.8xl06
cyclohexane
Hexachloro- 2.5xlO'7 1.2xl06 5.4xlO"6
benzene
Hexachloro- 7.1xlO"9 3.3x10* l.SxlO7
butadiene
Heptachlor * * *
Heptachlor
Epoxide 8.4xl()'7 3.9xlO"6 1.8xlO"5
Mirex 7.4xlO"7 3.4xlO"6 1.6xl05
Pentachloro 1.9xlO"9 8.9xlO"8 4.2x10*
anisole
Trinuralin 1.7xlOv 7.8xlO'9 3.6xlO"s
Median
Background 6.5 30 140
PCBs
DDE 1.4xl()7 6.4xl07 3 OxlO"6
Taryeted 6.5 30 140
PCBs 6.0xI05 2.8xl04 1.3xl03
DDK 4.6xl()7 l.lxUY6 9.9xHV6
Combined 5.6xl07 2.6xl06 1.2xl05
Chlordane
Dicofol
Dieldrin 1.2xl06 5.5xlO'ft 2.6xl05
a-Hexachloro-
cyciohexane
y-Hexachloro-
cyclohexane
Hexachloro-
benzene
Hexachloro-
butadiene
Hcptachlor
Heptachlor
Epoxide
Mirex
Pentachloro-
anisole
Trifluralin
Basis: Used upper-bound CPFs f lable 6-2) fish consumption taws of 6.5, JO, and 1 40 g/day.
Dash indicates concenlraUon was reported as not delected.
Only one value was above delecliun, so risk not computed.
Combined chlordane is the sum of cis- and trans- chlordane istxners. cis and trans- nonachlor isomers. and oxychliiranc.
757
-------
.2
DC
i_
-------
TABLE 6-7
Noncarcinogenic Hazard Index Values at Targeted and Background Sites
Based on Fillet Samples
TARGETED
Chemical
Biphenyl
Combined Chlordane
Chloropyrifos
DDE
Dieldrin
Endrin
y-Hexachlorocyclohexane
Hexachlorobenzene
Heptachlor
Heptachlor Epoxide
Hexachlorobutadiene
Isopropalm
Mercury
Mirex
Pentachloronitrobenzene
Pentachlorobenzene
Pentachloroanisole
PCBs
1,2,4,5 Tetrachlorobenzene
1,2,4 Trichlorobenzene
Trifluralin
Maximum
9.8x10°
1.2
2.4x1 0"3
5.2x10"
7.5x10"'
43xlO"3
2.1x10,
5.9x10";
5.2x10 ~5
2.9x1 0'J
4.1xlO"3
ND
5.1x10"'
10.45
2.7x1 0"5
6.0x1 0"3
l.SxlO"4
4.78
8.8xlO"3
A
4.8x10^
1.4xlO"3
Mean
2.0x1 0"6
4.6x10'^
6.4x10"^
2.4x10";
2.8x10""
9.6x10",
9.3x10"
A
1.9x10*
5.6x10"^
7.1x10"*
4.6xlO"5
ND
9.0x10,
2.1xlO"j
2.5x1 0"7
1.3x10
40x10",
4.4X10"1
1.2X10"4;
7.2x10"^
2.9x10"
Median
3.5x10"^
7.1xlO"3
ND
2.7xlO"3
l.SxlO"3
ND
ND
ND
ND
ND
ND
ND
7.1xlO"2
ND
ND
ND
ND,
7.8x10""
ND
6.5xlO"7
ND
No. of
Sites with
Fillet Data
106
106
106
106
106
106
106
106
106
106
106
106
182
106
106
106
106
106
106
106
106
BACKGROUND
Chemical
Biphenyl
Combined Chlordane
Mercury
1 ,2,4 Trichlorobenzene
PCBs
p,p'-DDE
Maximum
3.7xlO"J
5.0x1 0'3
5.5x10"'
3.3x10"^
4.2x10";:
S.OxlO"3
(All other chemicals were not detected in
Mean
2.2x10"^
l.OxlO"3
1.5x10"'
1.6x10",
1.0x10,
2.0xlO'3
background samples)
Median
2.5xlO"7
ND
1.2x10"'
l.SxlO"6
ND
l.OxlO"3
No. of
Sites with
Fillet Data
4
4
1
4
4
4
Consumption rate of fish at at 6.5 g/day. RfD values used are given in Table 6-2.
ND, not detected.
Combined chlordane is the sum of cis- and trans-chlordane isomers, cis- and trans-nonachlor isomers, and
oxychlordane.
159
-------
p,p'-DDE NONCARCINOGENIC EFFECTS
100 -,
10
X
0)
£
"2
CO
N
1 -
0.01 -
0.001
1000
Consumption Rate (grams/day)
100 10
o.oooi
100
1000
0.001 0.01 0.1 1 10
Fish Tissue Concentration
(mg/kg wet wt)
Figure 6-2. Graphical tool for estimating upper-bound noncarcinogenic hazard index of
p,p'-DDE for different fish consumption rates.
10000
760
-------
References
APHA (American Public Health Association). 1985. Standard Methods for Analysis of Water and
Wastewater. 16th ed. APHA.
ATSDR (Agency for Toxic Substances and Disease Registry). 1987. Draft Toxicological Profile
for 2,3,7,8-Tetrachlorodibenzo-p-Dioxin. ATSDR, U.S. Public Health Service, Oak Ridge
National Laboratory, Oak Ridge, TN.
Barnes, D.G., and J.S. Bellin. 1989. Interim Procedures for Estimating Risks Associated with
Exposures to Mixtures of Chlorinated Dibenzo-p-Dioxins and -Dibenzofurans (CDDs and
CDFs). U.S. Environmental Protection Agency, Risk Assessment Forum, Washington, DC.
Brown, J.F., Jr., B.L. Bedard, M.J. Brennan, J.C. Carnahan, H. Feng, and R.E. Wagner. 1987.
Polychlorintated Biphenyl. Dechlorination in Aquatic Sediments. Science 236:709-712.
Dorman, M. 1985. Memo to R. Frederick at U.S. Enivronmental Protection Agency from M.
Dorman of Versar, Inc. Toxic Weighting Factors, February 12, 1985, as referenced in U.S.
EPA, 1986a.
Glass, G.E., J.A. Sorensen, K.W. Schmidt, and G.R. Rapp. 1990. New Source Identification of
Mercury Contamination in the Great Lakes. ES&T 24 (7): 1059-1069.
Horwitz, W., ed. 1983. Official Methods of Analysis of the Association of Official Analytical
Chemists. 13th ed., pp. 404-406.
IRIS. 1988. Integrated Risk Information System. U.S. Environmental Protection Agency, Wash-
ington, DC.
IRIS. 1989. Integrated Risk Information System. U.S. Environmental Protection Agency, Wash-
ington, DC
Merhle, P.M., D.R. Buckler, E.E. Little, L.M. Smith, J.D. Petty, P.H. Peterson, D.L. Stalling, G.M.
Degaeve, J.J. Goyle, and W.L. Adams. 1988. Toxicity and Bioconcentration of 2,3,7,8-
Tetrachlorodibenzo-p-dioxin and 2,3,7,8-Tetrachlorodibenzofuran in Rainbow Trout. Environ.
Toxic. Chem. 7(l):47-62.
NAS (National Academy of Sciences). 1978. Kepone/Mirex/Hexachlorocyclopentadiene: An
Environmental Assessment. National Academy of Sciences, National Research Council, Wash-
ington, DC NTIS PB 280289.
161
-------
NTP (National Toxicological Program). 1982a. Bioassay of 2,3,7,8-Tetrachloro-dibenzo-p-dioxin
for Possible Carcinogenicity (Gavage Study). DHHS Publ. No. (NIH) 82-1765. Carcinogenesis
Testing Program, NCI, NIH, Bethesda, MD; National Toxicology Program, Research Triangle
Park, NC
NTP (National Toxicological Program). 1982b. Bioassay of 2,3,7,8-Tetrachloro-dibenzo-p-dioxin
for Possible Carcinogenicity (Dermal Study). DHHS Publ. No. (NIH) 82-1757. Carcinogen-
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Olson, G.F., D.I. Mount, V.M. Snarski, and T.W. Thorslund. 1975. Mercury Residues in Fathead
Minnows, Pimephalespromelas Rafinesque, Chronically Exposed to Methylmercury in Water.
Bull. Env. ConL Tox. 14:129-134.
Palmer, F.H., R.A. Sapudar, J.A. Heath, NJ. Richard, and G.W. Bowes. 1988. Chlorinated
Dibenzo-p-Dioxin and Dibenzofuran Contamination in California from Chlorophenol Wood
Preservative Use. California State Water Resources Control Board, Report No. 88-SWQ.
PHRED. 1988. Pub lie Health Risk Evaluation Database. U.S. Environmental Protection Agency,
Office of Emergency and Remedial Response, Washington, DC.
Rappe, C, H.R. Buser, and H.P. Bosshardt. 1979. Environmental Science and Technology
18(3):78A-90A.
Resources for the Future. 1986. A National Pesticide Usage Data Base. February 1986.
Robins, C.R., et al. 1980. A List of Common and Scientific Names of Fishes from the United States
and Canada. 4th ed. American Fisheries Society. Special Publication No. 12.
Scott, W.B., and E.J. Grossman. 1973. Freshwater Fishes of Canada. Fisheries Research Board
of Canada. Bulletin 184.
Smith, P. W. 1979. The Fishes of Illinois. University of Illinois Press, Chicago, IL.
Smith, L.M., T.R. Schwartz, K. Feltz, and T.J. Kubiak. 1990. Determination and Occurrence of
AHH-Active Polychlorinated Biphenyls, 2,3,7,8-Tetrachloro-p-dioxin and 2,3,7,8-
Tetrachlorodibenzofuran in Lake Michigan Sediment and Biota. The Question of Their Relative
Toxicological Significance. Chemosphere 21(9): 1063-1085.
Takamiy a, K. 1987. Residual Levels of Plasma Oxychlordane and Trans-nonachlor in Pest Control
Operators and Some Characteristics of These Accumulations. Bull. Environ. Contain. Toxicol.
39: 750-755.
Tobin, P.M. 1984. Memo to S. Schatzow of U.S. Environmental Protection Agency, Office of
Water Regulations and Standards. Priority pollutant ranking system, May 29, 1984, as refer-
enced in U.S. EPA, 1986a.
162
-------
Trautman, M.B. 1957. The Fishes of Ohio. Ohio State University Press, Columbus, OH.
U.S. EPA. 1972. Water Quality Criteria, 1972 (the Blue Book, NAS/NAE, 1972). U.S. Environ-
mental Protection Agency, Office of Water Regulations and Standards, Washington, DC. EPA
R3-73-033.
U.S. EPA. 1980a. Ambient Water Quality Criteria Documents (various). U.S. Environmental
Protection Agency, Office of Water Regulations and Standards. EPA 440/5-80 Series.
U.S. EPA. 1980b. List of Chemicals Having Substantial Evidence of Carcinogenicity. U.S.
Environmental Protection Agency, Carcinogen Assessment Group, Washington, DC.
U.S. EPA. 1980c. Exposure-Based Candidates for Existing Chemical Review, U.S. Environmental
Protection Agency, Office of Toxic Substances memo from J. J. Merenda to M.P. Halper, as
referenced in U.S. EPA, 1986a.
U.S. EPA. 1984. Sampling Guidance Manual for the National Dioxin Study. U.S. Environmental
Protection Agency, Washington, DC.
U.S. EPA. 1985a. Ambient Water Quality Criteria Documents (various). U.S. Environmental
Protection Agency, Off ice of Water Regulations and Standards, Washington, DC. EPA 440/5-85
Series.
U.S. EPA. 1985b. Guidelines for Deriving Numerical National Water Quality Criteria for the
Protection of Aquatic Organisms and Their Uses. U.S. Environmental Protection Agency,
Office of Water Regulations and Standards, Washington, DC. PB85-227049.
U.S. EPA. 1986a. Work/Quality Assurance Project Plan for the Bioaccumulation Study. U.S.
Environmental Protection Agency, Office of Water Regulations and Standards, Monitoring and
Data Support Division, Washington, DC. July 1986.
U.S. EPA. 1986b. Superfund Public Health Evaluation Manual. U.S. Environmental Protection
Agency, Office of Emergency and Remedial Response, Washington, DC. EPA 540/1-86/060.
U.S. EPA. 1987a. Ambient Water Quality Criteria Documents (various). U.S. Environmental
Protection Agency, Office of Water Regulations and Standards, Washington, DC EPA 440/5-
87 Series.
U.S. EPA. 1987b. The National Dioxin Study. U.S. Environmental Protection Agency, Wash-
ington, DC. EPA 440/4-87-003.
U.S. EPA. 1987c. Interim Procedures for Estimating Risks Associated with Exposures to Mixtures
of Chlorinated Dibenzo-p-dtoxins and -Dibenzofurans (CDDs and CDFs). U.S. Environmental
Protection Agency, Risk Assessment Forum, Washington, DC. EPA/625/3-87/012.
163
-------
U.S. EPA. 1989a. Analytical Procedures and Quality Assurance Plan for the Determination of
Mercury in Fish. U.S. Environmental Protection Agency, Environmental Research Laboratory,
Duluth, MN. April 1989.
U.S. EPA. 1989b. Exposure Factors Handbook. U.S. Environmental Protection Agency, Office
of Health and Environmental Assessment, Exposure Assessment Group, Washington, DC.
EPA/600/8-89/043.
U.S. EPA. 1989c. Health Effects Assessment Summary Tables (HEAST). U.S. Environmental
Protection Agency, Office of Solid Waste and Emergency Response, Washington, DC.
U.S. EPA. 1989d. Risk Assessment Guidance for Superfund: Human Health Evaluation Manual.
Part A, Interim final. U.S. Environmental Protection Agency, Washington, DC. Report No.
05-230.
U.S. EPA. 1990a. Aquatic Toxicity Information Retrieval (AQUIRE) Data Base. U.S. Environ-
mental Protection Agency, Environmental Research Laboratory, Duluth, MN.
U.S. EPA. 1990b. Analytical Procedures and Quality Assurance Plan for the Determination of
PCDD/PCDF in Fish. U.S. Environmental Protection Agency, Washington, DC. EPA/600/3-
90/022.
U.S. EPA. 1990c. Analytical Procedures and Quality Assurance Plan for the Determination of
Xenobiotic Chemical Contaminants in Fish. U.S. Environmental Protection Agency, Washing-
ton, DC. EPA/600/3-90/023.
Wydoski, R.S., and R.R. Whitney. 1979. Inland Fishes of Washington. University of Washington
Press, Seattle, WA.
Additional specific references for the study compounds are included in the chemical profiles,
Appendix C. These references include physical/chemical properties, standards and criteria, major
compound uses, health effects, aquatic life effects where available, and factors used to estimate risks
(e.g., CPF, RfD, BCF).
164
-------
Glossary
Bioaccumulation
BCF
CPF
Combined
Chlordane
Congeners
GC/MS
Hazard Index
The net accumulation of a chemical from combined exposure to water, food,
and sediment by an organism. This may be further defined as accumulation
under a non-steady-state or equilibrium condition of exposure.
The bioconcentration factor (BCF) is the partition coefficient for the distri-
bution of chemical between water and an organism exposed only through
water. BCF = Ct/Cw, where Ct = concentration of a chemical in wet tissue
(either whole organism or specified tissue) and Cw = concentration of a
chemcial in water. The higher the BCF value, the greater the potential for
high concentrations of a chemical to occur in fish tissue samples. BCF values
given in the chemical profiles in Volume II are based on water and fish tissue
concentrations.
Cancer potency factor expressed in units of (mg/kg/day)" based on experi-
ments to determine whether a chemical causes cancer. The method used by
EPA to derive this value is to set the CPF equal to the upper 95 percentile of
the slope of the linearized multistage model for extrapolation of cancer from
high to low doses. Cancer risks derived using this approach are referred to
as upper-bound risks.
Combined chlordane is the sum of cis- and trans-chlordane isomers, cis- and
trans-nonchlor isomers, and oxychlordane.
Related chemical compounds with same basic structure but different number
of substitutions (e.g., chlorine). Examples of congeners investigated in this
project include the chlorinated dibenzo-p-dioxins (e.g., 2,3,7,8 TCDD with
four chlorines and 1,2,3,7,8 PeCDD with five chlorines). Such congeners
are sometimes referred to as homologs.
Gas chromatography/mass spectrometry, a laboratory analytical method
used in this study for PCDDs, PCDFs, and other xenobiotic compounds.
Ratio of dose of a chemical to the level at which noncarcinogenic effects are
not expected to occur (reference dose or RfD). If the value of the hazard
index is less than 1, no toxic effects should occur from the dose tested (e.g.,
ingestion of fish at a given consumption rate with a specified contaminant
concentration).
165
-------
Isomers
NPL
PCDDs
PCDFs
RfD
TEC
TEF
TEQ
Total Chlordane
TTR
Xenobiotic
Related chemical compounds that have the same molecular formula but are
structurally different. An example of isomers investigated during this study
include cis- and trans-chlordane.
Waste disposal sites included on the National Priority List for clean-up under
CERCLA/SARA, also referred to as Superfund sites.
Polychlorinated dibenzodioxins
Polychlorinated dibenzofurans
Reference dose expressed in units of mg/kg/day. The RFD is the estimated
single daily chemical intake rate that appears to be without toxic effects if
ingested over a lifetime.
Toxicity equivalency concentration for dioxins and furans. This represents
a toxicity-weighted total concentration of all individual congeners using
2,3,7,8 TCDD as the reference compound. The 1989 interim method advo-
cated by EPA was used for this study (Barnes et al., 1989).
Toxicity equivalency factors for dioxins and furans. These factors express
the relative toxicity of the 2,3,7,8-substituted congeners. The values used in
this study were from the 1989 interim method (Barnes et al., 1989).
Toxicity equivalents for dioxins and furans (Barnes et al., 1989). This term
has the same meaning as TEC.
Total chlordane refers to the sum of the measured concentration of cis- and
trans-isomers of chlordane measured in the same sample.
Total toxic residue equals the combined concentration of cis- and trans-chlor-
dane, cis- and trans-nonachlor, oxychlordane, and the four chlordene iso-
mers. This combined concentration is used by EPA's Office of Pesticide
Programs.
Compounds that do not naturally occur in living organisms.
166
-------
APPENDIX A
Laboratory QA/QC Procedures and Results
-------
APPENDIX A-l
Analysis of Laboratory QA/QC Data
-------
Appendix A-l - Analysis of Laboratory QA/QC Data
The QA/QC procedures, as mentioned in Chapter 2 and listed in Table A-1, included analysis
of reference fish spiked with the chemicals being studied, analysis of method blanks and duplicate
tissue samples, and confirmation sampling using a second GC column. The total number of QA/QC
samples of each type is listed below:
Number of Analyses
Reference Fish 142
Method Blanks 135
Duplicate Samples 117
Confirmation Samples 41
These data were used by the EPA Duluth laboratory to estimate analytical precision and
bias.
BIAS
Bias is a systematic error resulting in values that are too high or too low. It can be measured
using spiked samples and is defined as follows:
B = (100(Ca - Cb)/T)-100
where:
B = percent bias
Ca = measured concentration of anaiyte after spiking
Cb = original concentration in sample
T = amount of spike added to sample.
Reference fish, not containing dioxin/furan, were used in this study to determine bias. The
QA/QC criteria, listed in Table A-2, specify that the bias be ± 50 percent for tetra- and penta-
dioxin/furan congeners, + 100 percent for hexa- and hepta-dioxins and hexa-furans, and ± 200
percent for hepta-furans. Method bias achieved is reported in Table A-3 for PCDD/PCDF analysis.
The reported values are for standard solutions in tridecane solvent and represent the three spiking
levels indicated in the Analytical Procedures and Quality Assurance Plan for the Determination of
Mercury in Fish (U.S. EPA, 1989a). Method bias prior to the use of the tridecane solvent was, in
general, lower. Mean recovery for the dioxins/furans ranged from 94 percent to 109 percent. The
percent bias ranged from +9 percent to -6 percent Thus, the above criteria for bias were met.
The bias QA/QC criteria for xenobiotics were defined in terms of individual anaiyte recovery
and total anaiyte recovery. The bias for specific analytes must be between +50 percent and +130
percent, except for the following compounds:
A-l-l
-------
TABLE A-l
Laboratory Quality Assurance Procedures
1. All instrument maintenance schedules maintained according to the manufacturer's
recommendations
2. Gas Chromatography (GC) performance
a) Xenobiotics
1. Column resolution (number of theoretical plates of resolution must not
decrease by more than 20%)
2. Relative retention times ( 3%) of internal standards
b) PCDD/PCDF
1. Resolution of 1,2,3,4 TCDD from 2,3,7,8 TCDD must be 0.75
2. The R value of the regression of the relative retention time of all
biosignificant PCDD/PCDF to the library relative retention should not be
<0.995
3. Elution of all PCDD/PCDF during analysis from a GC window defining
solutions of select PCDD/PCDF congener groups (first eluted/last eluted)
3. Mass Spectrometry (MS) performance
a) Xenobiotics
1. Sensitivity (signal-to-noise ratio, 3.0 for m/z 198 from injection of 10.0 ng
decafluorotripnenylphosphine [DFTPP])
2. Spectral quality (intensity of ions in the spectrum of DFTPP must meet
specified criteria)
b) PCDD/PCDF
1. Sensitivity and linearity were evaluated using calibration standards (in pg/p.1
tridecane) which varied in concentration
2. Mass resolution was a minimum of 5,000 (10% valley definition)
3. Percent relative standard deviations for the mean response factors were <20%
4. Gel Permeation Chromatography (GPC) performance
a) Xenobiotics
1. Column flow rate (not vary by more than 0.2 ml/min)
2. Column resolution (daily injection of performance solution)
3. Collection cycle (start and end of the collect cycle must not deviate by more
than 2 ml)
5. Silica Gel Chromatography performance
a) Xenobiotics
1. Evaluated by its ability to resolve cholesterol from a select model target
analyte, dieldrin
A-l-2
-------
TABLE A-2
Quality Assurance Parameters for Dioxins and Furans
TCDD
PCDD
HxCDD
HpCDD
TCDF
PCDF
HxCDF
HpCDF
Ion Ratio
0.76±15%
0.61±15%
1.23±15%
1.02±15%
0.76±15%
1.53±15%
1.23±15%
1.0211 5%
* Variance of measured value from actual.
b Variance of difference of duplicates from
Method3
Efficiency
>40%,<120%
>40%,<120%
>40%,<120%
>40%,<120%
>40%,<120%
>40%,<120%
>40%,<120%
>40%,<120%
mean.
Accuracy3
at 10 pg/R
±50%
±50%
±100%
±100%
±50%
±50%
±100%
200%
Precision
at 10 pg/g
±50%
±50%
±100%
±100%
±50%
±50%
±100%
200%
S/N
Minimum
3.0
3.0
3.0
3.0
3.0
3.0
3.0
3.0
A-l-3
-------
TABLE A-3
Bias Analysis for PCDDs/PCDFs
Chemical
2,3,7,8 TCDF
2,3,7,8 TCDD
1, 2,3,7,8 PeCDF
2,3,4,7,8 PeCDF
1, 2,3,7,8 PeCDD
1, 2,3,4,7,8 HxCDF
1, 2,3,6,7,8 HxCDF
2,3,4,6,7,8 HxCDF
1,2,3,7,8,9 HxCDF
1, 2,3,4,7,8 HxCDD
1, 2,3,6,7,8 HxCDD
1,2,3,7,8,9 HxCDD
1, 2,3,4,6,7,8 HpCDF
1, 2,3,4,7,8,9 HpCDF
1,2,3,4,6,7,8 HpCDD
Mean
Recovery
109
102
104
104
100
95
104
96
94
99
108
96
99
104
103
Stan. Dev.
16
13
14
12
13
10
17
11
12
24
13
11
11
14
12
% Bias
9
2
4
4
0
-5
4
-4
-6
-1
8
-4
-1
4
3
A-l-4
-------
Trichlorobenzenes (1,3,5-; 1,2,4-; and 1,2,3-);
• Tetrachlorobenzenes (1,2,4,5-; 1,2,3,5-; and 1,2,3,4-);
Pentachlorobenzene; and
Biphenyl.
The recovery for these analytes is low due to some losses during the evaporation steps. The
average analyte recovery for the spiked analytes was then determined for these analytes. The
QA/QC criteria specified that this value be greater than 35 percent and less than 130 percent (Table
A-4).
The bias results are shown in Table A-5 for PCBs and Table A-6 for the remaining
xenobiotics, excluding mercury. Mean recoveries for PCBs were estimated using data for PCBs
with 3 to 7 chlorines with the recoveries ranging between 58 and 101 percent. The recoveries were
higher for the more heavily chlorinated compounds. Bias for the above PCBs ranged between + 8
and -37 percent and thus met the criteria.
Method bias values for xenobiotics were determined from two spiking levels (Analytical
Procedures and Quality Assurance Plan, U.S. EPA, 1989a). Method bias for xenobiotic analytes
varies considerably compared to PCDD/PCDF analysis. As expected, low recoveries are exhibited
by the chlorinated benzenes and other semivolatile compounds due to the concentration steps in the
analytical procedure. The percent bias for the analytes other than chlorinated benzenes and biphenyl
ranged from -45 to +14. The average analyte recovery was 73.8, well within the overall QA/QC
criteria.
The QA/QC criteria for mercury are listed in Table A-7. The amount of tissue analyzed
decreased from 1.0 g to 0.2 g in 1990 to obtain results within the instrument calibration range
established at a lower detection limit. The detection limit for samples analyzed in 1990 was 0.0013
Hg/g tissue. Analysis and EPA reference fish (mean value 2.52 |J.g/g, standard deviation (s) = 0.64)
throughout the study gave a mean mercury value of 2.87 ng/g (s = 0.08). This gives a bias of +14
percent for mercury'.
PRECISION
Precision (P) measures the reproducibility of the analyses. It can be determined as follows:
P = difference between duplicate samples x 100
mean of duplicate
The precision criteria for dioxin/furan congeners are the same as those listed earlier for method bias.
Specific precision criteria for the individual xenobiotics were not listed in the Analytical Procedures
and Quality Assurance Plan (U.S. EPA, 1989a). The original Work Plan for the study (U.S. EPA,
I986a) listed a general criterion for precision of ± 50 percent.
Estimates of intralaboratory precision expressed as the standard deviation for replicate pairs
are presented in Table A-8 for dioxins/furans and in Table A-9 for selected xenobiotics. The
A-l-5
-------
TABLE A-4
QA/QC Criteria for Xenobiotics Analyses
1. GC relative retention time for the target analytes could not deviate by more than + 3%
from calibration curve values.
2. Analyte identification criteria - reverse search identification of an analyte must have an FIT
value of 800.
3. Signal-to-noise ratio - quantification ion must have a ratio of 3.0.
4. Relative response factor for each analyte quantification ion relative to the appropriate
internal standard quantification ion must not deviate by 20% from the previous day's
value, and must be within 50% of the mean value from the calibration curve.
5. Percent recovery of each surrogate standard must be determined and must be within 25 and
130 percent for iodonaphthalene and 50 and 130 percent for 4,4'-diiodobiphenyl.
6. Average analyte recovery for all target analytes must be greater than 35% but less than
130%, and for the fortified analytes (except several chlorobenzenes, biphenyl, and
hexachlorobutadiene) recovery must be within a range of 50 to 130 percent.
TABLE A-5
Bias Analysis for Polychlorinated Biphenyls
Chemical
Tetrachlorobiphenyl
Pentachlorobiphenyl
Hexachlorobiphenyl
Heptachlorobiphenyl
Mean
Recovery
63
90
108
99
Stan. Dev.
16.5
12
11
23
% Bias
-37
-10
8
-1
A-l-6
-------
TABLE A-6
Bias Analysis for Xenobiotics
Chemical
1,3,5 Trichlorobenzene
1 ,2,4 Trichlorobenzene
1,2,3 Trichlorobenzene
1 ,2,4,5 Tetrachlorobenzene
1,2,3,5 Tetrachlorobenzene
Biphenyl
1 ,2,3,4 Tetrachlorobenzene
Pentachlorobenzene
Trifluralin
alpha-BHC
Hexachlorobenzene
Pentachloroanisole
gamma-BHC (Lindane)
Pentachloronitrobenzene
Diphenyl disulfide
Heptachlor
Chlorpyrifos
Isopropalin
Octachlorostyrene
Heptachlor epoxide
Oxychlordane
Chlordane, trans
Chlordane, cis
Nonachlor, trans
p,p'-DDE
Dieldrin
Nitrofen
Endrin
Perthane
Nonachlor, cis
Methoxychlor
Dicofol
Mirex
Mean
Recovery
25
25
21
32
39
27
33
43
86
67
58
67
64
71
82
68
106
84
96
88
76
92
97
96
95
100
114
102
78
99
55
96
90
Stan. Dev.
7
11
11
16
12
10
15
16
25
18
16
18
16
19
26
18
16
49
24
11
14
15
24
22
23
14
20
14
32
22
27
27
20
% Bias
-75
75
-79
-68
-61
-73
-67
-57
-14
-33
-42
-33
-36
-29
-18
-22
6
-16
-4
-12
-24
-8
-3
-4
-5
0
14
2
-22
-1
-45
-4
-10
A-l-7
-------
TABLE A-7
QA/QC Criteria for Mercury Analyses
1. Samples are analyzed in batches of 20 to 25, with at least 20% additional reagent blank
and duplicate samples per batch.
2. The detection limit for a batch analysis is not to exceed 50% above the detection limit of
0.050 ng/g tissue, or samples are reanalyzed.
3. Complete reagent blanks are to produce a mercury signal equivalent to less than 0.15
(ig/g tissue.
4. Signal response to the standards is not to drop below 50% of the optimum value. The
instrument is reoptimized if this criterion is not met.
5. The standard deviation for batch duplicates is not to exceed two times the standard
deviation for the optimum determined value. Samples outside this range are reanalyzed.
6. Analysis of EPA reference samples for mercury in fish is used to assess accuracy.
A-l-8
-------
TABLE A-8
Intralaboratory Precision Measurements for Replicate Pairs for PCDD/PCDF Analysis
Chemical
2,3,7,8 TCDF
2,3,6,7 TCDF
2,3,7,8 TCDD
1,2,3,7,8 PeCDF
2,3,4,7,8 PeCDF
1, 2,3,7,8 PeCDD
1,2,3,4,7,8 HxCDF
1,2,3,6.7,8 HxCDF
2,3,4,6,7,8 HxCDF
1,2,3,4,7,8 HxCDD
1,2,3,6,7,8 HxCDD
1,2,3, 7,8,9 HxCDD
1,2,3,4,6,7,8 HpCDF
1, 2,3,4,6,7,8 HpCDD
aX = concentration
s = standard deviation
#of
Observations
51
13
41
14
29
25
18
9
11
11
29
8
11
33
Precision2 (pg/g)
s=0.07X
s=0.08X
s=0.08X
s=0.21
s=0.09X
s=0.91
s=1.37
s=0.11X
s=0.17X
s=0.13X
s=0.11X
s=0.11X
s=0.77
s=0.08X
Concentration
Range (pg/g)
1 to 100
1 to 30
1 to 120
1 to 10
1 to 50
1 to 30
1 to 50
1 to 30
1 to 5
1 to 10
1 to 35
1 to 10
1 to 15
2 to 150
A-1-9
-------
Intralaboratory Precision
Chemical
1 ,3,5 Trichlorobenzene
1 ,2,4 Trichlorobenzene
1,2,3 Trichlorobenzene
Hexachlorobutadene
Biphenyl
1 ,2,3,4 Tetrachlorobenzene
Pentachlorobenzene
Trifluralin
alpha-BHC
Pentachloroanisole
gamma-BHC (Lindane)
Pentachloronitrobenzene
Heptachlor
Chlorpyrifos
Isopropalin
Heptachlor epoxide
Oxychlordane
Chlordane, trans
Chlordane, cis
Nonachlor, trans
p,p'-DDE
Dieldrin
Endrin
Nonachlor, cis
Dicofol
Mirex
Tetrachlorobiphenyl
Pentachlorobiphenyl
Hexachlorobiphenyl
Heptachlorobiphenyl
Octachlorobiphenyl
Hexachlorobenzene
8X= concentration
s = standard deviation
TABLE
Measurements for
Number of
Observations
5
5
5
6
5
6
5
6
7
10
8
5
6
8
7
6
11
14
13
21
29
17
5
13
5
5
14
26
28
21
6
4
A-9
Replicate Pairs for
Concentration
Precision3 (ng/g)
s=13.05
s=0.28X
s=5.39
s=0.39X
s=0.19X
s=0.35X
s=0.04X+5.04
s=0.19X
s=0.05X+1.70
s=0.25X
s=0.12X
s=38.81
s=7.44
s=0.05X+8.09
s=38.43
s=0.13X
s=0.12X
s=0.10X
s=0.10X
s=0.16X
s=0.17X
s=0.10X
s=0.10X
s=0.13X
s=0.03X+5.66
s=0.07X
s=0.17X
s=0.16X
s=0.14X
s=8.33
s=0.15X+1.41
N/A
Xenobiotic Analysis
Range (ng/g)
40 to 100
8 to 120
15 to 120
30 to 150
4 to 110
30 to 150
50 to 200
2.5 to 150
2.5 to 250
2.5 to 240
3 to 240
70 to 280
50 to 250
4 to 300
10 to 500
15 to 260
4 to 300
3 to 300
3 to 200
4 to 400
10 to 400
3 to 400
100 to 500
5 to 300
20 to 300
4 to 300
10 to 280
7 to 1000
8 to 1000
7 to 120
6 to 100
2 to 36
A-I-10
-------
standard deviation, s, and coefficient of variation (CV) for each duplicate pair were determined and
then plotted against the mean concentration. For most analytes, s increased as the mean increased
and CV appeared constant. For these analytes the average CV was used as the precision summary.
The precision is reported as s = (average CV)X, where X is the mean concentration of the duplicate
pair. The pooled standard deviation value was used as the precision summary for 1,2,3.7.8 PeCDF;
1,2,3,4,7,8 PeCDD; 1,2,3,4,7,8 HxCDF; 1,2,3,4,6,7,8 HpCDF: 1,3,5 and 1,2,3 trichlorobenzene;
pentachloronitrobenzene; and isopropalin.
CV decreased with increasing concentration, and s appeared constant over the concentration
range for these analytes. For pentachlorobenzene, alpha-BHC, chlorpyrifos, dicofol, and oc-
tachlorostyrene, precision was determined by a least-squares linear regression since s increased with
concentration and CV decreased with concentration. Precision is not reported for some analytes
since not enough data were collected to make any conclusions.
Mercury precision for replicate pairs was estimated as s = 0.047 (ig/g in the concentration
range of 0.08 ^ig/g to 1.79 (ig/g for 20 samples.
DATA COMPLETENESS
The original work plan (U.S. EPA, 1986a) specified a target for data completeness of 80
percent. This was to be based on verified data as a percentage of all reported data. For the dioxins
and furans, 4 percent of all values did not meet the QA/QC criteria and are reported as "QR" in the
data base. The xenobiotic data were tested throughout the study and if a run did not meet the 80
percent completeness criteria, the set of samples was rerun. No "QR" values were reported for
xenobiotics. Thus, the criterion of 80 percent valid data was met.
A-l-ll
-------
APPENDIX A-2
Analytical Procedures and Quality Assurance Plan for
the Determination of PCDD/PCDF in Fish
-------
United States
Environmental Protection
Agency
Environmental Researcn
Laboratory
Duluth MN 55804
EPA600 3-90*022
March 1990
Researcn and Deveiooment
oEPA
Analytical
Procedures and Quality
Assurance Plan for the
Determination of
PCDD/PCDF in Fish
-------
EPA/600/3-90/022
March 1990
U.S. tnv
-------
HOTICI
ir«tor««t(on in this docw««nt hat boon fundad wholly or in part by th« u.S
tnv(ron«««t•I Protection *9«ncy. It *»• b««n rtvi«««d ttehnleclty tnd
td»lnI•tratfvt(y. »«ntten a* tradt na««a or eoaaxreial product* do«* not
con*tftutt «ndor*«a*nt or r ac •••enda t I or> tor u««.
12/89 QA/QC PC»0/»COr H
-------
ACKNOWKOCINC NTS
Ttehnlcal eantributIent to tMi rtaoarch woro ••«• by:
U.S. giY'ron««ntai »rat«etI on A«anev
Irian C. lut tarworth
Oouiiaa w. KuaM
Ai e I C o roor11 ian
Phillip j. Hcrquil
Miri* I. I »rt«n
Ltrry G. Holland
Christlno C. todtrborf
j tnnt ftr A. j ohnton
Ktvln i. Hogftldt
Un i vtrt(tY of Wlieonitn-luporior
E I I xabotlt A . Lun4«*r k
0«n i »I N. F rt«g«n
Sandra Mau«ann
Nurrty Naekot t
Kint Johnton
Hi rvty 0. Corbin, jr.
Or . lay L. Hanion
wr 1 ah t S t att Unixartitv
0 r . Tho*at T f trnan
Or. Ml ehaol Taylor
it/it QA/oe •coo/»eor
HI
-------
FOREWORD
Directed by Congressional mandate, the U.S. Environmental Protection Agency
during 1983 initiated the National Oioxin Study, • survey of environmental
contamination by 2,3 , 7,8 - tetrachIorodibenzo-p-dioxin (TCOO) in the United
States. Results of this study are published in the National Dioxin Study:
Tiers 3,5,6, and 7, EPA 400/4-82-003. This laboratory, the Environmental
Researcn Laboratory- Duluth, was responsible for one pert of the Study, the
analysis of fish samples. The most significant finding* of these analyses was
the observation that fish contamination wet more videapread then previously
thought, and that a primary source of TCOO was discharge from pulp and paper
production using chlorine.
A second more detailed characterization of anthropogenic organic chemical
contaminants in fish was conducted in subsequent analyses during what is now
called Phase II of the National Oioxin Study. This document describes the
analytical methods used for the determination of the level of contamination of
fifteen biosignificant poIychIorinated dibenxo-p-dtoxin* and dibenzofurens in
fish. A companion document (EPA /600/3 - 90/023 ) deacribes the analytical methods
used for the determination of levels of contamination of poIychI orinated
biphenyls, pesticides, and industrial compounds in those same fish.
12/89 OA/QC PCOD/PCOF iv
-------
TABLE OF CONTENTS
DISCLAIMER ii
ACKNOULEDGENENTS iii
FOREWORD i v
I. Introduction 1
II. Sample Preparation
A. Grinding 3
8 . Extraction 3
C . Percent Lip id Dat«r
-------
VI. Quantification Procadura* 25
A. Initial and Oatly Citibrition of tha H(HS 25
I. Signal Quality 27
C. Quantification of PCDD/PCDf 29
0. Ntthod Efficiency JO
E. integration at Automated Data Proee*»ing and Quality
Ai»urance J 1
TAJLtS
Table 1 •• liotignif leant PCODt/PCDf* 1
Table 2 • • Minifflun level of Detection L i » i t 2
Tabla 3 •• Intarnal Standard Solution* 4
Tabla 6 •• Calibration Standarda 9
Tabla 5 •• Ralativ* Katantion rinat 4-8 PCOO I»o«ar» 10
Tabla 6 •• ftalativa Ratantion rina* 4-S PCOr !to«ari 11
Tabla 7 •• MRCC/HIMS Oparating »ara«atara 12
Tabla 8 -• Nativa PCOO/PCOF Soiking Solution 14
Tabla 9 -• Coda* for tha SCC Numbar and Matrix Typa 19
Tabla 10-- CC Column Parforwanca Quality Control 20
Tabla 11-- GC Elution Uindow Oaflntng Solutions for
01-5 Column 21
Tabla 12-- Quality Atiuranca Paranatart 22
fi jurat
Mgura 1 •• Oatabaia 'oraat for Savpla Information .....17
Mgura 2 -• 2,3,7,8-TCOO waightad Calibration Curvt 26
Mgura S •• Data laduetion for PCOO/PCOF National Oioxin Study.32
12/S9 QA/QC PCOO/PCDF vi
-------
Thi» document, "Analytical Brocedure» «no) Quality Asajrance 9 I an far t^t
Determination of PC3D/PC3F in FISH" hit been drafted in rtjoon,t t: •«» ited
for the Environmental Research .aboratsry o< DuiutM (ESl-3) :a per^srn analysis
for tetraehiora- ta aetachioro- congeners/isomers of oolychiorinatea a •• a e n t a •
p-diox-ns and diben 10furans (PCOO/PCOF), Table 1.
2378- TCI F
2367- TCO F
3467-TC3F
2378- TC3D
12378- PeCO F
23473-PeCOr1
23467- PeCOf
12373-PeCDO
123467-HxCOF
1 23478-HxCDF
1 23678-MxCOF
234678-KxCOF
123789- HxCDF
123478 -HxCOO
123678- HuCOO
1 23789- HxCDO
1234678-NpCOF
1 234789-MpCOF
1 234678-MpCDO
51207-
1746-
57117-
57117-
70648-
40321 •
70648-
57117-
60851 -
72918-
32598-
57753-
19408-
67562-
55673-
37871 •
31
01
4 1
31
29
76
26
4 4
34
21
13
85
74
39
89
00
• 9
- 6
- 6
•6
•9
• 4
• 9
- 9
•5
•9
-3
-7
-3
-4
• 7
• 4
12/89 QA/QC *COO/*CDF
-------
These analyses art I i • i t e d by lick of analytical Standards; however i $ 0 m * r
specificity «ay be determined usinf, specially developed standards. Analytical
results nIll, therefore, bo reported a* conetntration (pg/g) for tacn gat
ehronatography (CC) ptak in a congtnar claat by ««king th« attunption chat
tht rttponst for tft• noltcular ion of til isoatrt in that class is *qual to
th« rtspons* obstrv«d for tht i»o««r for which E*L-0 dota ftav* a standard.
Th« target ninimun l*vtt of detection (HLO) for specific PCOO/PCOF ijomtrj
-------
I I . S lino I • » rtoar a t i on
A. grinding: Froten fish wrapped in aluainua (oil are tent to
tht ERL-Duluth laboratory, now the fish it ground, (»hole body
or fillet), it dependent on t h• tpteit*. lotto* f e e d e r j » r « ground
whole and predators are filleted with the skin off. Mth tistu* is
ground frozen in t stainless ttttl pow*r mtat grindtr. Each
ia«pt* ii processed through tht grindtr thrtt tints uhicn
lio*ogtn and then the remainder of the sample
is added to the thlnble. The staple is extracted at least tueive
hours with a 1:1 aiiturt of hexane end «ethylent chloride in a
Soxhlet extractor. The staple is quantitatively transferred to
a 500 ml Kudtrne-Otnith apparatus and prtutshtd boiling chips
are added.
C. Percent L t o)d P111r«i ntt i on; Tht staplt titracttd in
stction 1.1. of staple prtparation is ustd to determine percent
llpld. After saaplt concentrtt
-------
tufte «nd contents «re neighed. The I i p i d is Chen a,u«n t t t * t i v t i y
tr»n»ferred to the macro column It described in Section 1.3. of
(••pit preparition. After trensfer, the ciipty loner t^Dt and
boiling ci • pj tri neighed. The percent lipid is ciicjijttd f-sm
the weight differences.
57c
13c
13c
1 T
'3C
t T
13c
« t
3C
1 t
3C
1 -t
13c
< T
l3c
1 t
13c
t 7
37c
1 ,2
i ,2
1 ,2
1 ,2
13c
I,
k
12
12
12
12
12
12
12
12
1^
2
,3
, 4
,3
,3
12
2
2
2
1
1
1
1
1
1
,3
.3
,3
, 2
,2
,2
.2
,2
j
,7,
, 7,
.7,
.3,
,3 ,
.3,
,3.
,3,
3
I
S-
S-
8-
7 ,
7,
4,
4,
4 ,
4
n
T
T
T
8
8
7
7
6
6
ternel Standard
coo
coo
CDF
•PeCOO
•PeCOF
, a • H»COO
, 8 • HxCDF
,7,8- HpCDO
7 8- HpCOF
ocoo
2
<4
, 7
, 4
.6
1
, 3
• T
.8
,7.
COO
a-
T
COF
Internet
•PeCOO
•TCOF
,7
.2
•PeCO
,3.
4 •
F
Internal
TCOO
2
5
5
5
5
12
12
12
1 2
25
2
Solution A. (100 uL)
. 0
.0
.0
.0
.0
.5
.5
.5
.5
.0
.0
10
25
25
25
25
62
62
62
62
125
10
.0
.0
.0
.0
.0
.5
.5
.5
.5
.0
.0
St|nderd Solution 1.
1
1
1
1
.0
.0
.0
.0
5
5
5
5
.0
.0
.0
.0
Standard Solution C .
50
.0
SO
.0
• 20 9 simple.
12/89 QA/QC PCOO/PCOF
-------
0. *nthreoao>n i g ^ h em i e 11. Isolation: Tht sample t * t r i e t is
quantitatively trantferrtd to i JO e* « 2.5 em g l •«» ehramit09r*Bnv
column (MACI 0•co I umnt ) fitted with i 300 mi reservoir on too.
The column his b«in packed with • plug of glass wool (bottom to
top), 2 9 silica gel, 2 g potassium silicatt, 2 g sodium su l f a t e
10 g c11 i11/su I furic *cid and 2 g sodium sulfate, and prtviously
waihed with 100 ml he»ane. The column is «luttd with 100 mi.
beniene/he«ane ( 5 X ) and tht « I u t n t is collected iri a Kuderna-Oanisn
(K0> apparatus (Caution: benzene is a known carcinogtn}. Isooctant
(1.0 ml 1 is added, the volumt is reduced and thtn transferred to tht
f I or i * i I column.
E. F I a r t s i I Chrematearaphy: A 1.0 em * 20.0 en gilts chramatography
column fitttd with a 100 ml rastrvoir is packed with a plug of glass
wool (bottom to top), 5.0 cm (1.5 g) activated florisil and 1.0 cm
sodium sulfatt. Tht florisil is acttvatfd at 120° C for 2t hours.
Tht column is washad with 20 ml mttnyltnt chloridt folloutd by 10 ml
haxant. Sample and two 1 ml hexant rinses are quantitatively
applied in small "plug*". The column is eluted with 20 ml 2X
methylene ch lorfde/ht*ane and tht tluate discarded. This wash is
followed by 50 ml methylene chloride which flows directly onto the
micro carbon/silca gel column for PCOD/PCDF isolation.
f. >CQO/»CO F Isolation! Efflutnt from the florisil column is
passed onto a 4 mm x 200 mm column (mtero•coIumn ) containing
300 •• silics gtl/csrbon (set stc. III.A.6) which wsi previously
rinsed with 10 ml toluene followed by 10 ml methylene chloridt.
Tht coluam ft fitttd with s solvent reservoir. After tht sample
has almost completely eluted from tht micro•coIumn, tht rtitrvoir
U wiihtd twict with 2 ML 25X benzene/methyIene chloride and the
12/8* OA/OC PCOO/PCOF s
-------
column is finally e i u t ed with in additional 1 1 mi. JSS otniene/
methylene chloride. '1« column is invtrttd on the reservoir and
the PCDO/PCOF art eluted yich tolutnt (25 nL). Th« toluene
fraction s collected in a pear maped Mask (25 ml) and reduced
in volume 'o O.1 mi in a 60 C water bath under a gentle
strean of dry carbon filtered air. The sample is transferred to
a microvial using toluene ta rinse the flask. Prior to GC/MS
analysis, the sample is allowed to evaporate to dryness and is
spiked with 20 ul of Standard Solution C (Table 3).
I ! I . 8 e a a en t s and Standards:
* . » eaaent s:
1. Solvents: Only pesticide grade distilled in glass solvents
are used. They are: hexane, ijooctane, lethylene chloride, benzene,
toluene, acetone, and methanol (lurdick and Jackson, Fischer
Scientific).
2. Sodium S uIf a 11: Sodium sulfate (laker Chemical Company reagent
grade anhydrous) is baked at 650°C in a furnace for 24 hours,
coaled, and stored in an empty hexane solvent bottle.
S. Silica Gel: St I ica•Gt I •60 (Merck•0•rmttadt), it Soxhlet
extracted eight hours with methanol, placed on solvent rinsed foil,
air dried for 12 hours, and vacuum oven dried (125°C) for 2 <•
hours. It is stored in an empty hexane solvent bottle. Prior to
use it is activated at 105° C for 24 hours.
4. Sul fur i c *.c i d/Ce I t t e : Sulfuric acid (laker Chemical Company,
Ultrex) (i me) i* blanded in • 250 ml b«aker with Celite 545
(laker) (10 g) .
12/89 QA/QC PCOO/PCOf
-------
5. Potassium Si I i e a 11: High purity potassium hydroxidt (Aldriclgt
Cht«lcal Company) (56 g) it dissolvtd in mtthanol (300 ml).
S)lfca-gti (100 g) i* addtd to tht mixturt and stirr«d (1 hour,
Q
60 C). Tht mixturt is eooltd and tht solvent is removed using
a luchntr funnel. Tht potassium silicate is rinstd twice »ith
'00 ml of mtthanot and onct with 100 ml of mtthyltnt chlorid*.
Tht solids art placed on aluminum foil in a f u m t hood and allowed
to dry for approximately 2 hours. Tht solids art placid in a v a c u w "i
ovtn and dritd ovtrnight at 105 C. T h a rtagtnt is plaetd in a
rinitd btaKtr and stortd (activattd) at 120°C until ust.
6. S i I i c i C*I/C a rfrpn: Silica Gtl-60 (100 g) ( Mt re It - 0 a rms t a a t ) is
S o * h111 txtracttd with mtthanol (200 ml) for 24 hours, air dritd
in a hood, and furthtr dritd in vacuum ovtn for 24 hours. AMOCO
PX-21 Carbon (S g) is addtd and thtn bltndtd until uniform in
color. Tht Silica Ctl/Carbon ii stortd in a cIo s t d jar at room
temperature until ust.
7. f\o r i s iI : Florisil 60-100 m t s h (Baker Analyztd) is soxhltt
txtracttd with mtthtnol for 24 hours, plactd on solvtnt rinstd
foil, air dritd and stortd in an empty htxant bottlt. Prior to
uat ft i » activattd at 12 0 ° C for 24 hours.
• . S tandtrds :
1 . Ant t vt t ea I S tandard S o i k i n a Solution
Tablt 3 providts dttails of tht spiking solutions. Tht surrogate
analytts art ustd by tht data rtvitwtr to insurt that calculated
NLD valuta art rtasonablt.
2. Quanttf
-------
chockod ttalntt * primary ttandard obtained fro* tho U.S. national
lurtog of Standard!. * table of the cone entratI one of each itenor
In eoch standard It flven In Table 4.
3. Qualitative | \ indirdi: t» L • 0 h«t dovolopod two qutUtitivo
•n»lyt1c»l ttindardt, ono eonttlnlnf all 7) »CDO'i and ill 118
PCOF't M«I dovolopod fro« tn txtractlon of •unieiptl inein«r«tor
fly **h (Tablet S «nd 6) «nd tho othtr eontttninf only th« biotif
nlfleint i»o«ort vtt dtvoloptd by cipoturo of flth to «n oitrtet
of «unieiptl ineinorttor fly ««K tnd procottlnf tho oipotod fith
for PCOO/PCOf. Thoto tttndtrdi u
-------
4; C«Ubr«tlon
Conctntr«tion* in Calibration Solution* in pg/ul Tridtctnt
W1
W4
2,3,7,3-TCOO
2,3,7,8-TCOF
1,2,3,7,8-MCOO
1,2,3,7,8-MCOJ
2,3,4,7,8-MCDF
1,2,3,4,7, -MxCOO
1,2,3,6,7, • MxCOO
1,2,3.7,8, • MxCOO
1,2,3.4,7, -HuCOF
1,2,3,6,7, -lUCOf
1,2,3,7,8, -HaCOF
2,3,4,6,7, -MxCOr
1.2,3,4,6,7,8-HpCOO
1,2,3,4,6,7,8-HpCOF
1.2,3.4,7,8,9-HpCDf
OCOO
ocof
13C,2 2,3,7.8-TCOO
13C12 2,3,7,8-TCOF
13C,2 1,2.3,7,8-HCDO
J3C,2 ,2, ,7,8-MCOf
3C12 ,2, ,6,7,8-IUCOO
3C12 ,2. ,4,7.8-tUCO*
3C12 ,2, ,4,6,7.8-HpCOO
3C12 ,2, ,4,6,7.8-HpCOf
13c12 ocoo
37C14 2,3,7,8-TCOO
37C14 2,3.7,8-TCTf
13C,2 1,2,3,4-TCOO
200
200
200
200
200
500
SOO
500
SOO
SOO
SOO
SOO
SOO
SOO
SOO
1000
1000
so
50
50
SO
125
125
125
125
250
20
20
50
100
100
100
100
100
250
250
250
250
250
250
250
250
250
250
500
500
SO
SO
50
SO
125
125
125
125
250
20
20
50
SO
SO
50
50
50
125
125
125
125
125
125
125
125
125
125
250
250
50
50
SO
50
125
125
125
125
250
20
20
50
25
25
25
25
25
62.
62.
62.
62.
62.
62.
62.
62.
62.
62.
125
125
50
50
50
50
125
125
125
125
250
20
20
50
10
10
10
10
10
25
25
25
25
25
25
25
25
25
25
50
50
50
SO
50
50
125
125
125
125
250
20
20
50
S
5
5
S
5
12.
12.
12.
12.
12.
12.
12.
12.
12.
12.
25
25
50
SO
50
50
125
125
125
125
250
20
20
50
2.
2.
2.
2.
2.
6.25
6.25
6.25
6.25
6.25
i.25
6.25
6.25
6.25
6.25
12.5
12.5
50
50
SO
50
125
125
125
125
250
20
20
SO
1
1
1
1
1
2.5
2.5
2.5
2.5
2.5
2.
2.
2.
2.
2.
5
5
50
50
50
50
125
125
125
125
250
20
20
50
12/M QA/OC PCOO/PCOF
-------
Compound
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
t
366
379
369
378
469
247
248
246
249
268
478
279
234
234
269
237
238
2378
1
1
1
1
1
1
1
1
1
239
278
267
289
2468
2479
2469
2368
2478
Q
0
a
a
a
0
0
0
0
0
0
0
0
0
0
0
0
1
1
1
1
1
1
1
1
1
1
(IT
01)
.814
.838
.361
.912
.912
.912
.912
.921
.921
.934
.940
.960
.98)
.98)
.98)
.991
.993
.000
.009
.028
. 048
. 079
.224
.224
.26)
.293
.308
IIT
JP2330
0
0
0
0
1
0
0
1
1
0
0
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
.826
.871
.948
.916
.072
.948
.948
.014
.014
.972
.990
.027
.014
.027
.10)
.014
.014
.000
.088
.072
. 130
.216
.111
.111
.268
.148
.188
Compound
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
2379
2369
2467
2489
2347
2346
2378
2367
2389
24679
24689
23468
23679
23689
21469
23478
23678
23467
23789
234679
234678
2346789
(IT
01)
1 .320
1 .348
1 .348
1 .348
1 .368
1 .368
1 .400
t .415
1 .443
1 .620
1 .620
1 .673
1 . 700
1 . 700
1 . 700
1 .764
1 .77)
1 .802
1 .802
1 .976
2.023
2.234
(IT
SP2330
1 .
1 .
1 .
1 .
1 .
1 .
1 .
1 .
1 .
1 .
1 .
1 .
1 .
1 .
1 .
1 .
1 .
1 .
1 .
2.
2.
3.
209
307
321
321
268
3)2
288
J63
463
473
473
473
)46
546
681
604
618
789
721
13)
297
22)
12/89 OA/OC PCOO/PCOF
10
-------
C oapound
1368
1468
2468
1247
1347
1378
1346
2368
1367
1348
1379
1268
1248
1467
1478
1369
1237
2467
1234
2349
1236
1469
1238
1278
1349
1267
2378
2348
2347
2346
1246
1249
1279
2367
1239
1269
3467
1289
13468
12468
23479
12368
12478
13467
12467
Mr
01)
0.730
0.752
0.763
0.782
0.782
0.782
0.782
0.782
0.801
0 .801
0.801
0.835
0.835
0.853
0.853
0.863
0.863
0.863
0.880
0.880
0.880
0.880
0.880
0.902
0.920
0.920
0.939
0.939
0.939
0.939
0.939
0.939
0.939
0.973
0.988
0.988
0.988
1 .071
.120
.120
.190
.202
.202
.202
.202
II T
S»2330
0 .777
0.875
0.989
0.885
0.865
0.853
0.919
1 . 071
0.881
0.900
0.853
0.943
0.919
0.989
0.943
D.943
0.943
1 .109
0.977
0.977
0.989
1 .061
0.989
1.017
1.013
1 .049
1 . 169
1 .175
1.140
1 .193
0.940
.071
.049
.206
.140
.162
.264
.341
1 .008
.028
.065
.103
. 121
.142
.160
Compound
13478
13479
23469
1 2479
13469
23468
12469
12347
12346
12348
12378
12367
23489
12379
23478
12489
13489
12369
23467
12349
12389
123468
134678
124678
134679
124679
124689
123467
123478
123678
123479
123469
123679
123689
234678
123789
123489
1234678
1234679
1234689
1234789
12346789
MT
015
1 .202
1.217
.217
.233
.253
.253
.253
.253
.253
.280
.280
.295
.309
1 .309
1 .339
1 .339
1 .359
1 .359
1 .371
1 .392
1 .446
1 .556
1 .570
1 .570
1 .570
1 .602
1 .621
1 .663
1 .663
1 .676
1 .676
1 .712
1 .730
1.744
1.744
1.827
1.827
1.954
1 .979
2.024
2.043
2.240
II T
SP2333
1 .083
1.103
1.173
1.142
1 .204
1 .278
1 .278
1 . 173
1 .231
1.216
1 .216
1 .252
1 .388
1 .237
1 .557
1 .446
1 .350
1 .373
1 .612
1 .420
1 .590
1.336
1 .370
1 .348
1 .348
1 .428
1 .521
1 .533
1 .489
.502
.489
.668
.562
.668
2.012
1 .871
1 .940
1.936
2.001
2.161
2.463
3.169
12/89 QA/QC PCOO/FCOF
11
-------
I V. t n« t ruaent a i P arime t er i;
All gaa ehrone logrephy/*ass iQICtrouttry analyses (GC/MS) will be done
en • Mnnigan-MAT 8230 high resolution CC/high rtiolution MS
HINS) sytteei. In»truwenta I parameters are given in Table 7.
Data Acquisition: Multiple Ion Selection Electric Sector Scan.
Compound
Mess UindOM
TCDf
;7ci4-
C12'
rcoo
37c i -
13c *-
C12
PeCDF
13c
PeCOO
13c -
C12
MxCDF
13C -
C12
H«COO
13C -
C12
H|COr
C12"
HpCOO
13C -
C12
ocor
13c •
C12
ocoo
13c •
C12
TCO*
TCOf
TCOO
TCOO
PeCOr
PeCOO
Hicor
MxCDO
HpCDf
HpCOO
OCOf
ocoo
1
1
1
1
1
1
2
2
2
2
3
3
3
3
4
4
4
4
5
5
5
5
305
31 1
317
321
327
333
339
351
355
367
373
385
389
401
407
419
423
435
443
455
459
471
.8986
.8898
.9389
.8936
.8847
.9338
.8597
.9000
.8546
.8949
.8207
.8610
.8156
.8559
.7817
.8220
.7766
.8169
.7498
.7801
.7348
.7750
303
315
319
331
341
349
353
369
375
387
391
403
409
421
425
437
445
453
457
473
.9016
.9419
.8965
.9368
.8567
.9029
.8576
.8919
.8178
.8580
.8127
.8530
.7788
.8191
.7737
.8140
.7369
.7831
.7377
.7721
Staple Introduction;
t on iii t i on :
Source Pre$»ure:
laniztr Teapereture:
Nut letolut \ on:
Sean l*te:
GC Cotuan:
I I neer Veloe1ty:
Teeipereture Progrea:
Capillary Coluan, Splitleit Injection.
Electron Impact, 70eV, 1 nA Eaiiiion Current
1 X 10"S torr .
250° C.
5000, 10S valley.
1 MIS cyele per second.
30 • 08-5 , 60 • SP2330
35 c«/»ec Heli u«.
180° C (hold 1 «in); 13°/ai(n to 200°;
3°/eiin to 270°;
270 hold 4 ain.
Matt windows are monitored sequentially during the temperature
• Quant. • Ouantifeation ion; Confir. • Confirmation ion.
12/89 OA/9C
12
-------
V . Quit i t y Assurance/Quality Control (0* /9C )
A . General Procedural o f Qptrit • an
1. Ana I v^ i } o f Sime t 11: Samples •re analyzed in »eti a*
twelve consisting of:
a. 9 I inn : Mtthod (link (extraction apparatus) is prepared i i
the laboratory and subjected to the tan* sample preparation
procedures a* environmental samples. The Method 8l*ni i«
u*td in tvtry taaipla sat.
b. f9rt t» ita xat ri »: Nativt in«lyt«t (100 ui> (Tabla 8)
art addtd to a btank sanplt matrix. The Itv» t s of fortif'-
cation of n a t i v t analyttt in t h a Matrix spikt will b t aoovt
tht targtt dtttetion Unit to providt an tstimata of tht
method's sensitivity, and for dtttrmination of ptrccnt
accuracy of quantification. This saapte nay b« substituttd
with a rtftrtnct sadplt that has bttn analyzed at leaic
three tines and a mean value of contamination has been
established.
c. Detection Limit Verification Sano I e: Art environmental
sample with nondetectable amounts of native analyte (determined
from a previous analysis) will be spiked with native analyte*
(Table 8) and analyzed with the next tample set. The addition
of tht QA/QC sample will be done for only the first chree
sample sets of any matrix type to establish that the
calculated MID it achievable. If analytical results show
difficulty in obtaining the MID, then this QA/QC sample must
be in each set. If no problem is experienced, then this
QA/QC sample may be dropped.
12/8* QA/QC •COO/'COF 13
-------
Table I: native fCQO/fCQf Jpiktng solution (100 uL)
Compound
Cone ent ra t ton
(pg/uL T r i decane)
2,3,'
2,3,
'.2.3
1.2,2
2.3,<
1 ?
'.2.
',2,
1,2,
1,2,
2.3,
',2.
1 ?
1 ?
ocoo
fi£i'
',8-rc:
', S-TCC
», 7,8-1
», 7,8-1
>, 7,8-1
,4,7,
,6,7,
,7,8,
,4,7,
,6.7,
.6,7,
,7,8.1
,4,6,
,4,6,
>0
)f
>*CDO
>*COF
• eco?
- NxCOO
•NxCOO
• HxCOO
• Hxcof
•HxCOF
•HXCOF
>• HxCDF
T a-Hpcoo
7 8-HpCDF
0.50
0.50
0.50
0.50
0.50
1 . 25
1 .25
1 .25
1 .25
1 .25
1 .25
1 .25
1 .25
1 .25
2.50
....^50....
1 . 00
1 . 00
1 . 00
1 . 90
1 .00
2.50
2.50
2.50
2.50
2.50
2.50
2. 50
2. 50
2. 50
5 . 00
1*22...
1 .50
1 .50
1 .50
1 .50
1 .50
. 75
. 75
.75
.75
.75
3.75
3.75
3 . 75
3 . 75
7.50
7 . 5J
d. D UP M e § 11 S »mo I « : Two ttpant* portions of th* ISM*
tnviron*«ntsI ssnplt «rt processed *nd sntlyxtd.
«. tnv i ronntn111 i »»oI«s: Th* total nuabtr of tnviron*«nta I
taaplts analysed is tight if th* Detection li«it Verification
sa«pl* Is used; otheruis* nine taaipl** are analyzed.
2. Sanoie T raefc i n« and Label Ina of 5a«pi*t;
a. Loaal nt I neoaii na SaaiPl as ; Hl-0 coaipletet the chain of
custody foreis and informs th* $a«pl* Control Center (SCC)
that aa«pl«s arrived safely or inforns SCC of any probleais
with the ia*)pl*s. Each »a*pl* r*c*iv*d by ERL-0 had
previously been assigned two numbers by th* S*«pl* Control
C*nt*r, th* faaipl* Control C*nt*r nu*)b*r (SCC*) and an Episod*
nu«b*r. Th* ICCf nuab*r I* uniqu* for **ch saaipl* and provides
QA/QC
14
-------
• * t•n » for tracking t g i v t n s a • p t t throughout iti i n • t y « i >
•nd its ptrmantnt storage it tht locktr plant, tht tamoiti
• ra piactd into frttxtr A upon arrival »t E R I • 0 u I u t h
homogtniitd, (»*• I I. A.), and an aliquot (100-500 g> i» pi»eto
into frttztr I. Afttr tht sa*plts art txtracttd ti*y art out
into frttztr C. If all tht data mttts QA rtquirtmints afttr
• ass tptctral analytit and quantification, (ht sampltt art
trantftrrtd to a locktr plant for ptr»tntnt storaga C-20S C).
b. Loaa i na and L abt( i na SameIti 0 ur t na Prtparat ion; A laboritory
idtntifieation codt (lab ID) it randomly assigntd to tach
samplt in a sat of twtlvt at tht start of samptt pr tot <~ 11 < 3 ^,
Tht codt consist* of a Ittttr, A through L, datt of
txtraction, and two initials of tht saaplt prtptration
chtmist, n fit*:
Saaplt Tracking Oatabast to facilitatt rtcord kttping and
*u»tiary rtport gtntration for tach sa*plt on tht OCC-VAX 11/785
(Digital Iquipatnt Corporation). For tach sanplt, including QA
savplts, inforaation ptrtintnt to tach sttiplt it tnttrtd into tht
12/lf 8A/OC rCDO/»COC IS
-------
database. Quantification data (final concentration, ion ratio*
percent recovery, MiOs, and signal to noise) are automatically
uploaded to tha databaia onct all OA erittria neve bttn met.
Figure 1 it an example of th« M D S databaia.
The first two latter* of the SCC number indicate whether
the sample it an Environmental, Method or Matrix Hank,
Duplicate Saaple or a mat a spectral confirmation analysis of
an environmental sample. All environmenta I samples begin
with the letter 0, or S if it i* a mass spectral confirmation
analysis of a previously analyzed environmental sample.
The Hank and Duplicate samples begin with the letter Q
followed by a 0 or an R for duplicate or reference fish
sample, respectively. Table 9 lists the; possible codes
for the SCC number, and metrtx type. Episode numbers for
Hanks and Fortified Matrix sample! are entered at 0000.
u/89 QA/AC »coo/*cor 16
-------
N 0 S 'hist M: Bioaccymutative P o I I u t a n t I
Sampi* Tracking System
Fish:
E»L-0 loe:25
1 S03E I : 3300
Sampling [nformat'or:
Sampling 0^'iet:
Stat* I City:
Sampling Contact:
Oat* Samp icd: O/ 0 /
Sit* Location:
lacitud*: M 0 0'
»n» l /» i i tap; 3
Matrix Typ*: 9
SCC *: 911071486
L ong i t uda : U 0 0 ' 0
Oat* l*c*
-------
*0t
I i oceeuMul • t t vt Pollution in Mth
EP1SOOC •: 0000
sec •-. QR071486
Ell-0 Loe: 25
DATA FOR I [OS I CM I t \ CANT P0 ITCHL0*IK*TE0 0 I ICNZ00 I OX I NS AMD FURANS:
»n« I
2,3.
2,3,
3,4,
2,3,
1 ,2.
2,3,
2,3,
1,2.
1 ?
1 ?
',2.
2.3,
1.2,
',2.
1,2.
1 ?
1,2.
',2,
yt.
7,8-
6, 7-
6,7-
7,8-
3, 7,
4,7,
TCOF
CAS
51207
NO.
•31
I/R
-9
TCOF
TCOF
TCOO
a-(
».COF
8-MCOF
4,6, 7-P«COF
3,7,
3,4,
3,4 ,
3,4,
4.4,
3.7,
3,4.
3.4.
3, 7.
3,4.
3,4.
a-.
'•COO
1744
57117
57117
70648
40321
•01
•4 1
•31
•29
•76
•6
•6
•6
•9
• 4
0 .
1 .
1 .
0 .
1 .
1 .
0 .
0.
74
00
71
78
33
10
00
25
S/N
55.
8.
16.
40.
16.
1 1 .
a.
4 .
75
28
56
75
72
15
36
24
XRCC
62
62
62
73
54
54
54
57
0
0 .
a .
0.
0.
1 .
1 .
2.
4 .
L
0000
9726
4863
0000
0892
6357
1784
0729
A«ount (
5 .
NO
NO
15
NO
NO
NO
NO
26
.63
6 7-N*COF •
7
7,
7.
a,
7,
7,
a
• NxCOF
• NiCOF
• NxCOF
- HxCOF
•NiCOO
•HxCOO
• NiCOO
6, 7,8-HpCOF
7,8,9-MpCOF
70648
571 17
60831
72918
32598
57753
t 9408
67542
55473
•26
• 44
•34
•21
•13
• as
•74
•39
•89
•9
•9
•5
•9
•3
•7
•3
• 4
-7
0.
0.
1 .
0.
0.
1 .
0.
0.
0.
00
67
25
00
00
31
00
62
00
57.
28.
57.
57.
29.
4 .
29.
18.
37.
03
52
03
03
08
67
08
97
94
47
47
47
47
49
49
49
39
39
0.
1 .
0.
0.
1 .
0.
1 .
0.
0.
7327
4654
7327
7327
3843
0000
3843
0000
0000
NO
NO
HO
NO
NO
3.
NO
NO
NO
23
1 ,2.3,4,6,7,8-HpCOO 37871-00-4
1 .13
10.50
39
0.0000
5.93
Cottut** Mitft 1 ,2,3,4,6,7-H*COF on • 085.
I/I • Ion Ratio; S/N • signal to Noist; 01 • Otttetfon ii«ft
12/89 8A/OC PCDD/PCOF
18
-------
SCC n u • b e r first letter options:
0 •• Jnv i ronmn t a I staples
Q • • QA samp I ti
S •• HS confirmation analysis
Second letter optioni for Environmental Samples
A • » t J i o n 1 G • * « 9 i o n 7
I - Ktgion 2 N • Ktgion 8
C • » t9 i on 3 T • » 19 i on 9
D - K*gion 4 J • Itgion 10
I • t • g i o n 5 r-Allrtgion«tdat«
f • I tg i on 6
S«cond l«tttr options 'or QA i««pl«i:
I • Hethod or nttrix blank
D • Ltbrotory dupticatt
R • A*ftr*net flsft or fortified matrix
Matrix Typ« :
Pf • Predator Fillet
Wl • Whole lotto*
UP • Who I • Predator
BF • lotto* Fillet
I • leferenee
r • Hank
L • Laboratory Duplicate
12/89 OA/OC »COO/fCOr 19
-------
I . I nitpuaant|^ Quit I t Y Control
1. fiXL Ch. r Baa, t p a r aph
«. QB«r a t i on and. * Ii n t ananc a : Oparation ind ••inttninet of
tht gat ch r oiaa t ogr apn Mill b« don* according to *anuf»ctgrtr•$
raco««andat i ont.
b. Col umn »«r f ormnet : GC column p«rfor«tnc* will ba
•vtluattd by:
f. Ittolution of 1,2.3,4-TCOO froai 2,3,7,8-TCOO
(Tabl* 10).
if. Tha * valua of tht ragratiion of tha laapla
ralativa ratantion ti•• of all bIoaigntf1eant PCOD/PCOF,
to tha library ralativt ratantion ihould not ba lat*
th»n 0 .995 .
Hi. tlution of all PCDO/PCOF during analytit fro* a GC window
defining solution of taltet ?COO/»COF (Tibia 11).
latolgtlon of 1,2,3,4-TCDO fro* 2,3,7,8-TCOO will
b* uttd to avaluata ganaral column parforaanca.
Ittolution (R) nutt ba 0.75 or graatar.
R - 2d
12/1* QA/QC »C09/»COF
20
-------
',3,6,8 1,2,8,9
TCOf 1,3,6,8 1,2,8,9
PeCOO ',2,4,7,9 /1,2,4,6,8 1,2,3,8,9
PtCOf 1,3.4,6,8 1,2,7,8,9
H«COO 1,2,4,6,7,9 / 1,2,4,6,8,9 1,2,3,4,6,7
H »C3 f 1,2,3,4,6,8 1,2,3,4,8,9
wpCDO i ,: 3 , 4 , 6 , 7, 9 1,2.3,4,6,7,8
1,2,3,4,6,7,8 1,2,3,4,7,8,9
2. H 11 » S o e e t • a I a»r»3rTianee: T * • performance of the mass
spectrometer i$ evaluated for resolution, sensitivity and
linearity. The mats resolution u s t d for t h t»t •n•t y j e t ij set at
a minimum of 5300 ( 10 X vallty otfinition). T h• mass spectrometer
is tuned caeri day to the required resolution according to tie
procedures established by tne instrument manufacturer. S «n s ' T• *i
and Linearity is evaluated by the us* of calibration standards
varying in concentration (Table 4). A calibration curve ts
established for each standard. The curve mutt be linear over tie
rang* of concentrations used in the calibration standards. The
percent relative standard deviations for the mean response factor
must b* lest than 20 percent.
C. Evaluation o f Data;
1. Accuracy; Accuracy, the degree to which tht analytical
measurement reflects the true level prettnt, Mill b* evaluated in
two ways for each sample tet. These are: the difference of
•eaturenent of a PCOD/PCOF itoner added to a blank matrix, or
difference of measurement of a PCDO/PCDF fro* tht level in an
ettablfthed reference material; and the efficiency for recovery
12/89 QA/QC *COO/*COF 21
-------
o* t he internal standard added for each congtntr jroup. ' h * Q*
requirements 'or accuracy and method efficiency art proviaeo '
Table 12. Percent Accuracy and Percent Mtthod Efficiency
art defined as follows:
measured value
X accuracy «
amount native isomer
added to blank matrix
X 100
measured value
X Het h od efficiency
amount internal standard
added to eten sample
X 1 00
TCOO
PCOD
HxCOO
HpCDO
OCOO
TCOf
PCOF
HxCDF
HpCOf
OCOF
ton Hat
0 .76^
0 .61 +
1.23 +
1.02*.
0.88*
0.76 +
1 .53 +
1 .23 +
1 .02 +
1 .53+.
: i o
15X
15X
15X
15X
15X
15X
15X
15X
15X
15X
Method Accuracy Precision
Efficiency at 10 pg/g at 10 pg/g
>40X, <120X »50X »50X
>40X, <120X »50X »50X
>40X, < 1 20X • 1 OOX * 1 OOX
>40X, <120X ilOOX J.100X
>40X, O20X *200X +.100X
>40X, O20X -50X »50X
>40X, <120X +50X ;?OX
>40X, <120X +100X +100X
>40X, <120X +200X +200X
>40X, <120X +200X +.200X
S/«
N i n i mu
3.
3-
3 .
3.
3 .
3.
3.
3.
3.
3.
m
3
0
0
0
0
0
3
3
0
0
' Variance of measured value fro* actual.
•• variance of difference of duplicates fro* "aan.
12/89 OA/OC PCOO/PCOr
22
-------
2. P r e e i « i a n ; Precision, • measure of Mutual agreement anon?
individual measurement* of the same pollutant in rtplicate
samples, it evaluated for each sample ttt by the ratio of
tht difference of duplicate value* to their nean valut.
Table 12 provide* QA requirements for precision. Precision 11
determined only when both value* ere above the detection limit.
Prtcition i* defined •* follow*:
difference between duplicate samples
Precision x 100
••an value for the duplicate*
3. Signal Qua I< tY; The quality of the naia ipectrel signals used
for qualitative and quantitative analyti* i* evaluated
uaing two parameters: the ion intensity ratio for the tuo ions
•onitored in each congener group, and the signal to noise (S/N)
ratio. Table 12 provide* 0* requirements for signal quality.
In addition, qualitative identification will be based on
coelution with the atable isotope labeled compound, or relative
retention time correlation (Table* 5 and 6).
4. Polar Ga* Ch ronatoaraohi e Conf i rmat i on Analysis: Ten
percent of the sample extracts analyzed are aaleceted for
GC/HS confirmation analyti* on th* more polar JP2330 column,
-------
0 . Q u 1I i t y Assurance P r obIeas and Corrtet i vt
I On* !
MS performance outside 4*
SC column performance
outside 9A .
Method efficiency outside
of QA .
Accuracy outside of QA for
t p i k e d matrix.
Precision of duplicates
outside QA .
Detection of analyte in
blank for 2.3,7,8-TCOO,
2,3,7,8-TCDF and
1,2,3,7,S-PCDO
For other analytes in
bl ank
Analyte exceeds calibration
standard range.
Method efficiency for blank
outside of QA or blank lost
Adjust MS parameters for resolution,
rerun initial curve end reenalyie
iamp Ie(s ) .
(eanalyze standards and ssmpits on
modified or alternate column.
If 2378-rCDO method efficiency
-------
V I . Cjuant''ieati3n Procedures
Quantification of analytes is accomplished by assigning isomer
identification, integrating the a r•i of miss specific GC peaks, » n d
*
calculating an a n a t y t a concentration based upon an ion relative
response factor between the anaiyte and standard.
*• 1 n ' t i » I and 3 a i I y Cat ibration o f t he *»".
-------
Figure 2
2,3,7,8-TCDD
WEIGHTED CALIBRATION CURVE
2 3
CONCENTRATION
SLOPE » RESPONSE FACTOR
CONCENTRATION/
12/89- QA/QC PCDD/PCDF
26
-------
S i a r> i l Q >j a I i t v
1 . » i n i n> u m level o f Detection ( * i Q 3 : * i n i mun i.»v«l of Detection
is defined as the concentration predicted from the ratio of
baseline noise area to labeled standard area, plus thru times
the standard error o' the estimate derived from the initial
calibration curve for the analyte of interest.
Initial Cal 'bration Based *e t hod o f_ "10: MID is estimated
from the ratio of tne noise area to the isotopicaliy labeled
internal standard area, plus three time* the standard error of t«e
estimate (SE) for the area ratio, or Y-axis, of the initial
calibration curve. The Y-intercept (INT) is subtracted from 11 < s
quantity, in keeping with the normal formalism for "inverse
prediction" of a point on the X, or concentration ratio axis, from
a point on the t, or signal ratio axis. The SE term is derived
f r o• an analysis of variance (ANOVA) performed during the weighted
least squares fit of the initial calibration curve. This term
represents the random error in the replicate injections used to
generate the calibration curve, the error not accounted for by the
linear model. The weighting is necessary because of the relation
often observed in instrumental analysis, of increasing variance
with increasing concentration. KL0, according to this scheme,
is def i ned below:
[
-------
w h t r t: N. • noil* area in tht window for t h• * a j o r ion
of tht native analyte,
1334 • labeled internal standard peak art* in the
(••pit,
INT • the T-e»is inttrcept on the initial ciUbrition
curve,
C33* * labeled internal standard conetntration,
K • constant to adjust for samplt size and final
volu**,
*f(N/[33«) • r«spon«t factor for major native ion to
1JC12 1,2,3,4-TCOO ion, tht slop* of th*
initial calibration curva,
SI • standard error of the tstinatt of th» initial
calibration curva.
tn addition, fish tissua is spiked with surrogate analytes
(sta Internal Standard Solution I, Table 3) prior to extraction.
Tht surrogate analytts strvt ai an added check to insure that
HID values calculated fro* tht initial calibration curve,
a* discussed above, are reasonable.
2. Signal t o Noise (S/N) i The method of determining the signal
to nolat ratio is shown btlow.
Analyte signal
Noise Signal
Analyta Signal PaakAraa
^m^m^^mmmmmmmmfmmmmmmmmmmmmmmmmm^mm
Noise Signal Peak Area
12/19 O.A/8C •COD/PCOP 28
-------
S/M •
Analyte Signal Beak Artl
Noiit Signal Peak Artl
The noiit art* it calculated by integrating ov»r a peak •ioth
equivalent to the analyte signal, typically about 10 second*.
C. a iia n t i fieiti on o f PCOO/•CO F : The conetntration of a natural
PCDO/PCO' is dttarminad by calculating a rttpona* factor batwttn
PCOO/PCO^ and cht atabtt isotopa label ad PCOO/»COF for ttn congener
group. Calculations art performed a* follows:
Standard:
Saaip 11:
RFCN/L)
where:
• rttpentt factor native to labeled,
• peak area native,
• ptak area labeled,
* concentration of native standard,
• concentration of labeled standard,
• labeled tpik
-------
0. Mt t hod i M i e i t n c v : Tht atthod •fHeitney for tht rteovtry »f ttablt
isotopt labaitd compounds it dtttraintd by calculating tht tnount of
stablt isotopt labtltd compound in tht final txtract and dividing By
t h• •mount spik«d into tht t••pI• 11 tht »t•r t of tht eltanup
proctdurt. This i» dont by dtttr*ininf tht rtlativt rttpontt factor
Dttwttn tht inttrnal Standard Solution C, c^j 1 , 2 , 3 , 4 • rCOO
and tht itabtt iaotopt labtttd inttrnal standard (Solution A).
Otttrmint Itsponst factor:
*L « CH
*IS * CL
whtrt: KF « rttponat factor,
A « arta of itablt itotopt labtltd
intarnal standard, (solution A),
AtJ « arta of 13C12 1,2.3,fc-TCOO ,
C, • conctntration of stablt isotopt labtltd
inttrnal standard, (solution A),
CJ$ * conctntrat ion of 13C12 1,2.3,4 - fCOO .
Tht rttponst factor is thtn ustd in calculating tht conctntration
of tht inttrntl standard in tht final solution,
*ll * "'
C, • conctntrat
-------
Tha concantration in tha final solution tint* tht f •" n a I v o I u m a
• quail tha total a«ount prasant. rh • nathod affieiancy 11 than
ea I cul a t ad by.
C L found
X Racovary • X 100
Cl spi lead
Intaaratian o f Aut oma t ad Data Praeanina and Qua I I t v *s«uranc»:
QA paraaiatars for mathod affiei'aney, ion ratioa, ratantion tina
corraI ation», signal/noisa ratio, accuracy and pracision «ra
monitorad with t h a aid of softwara aithar davalopad in-housa, or
nodifiad from axisting progra«t includad with tha MINI data systaia.
(aw data is sortad and aditad using tha mass spactro«atar's dadicatad
data systan, tranafarrad to tha DEC-VAX systa* and procassad using
softwara programs (FACTOR and OFQUANT (Ffgura 3.). Data is raviawad
by tha Projact Ofrtctor bafora an tar ing into tha NDS data basa.
12/89 9A/OC »COO/PCOF 31
-------
Figure 3
DATA REDUCTION FOR PCDD/PCDF
NATIONAL DIOXIN STUDY
DAILY
CALIBRATION
STANDARDS
*5PT
SRT
|
RFACTOR
SOFTWARE
YES /DATAX
\P ASSES/
\QA?/
INITIAL
b» PAI IRRATION
LIBRARIES
i
SAMPLES
no
Un
IBM-PC
a
MASS
SPECTROMETER
DATA
SYSTEM
4
(BEGIN)
NO ' NO
^CORRECTIVE^
ACTION
REVIEV
DATABASE •«
SRT
i i
DFQUANT
SOFTWARE
/DATA\
V PASSES/
\QA?/
V \/
YES
GENERATE
FINAL REPORT
12/89 QA/QC PCDD/PCDF 32
nrrrua orriet iWO/'«-is»'»4jj
-------
APPENDIX A-3
Analytical Procedures and Quality Assurance Plan
for the Determination of Xenobiotic Chemical
Contaminants in Fish
-------
c/EPA
Stales
E~vronmertai P-
Agercv
-aooratorv
MN 55804
= = 4500 3-90 "'
Mar:- '990
qesearc~ ar.o C
Analytical Procedures and
Quality Assurance
Plan for the
Determination of
Xenobiotic Chemical
Contaminants in Fish
-------
EPA/600/3-90/023
March 1990
U.S. ENV1ROMNENTAl PROTECTION AGENCY
NAT I ONAl 0 I OX I N STUOT
PHASE I)
Antiytic.il Proctdurti and Quality Atiurtnct Plan for
tht 0 *11rtfl in»tion of Itnooiotic Chtnicil Cont»«inint» in Fisn.
0«etmb«r 1989
f nv i ronmtn 111 Msitrch L
-------
NOT ICC
T h• information in t h I « docuatnt h • • b«•n funded wholly or in part by t h •
U.S. Environmental Prottction Agency. It hi* been reviewed technically and
•dminiitr•tiv»Iy. Mention of trede »••«• of co««ereiil product! doe« not
eonstitutt endors•ment or r«eo««tnd«tI on for us*.
12/89 OA/OC X»r>obtot1c§ H
-------
ACKNOWLEDGEMENTS
Technical contributions to this research were made by:
Brian C. lutttrworth
0 oug I • t U . Kueh I
Phillip j. Marquis
H • r i « L . L • r j • n
Larry c . Holland
Christine E. Sodcrbtrg
Jtnniftr A. Johnson
Kevin L. Mogftldt
Alan E. Motoi
Elizabeth A. Lundmark
Daniel M. Fremgtn
Sandra M aumann
Murray Nackatt
(ant Johnson
Harvty 0. Corbin, jr.
Or. Raymond L. Hanson
John Oargan
Dr. T h omas T i•r nan
Dr. Michael Taylor
12/89 OA/OC X«nob
-------
FOREWORD
Directed by Congressional mandate, the U.S. Environmental Prottction Agency
curing 1983 initiated the National D i o x i n Study, a survey of environmental
contamination by 2 , 3 , 7 , 8 - tetrachIorodibtnzo•p-dioxin (TCOO) in the United
States. Results of this study are published in tht National Oioxin Study:
' i e r s 1,5,6, ind 7, EPA (.00/4-82-003, This laboratory, tht Environmental
Research Laboratory - Duluth, was responsible for on* part of the Study, the
analysis of Hsh samot«s. The most significant findings of these analyses uas
tie observation chat fish contamination was more widespread than previously
thought, and that a primary source of TCOD was discharge fro* pulp and paper
production using chlorine.
A second more detailed characterization of anthropogenic organic chemical
contaminants in fish was conducted in subsequent analyses during what is now
called Phase II of the National Oioxin Study. This document describes the
analytical methods used for the determination of the level of contamination of
po l ych I orinated biphenyls, pesticide*, and industrial compound* in fish. A
companion document (EPA /600 / 3 • 90/022) describes the analytical methods used
for the determination of levels of contamination of fitfteen biosijnificant
poIycnIorinated dibenzo•p-dio*ins and dibeniofuran* in those same fish.
12/89 QA/QC Xenobiotics fv
-------
TAILS OF CONTENTS
[. Introduction .......................................... 1
II. Preparation of Sanpl e Extract ......................... t
A. Staple Handling Methodology ...................... C
1. Shipment of Samples to ERL-Ouluth ........... 4
2. Sample Logging and Coding Procedures ........ <•
3. Tissue Preparation and Storage P r oc edur e s . . . <.
I. Extraction of Tissue Samples ..................... 7
1 . Soxhlet Extraction .......................... 7
2. Fortification with Surrogate Standards ...... 9
3 . Fortification with Target Analytes .......... 9
C. Isolation of Xenobiotie Chemical C on t am i na n c s . . . 1 1
1. Gel Permeation C h roma t og r aph y .............. 11
2. Silica Cel Chromatography .................. 11
3. Fortification with Internal Standards ...... 11
III. Standards and Reagents ............................... 12
IV. Analysis of Extracts ................................. 13
A. Gas Ch roma t og r aph i c Operating Parameters ........ 13
I. Nass Spec t rone t r i c Operating Parameters ......... 13
V. Quality Assurance/Quality Control Procedures
A. General Procedures of Operation
t. Sample Analysis Set ........................ 14
2. Sample Tracking ............................ 16
3 . Data Storage .......................... .....16
4. Data Review ................................ 16
12/89 QA/OC Xenobloties
-------
Proctdurts for Analytical Quality Atsuranct 16
1. Ga* Chromatography-Mass Sptctrouttry
i. Instrument Hainttnanc* 16
b. Ga* Chromatography 16
1. Column Rtiolution 17
2. * 11 a t i vt Rtttntion Tim* 17
e. *a»» Sptctromttry 17
1 . Sensitivity 17
2. Sptctral Quality , 17
2. Gtl Ptrmtation ch r on* t og r aph y 18
i . GPC Colunn flow Rat* 18
b. GPC Column R**otution 18
c. Colltction Cyel* 18
3. Silica Gtl Chronatography 18
C. Crittria for Quantitative Analyst* 18
t. Gat Chro>atographie Rtlativ* Rtttntion Tlma.18
2. Analytt Idtntification Crittria 19
3. Signal to Moist 19
4. Rtlativt Rtsponst Factor 19
S. Surrogatt Standard Rtcovtry 19
6. Total Analytt Itcovtry 19
0. Quality Control 20
1. Continual lias Asstssmtnt 21
2. Continual Prtcision Asstssntnt 21
3. Quality Control Chart 21
VI. Quantification of Targtt Analytt* 22
A. Quantification Proctdurt* 22
B. 0tttrmination of Minimu* Itvtl of
Quantification 23
12/89 OA/OC Xtnobiotlc* vl
-------
Tables
Table 1 •- list of Target Analytes, I n t (r n a (.
Standards, ana) Surrog*t« Compounds and
Their Ouentitation Ions 2
f»olt 2 •• Codes for cht 5CC Humo«r and
Nacrix Typt 7
Table 3 •• Surrogate Standard and
Internal Standard Solutions 6
Table <• •• Target Analyte Fortification
Solutions 10
Table 5 •- Cat Chronatogra DMy / * * *»
Spectronetry Operating Parameters 14
Table 6 •• Composition and Approximate
Concentrations o' Calibration Solutions for
Full-'ange Oata Acquisition 15
Table 7 --Target Analytes «itn lax recoveries
for this method 20
f i g u r e s
Figure 1 •• 8ioaccumulative Pollutant Study
Database Output S
Figure 2 •• Schematic of Analytical Procedures...i
2/89 3A/OC Xenobiotics vii
-------
! . I * ' «OOUCT t OX
rhi$ document, developed for Phase [I of the U.S. t f> A National Oioxin study,
deicribes the analytical procedures ind quality assurance plan for tn»
determination of xanobiotlc chemical contaminants in f i t It. The analytical
approach includes:
• a jimpli sample preparation ••thodolofy that product! a *in9it
txtraet wnich nini«is«t aoalyta loitti,
• a proc«dur« that it eo»t tffactiv*
-------
Tablt 1. LIST OF TAtGET ANALrTES, INTERNAL S T A N 0 A « 0 S , AMD
ANAL T T t
giQhtngl-d .internal Stanai
lodobtnztne (Surrogate)
1 ,3,5-Tricnlorobtnitnt
1 ,2,4-T-tcMorobenitne
1 ,2,3-TricMorobenzene
Htxachlorobutadiene
1 ,2,4,5-Tttrachlorobenzene
1 ,2,3,5-Tttrachlorobenztne
S i ph tny I
1 ,2,3,4-Tetracniorobenzene
P en c acn I orobenzene
?h tnan th rent -d .Internal $i
1 • 1 odonaph t h a I t nt (Surrogate)
T r i f I u r a I i n
A i pha • BMC
M exacfl I orobenzene
P en t ecu I o r oan i 10 I e
Gamma • B HC (Lindane)
Ptntichtoroni trobenzene
Oipntnyl dilulfide
MtptacMor
Chlorpyri t 01
I s opropa I in
Oc t ach I oro* t y rene
H ep t acM or E pox i de
Oxych I ordane
CM o rdane , Trant-
Ch 1 o rdane4 C i » -
chP3£ltn..- llnttrnil st.nd,
Nonachlor, Trans-
OOE , p, p' -
0 i e I dr i n
N i t r o f en
E nd r i n
Per than*
Nonachlor, Clt
4 , 4 ' • 0 i i odobi pheny I (Surrogate)
Me t h o * y ch I o r
0 i cot o I ( Ke I thane )
H i r ex
:AS NUMIER
irdj
138703
,.120821
876 1 6
87683
95954
634902
92524
634662
608935
: andard|
1 582098
319846
1 1 874 1
1 825214
58899
82688
882337
76448
2921882
33820530
29082744
1024573
2730413S
5103742
51037'9
•
39765805
72559
60571
1836755
72208
72560
5103731
72435
1 15322
2385855
QUANT
! ON
1 64
204
1 80
1 80
180
225
2 16
2 1 5
1 54
21 6
266
128. _
1 27
306
219
284
280
219
295
218
272
197
280
380
353
185
373
373
243
409
246
277
283
317
223
409
406
227
139
272
E
1
3
3
3
3
0
;
Z
1
1
1
.
3
3
3
3
0
0
3
•
1
1
1
1
1
1
I
,
3
3
0
0
0
0
0
0
1
4
1
(9 r
333
339
.461
. 5<.S
. 625
.629
.871
.891
. : • 3
.015
.173
1--
. 763
. 855
. 390
.912
.924
. 979
.974
. 376
. 185
. 308
.382
.395
. 406
.410
.477
.524
. :oo
. 779
.835
.307
.336
.340
.844
.875
.876
.017
.017
. 079
12/89 9A/QC Xtnoblotic*
-------
Tlbl« 1. LIST OF TAIGET ANAITTES, INTEHNAl STANDARDS, AND
GUAM T
: ON
4* T
9oI yen I or i nittd Biphtnyls, Cl 1-10
Nonoeh I orobiphtny 11 27323188
0ieh I orobipfttnyl» 25512429
rrich I orobiphtnyI• 25323686
Tttr«chtorobtphtnyIt 26914330
PtntlefttorobiphtnyI» 25429292
Ht*«chIorobipntny i s 26601644
Htpt»cMtorobiphtny I » 28655712
Oct«chtorobipntny i « 31472830
NontchIorobiphtny i $ 53742077
0te«chIorobiphtny I t 2051243
188
222
256
292
326
360
394
430
464
498
318
452
556
575
801
818
881
022
250
1 .288
12/89 QA/OC X«nobi«tfct
-------
I I . PRJPAMT I OH QL SAMPl E EXTRACT
A. Sample. Kindt i na Me th odoI oav
1. Sh i pmen t of S amot es t a EtL-Oulut**; The EPA Regional
Offices arc responsible for the collection of the fish samples.
Frozen fish wrapped in aluminum foil art sent to :h« E R I • 0 u I u ( h
laboratory.
2. 5 ampi« Logging and Cad i"a Procedures ; The Sample
Control Ctntar (SCC) or EPA Regional Office* notify Ell-Dulutn
when samples have been shipped. upon arrival, the samples are
checked to make sure they are in good condition and the Shipment
Records are complete. ERl-Ouluth personnel complete the chain of
custody form* and (hen notifies SCC that samples arrived safely or
if there were any problems with the samples (example: a
nislabeled sampled, no species identification).
Samples are initially placed in a large walk-in freezer.
AliquotsC100-500 9) of ground fish tissue sample* (sec. I.A.3.)
are transferred to laboratory freezer A. Extracted samples are
stored in laboratory freezer I. Completed samples are taken to i
locker plant for long term storage. A locker plant log is kept
according to Episode and SCC numbers.
A computerized data base was developed for sample tracking and
data storage. The episode number, SCC number, date sample was
received, matrix type, latitude, longitude, description of
sampling site, and state fro* which tne sample came are entered
into the data base. Figure \ is a sample output of the data base,
The first two letters of the SCC number indicate whether the
sample is an Environmental, Method or Matrix Blank, or Duplicate
Sample. All Environmental sample* begin with the letter 0. The
Hank and Duplicate samples begin with the litter Q followed by a
0 or an R for duplicate or reference fiih sample, respectively.
Table 2 lilt* the possible code* for the SCC number, and matrix
type. Episode numbers for llanki and Fortified Matrix samples are
entered a* 0000.
TIsiue preparation and storage pr oe edures: fish tissue is
ground frozen at ERL-Ouluth in a stainless steel meat grinder.
Each sample is processed through the grinder three times which
homogenizes it thoroughly. For whole fish samples, the entire fish
Including organs and fillets are ground. The ground tissue is
stored at -20°C in solvent rinsed glass jar* with aluminum lined
plastic lids.
12/89 QA/QC Xenobiotics
-------
EPISODE «: 4444
NOf *NASI II: I 10ACCUNULAM VE POLLUTANTS IN
Sanpl* Tracking Syttt* EIL-0 Loe.
SCC t. OP022030
FISH
1234
Sampling In*ormtion:
Sampling Offict: EKL-Ouluth
Stat* I City: HN Ouluth
Sampling Contact: l*g high«tt calibration standard
0 • b«lOM liwit of quantitatisn
L iati ti of Quant 1 tat i on:
***t
-------
E» I SOOE »: 4444 SCC * :
T t r 9« t Analyta
1 ,3,5-Trichlorobantana
' ,2,4-TrichloPobanzana
1 ,2,3-TpiehloPobanzana
HaxachlOPObutadiana
1 ,2.4,5-TatPachloPobaniana
1 , 2,3,5- TetPachiorooanzana
8 i ph eny I
1,2.3,4-Tatrachlorobaniana
Pantach I orobanzana
T P i f I u P a I i n
A 1 pha - INC
xaxach I opobanzana
P an t ach I oroan i to I a
G a ni* a -INC (Li ndana)
Pantachloroni trobanzana
0 i phany I d i * u I f i da
Haptacnlop
Chloppyp'fo»
Isoppopalin
Oe t ach lopoitypana
Haptachlor E pox i da
Oxyc h I opdana
Ch I o Pdana , T r ani •
Ch 1 ordana , C i • •
Nonachlor, T r ant •
OOE, p,p' •
0 i a I d P i n
N i t ro f an
E nd r i n
Parthana
Nonachlor, Cit
Ma t hox yen I or
0 i cof ol { Kal chana)
H i p ax
Total Nonoch l orobt phany l
Total 0 i ch I o rob i phany I
Total Trichlorobiphanyl
Total T a t r ach I or ob I phany I
Total Pant ach I orob i phany I
Total H ax ach I o r ob i ph any I
Total Haptaeh I orobi phany I
Total Oc t ach I orob i phany I
Total Nonach ( orob i phany l
Total Dacach ( orobi phany l
Total Po 1 ych I or i na t ad liphanyls
0*022030
CASKN OA Flaf
108- 70-3
120-82-1
87-6t-6
87-68-3
95-95-4
634 -90-2
92-52-4 o
634 -66-2
608-93-5
1582-09-8 0
319-84-6
1 18- 74- 1
1825-21 -4
58-89-9 0
82-68-8
882-33-7
76-44-8
2921 -88-2
33820-53-0
29082- 74-4
1024-57-3
26880-44-8
5103-74-2
5103-71-9
39765-80-5
72-55-9 E
60-57-1
1836- 75-5
72-20-8
72-56-0
3734-49-4
72-43-5
1 15-32-2
238S-8S-S E
27323- 18-8
25512-42-9
25323-68-6
26914-33-0
25429-29-2 E
26601-64-4 E
28655-71-2 E
31472-83-0
53742-07-7
2051 -24-3
Ell-0
CONC
NO
NO
HO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
loe . :
H {ng/4
0.25
2.34
U.2
23.4
1 .23
17.2
33.1
45.2
1234
21 .2
t8.4
1 18
11.4
60.6
265
187
39.8
564
1234
Nareury ( AA ana lyt i a )
SUMOGATI MCOVEIT:
I odobaniana
Iodonaph th a I ana
4,4'-0 i iodobi phanyI
7439-97-6 0.34
12
48
93
12/89 OA/QC Xanobiotie*
-------
Environmental samplt
Firtt Lttttr:
Stcond Lttttr:
A
1
c
0
E
F
C
H
T
J
• • Itgi
• - • t g i
-- Itgi
-- Rtgi
• - « tg i
-• Rtgi
• • 1 tg i
• • fttg i
• • Itgl
-• Rtgi
on
on
on
on
on
on
on
on
on
on
1
2
3
4
5
6
7
8
9
10
OA saaplt
a
•• Mtthod blank
•• Laboratory duplicate
• • R t ftranc a fi»« or
fortifitd matrix
Matrix Codt
F - • F iin
I •• Lib duplicate
* •- R t f trtnct fish
T • • Mtthod Hank
Matrix T ypt
Wl • • Who I• bot ton
If • • lotton f iILtt
M - - Prtdator f i I 11
W» •- Uholt prtdator
I. E«trie t i on of T t
-------
Figure 2. Schematic of Analytical Procedures
A) NET COLLECTION
B) SHOCK COUECnON
PREP FISH
AjGHMDFftinOfl
B)GflM) WHOLE
EXTRACTION
A) BLEND MB TISSUE
B) EXTRACT WITH
A)MUOERNA4MMSH
APPARATUS
QOETEflMNE TOTAL
UPD
ZlgSUCAGEL
SIICAGFI CHHQilATQGflAPHY
A) ACIWAIE IXC*. OttRMGHT
B)OEACnVATEl%HO
C) ELUIE ANALY1ES WITH
15% CH Ci 4CXANE
AGO M1FJUAL SIAMDAHDS
G£L PEHMEAnON CHHOMATOGHAPY
COIifCT FRACTION 17 TBCS THE
DISTANCE FROM APEX OF DC HP
TOTHEAPtXOfPYTtNE
A) ADO Iri TOLUENE
B) CONCENTRATE TO ttttl
KKU.
AMAJ
,j , , j j ELECTRON MPACT WfiZATWN
l
.1
I. L
POSITIVE CHEIiCALlOMZAIlON
NEGATE CHEMCAL tOMZATUN
QIMNTUSI
= ^—
^^ H^T
iMMMMKM
0V* «
^"~— ~~~~
=~~ ~ '
ll| 1.1 ll
l|ll.l ll
LiaLh-
12/89 QA/QC X«nobiotic« 8
-------
2. Port' f ' C « t i a n aich Surrogate, Standard! ;
Etch sample 11 fortified with Surrogate Standard Solution « <25
ut) prior to soxhlet extraction. Tht standards in this «oiut:sn
have btin stltcttd to represent various typts of chemicals ' 3 j r.
in tht list of target analytet, and are used to evaluate in*
recovery of target analytes in eleaned-up environmental samele s.
Surrogate Standard Solution A (25 uL)
C omoound £2n£201-ili20_
I odoben t ene 125
1 • I odonaph t h a I ene 125
125
Internal Standard Solution (10 ul)
Compound
I i pheny I -0 1 Q 50
Plttnan tnrejnfO j g 75
Ch ry i tnt - 0 "
fortification with Target *naIvtei : A blank
matrix sample is fortified with one of eight Target Analyte
Fortification Solutions (23 u L) , Table 4, to evaluate the
overall accuracy of a subset of tht target analytes. Two ot
matrix samples will be fortified with- the same solution
once in tvtry five (20X) sample sets to evaluate precision.
12/19 QA/QC Xenobiotics
-------
Solution A: Aroelor 1254 at 500 ug/«l
-------
C . I s o t i t i on o f onob'Qtie C h en i e i ( Contaminants.
1- Gel Permeation Ch r oma t o3 r a ehv ; A GPC system is u»«d ta
isolate xenobiotic chemical contininants from biological molecules
(fish lipid). The GPC column (2.5 t 50 em) (ACE Glass Company) is
packed with previously swelled Siobead SX-3. The GPC injection
port valve is fitted with a 0.075 mm stainless steel screen filter
to remove particu I ates. The solvent is pumped at 5 mi/min. The
absorbance of the effluent is monitored with a 254 nm j v detector
(Virian Aerograph). Each aliquot of extract is diluted with 2 -ni
of eluCion solvent. The supernatant is quantitatively transferred
into a sample loop of a 24 port auto-sampler with three additional
1 ml washes of the sample vial. The loops of the auto-sampler are
loaded sequentially onto the GPC column under computer control. A
GPC performance standard solution (sec. IV.B.I) is run to
determine the collection period. This sample is run prior to each
sample set. Xenobiotic chemical contaminants which elute 4
minutes after the elution apex of 0i•2•ethyIhexy I phtha I ate, OEHP,
and 1.7 times the elution volume between the apex of 0 E H P and
Pyrene are collected in a KB. Each sample (two loops) are
collected in a single KO. Hexane (10 ml) is added to the
-------
MI. Standard* and teagents
A . leegent*
1. Solvents: Only pesticide grade distilled in glass
solvents art uftd. They art: hexene, methylene e ft I o r i a« ,
toluene, acetone, and cytcopentane (Burdick and Jackson and
Fischer S c i tn t i f i e ) .
2. Sodium Sulfate: Sodium sulfate (laker Chemical Company
reagent grade anhydroua) is baked at 65Q9C in a furnac*
-------
6. Pesticides and PCI Standards: A stock solution it made
containing the ptttieidtt listed in Table 1 and tht PCI
congeners listed in Table 6. five calibration solutions
ar» «ade at the eone antrationa listed in rabla 6.
7. Fortification Solution!: Tha paaticida* ara dividad into
three fortification solutions at two diffarant concentrations
(Tabla 4). Aroelor 1254 i* uaad at tha PCI fortification
solution at tha concantrationa littad in Tabla 4,
I V. Analysis of Extract 1
Samples ara analytad on a finnigen-MAT Modal 4500 CC/MS
with SUPEIINCOS software and aupplementa I public domain software (1,2)
providad by tha U.S. EPA laboratoriaa in Cincinnati, OH. All Targat
Analytaa wilt ba quantified individually and tha rasulti raportad at unique
values, aicapt for PCIt, which will ba raportad by total congener at eacn
degree of ch I orination. An analyst* set includes an analysis of a mass
spectrometer performance check solution (sac. til.1.2), an analytical
standard, an unfortified solvent (instrument blank), and twelve prepared
samples. The CC/MS operator reviews the MS performance solution,
analytical standard, and instrument blank data before starting the analysis
o f samp lea.
Gas Chromatoaraoie Peer a t i na Parameters; A Mnnigan-MAT
Model 9610 GC is fitted with a 60 m X 0.32 mm 10 01-5 fused silica
capillary column (j 4 W Scientific) and operated in a temperature
programmed mode. The capillary column is interfaced directly »itn : • t
ioniier. Injections are made in splitless moda. Specific operating
peremeters ara providad in Table 5.
Spec t romet r i c Qoarati na Perimeters; A f Inntgan-MAT
Model 4500 maaa tpaetromater is used in the electron impact mode.
Specific operating parameters ara provided in Table S. The
positive identification of target analytas is based upon a reverse
library search threshold value and relative retention time (KIT).
Quantification of the target analytes is baaed on the response factors
(« F ) relative to one of tha three internal standards listed in Table 1,
Table 1 is formatted so that tha target analytea follow the internal
atandard used in quantification. »ITs and *Fs are initially
determined using data from triplicate analysis of each of five
target analyta quantification solutions (Table A).
12/M OA/flC xenobiotlca IS
-------
SC P • r erne t er * :
Injector Temp.: 250 C
Inttiil Temp.: 100° C held tor 1 win.
First Ramp: 5° C/min to 175° C
Second ttnp: 3° C/min to 280° C hold 'or 20 TI t n
NJ Parameters:
Cycle tint: 1.3 second
Acquisition tint: 0.95 second
Scan tate: 1.0 second
Scan lingi: 95 • 550 amu
Electron Voltage: 70 «V
Emission Current: 0.30 mA
Manifold Temp.: 95° C
Ionizer T emp. : 150° C
Oui M tv * *lu r tnet/OuiI 'ty Control (OA/QC 1
» . Central Procedures o f Ooeritipn,
1. S «mpIe *n« I y» i s Set: Analysis o* staples is
done in sets of twelve consisting of:
• . 8 I enlc : A METHOD ILANK (blank eitraction
apparatus) is analyzed with each set.
b. ro r t ifi e d Matrix; A blank matrix
sample is fortified with ont of eight different
mixtures of Target Analytet (Table 4) and analysed
with each set.
e. Oupli eate; Each analysis set contains
one duplicate sample. In four of five (SOX) of
the sample sets the duplicate is an environ-
mental sample previously chosen for
analysis in that set. In one of five (20X) of the
sample sets the duplicate is a blank matrix
sample that has been fortified with the same
target analyte subset at the fortified Matrix
Sample. This additional type of duplicate insures
that sufficient data is available at the end
of the study to evaluate precision on all target
ana Iyt es .
12/89 QA/OC Xenobiotic* U
-------
Ttbl* 6. CoMpoiicion and Approximate Concentration* of Calibration
Ana I y t •/ I nt . S td. /
C^ _______ Sik-l ___ £ik_2 ___ £ik-2 ___ Sik.i ___ £*k_l
0
0
0
0
0
0
0
0
1
.25
.25
.25
.50
.50
.50
.75
. 75
.25
0
0
0
1
1
1
1
1
2
.50
.50
.50
.00
. 00
.00
.50
.50
.50
1
1
1
2
2
2
3
3
6
.25
.25
.25
.50
.50
.50
.75
.75
.25
2
2
2
5
5
5
7
7
12
.50
.50
.50
. 00
.00
.00
.50
.50
.50
1
1
1
1
1
5
5
5
0
0
0
5
5
25
.00
.00
.00
.00
.00
.00
. 00
.00
. 00
PCI C * I . Congener*
Cl, 2-
C12 2.3-
Clj 2.4,5-
C14 2.2' ,4,6-
Cl, 2,2', 1,4,5'-
C14 2,2',4,4',5,6'-
C17 2, 2' , 3. 4, 5,6,6-
C l. 2,2',3,3',4,5,6'-
o
CI10
All Target Analyto
othtr than PCIt listtd
in Tabl* 1 0.50 1.00 2.50 5.00 10.00
[nttrnal Standard*
Chry»«nt-d12 7.50 T.50 7.50 7.50 7.50
Ph«nantrtrtn«-d,0 7.50 7.50 7.50 7.50 7.50
liphtnyl-d1Q 5.00 5.00 5.00 5.00 5.00
Surrogate Compound*
lodobanitnt 0.50 1.00 2.50 5.00 10.00
1 -lodonaphthaltnt 0.50 1.00 2.50 5.00 10.00
iififiS2ooioo
12/89 QA/QC Xtnobfottcs 15
-------
d. Envi r pmmn t i I s amp I es : Mint £ n v i r o nm t n t a l
Sample* are analyzed with each set.
I. Simp It r " «C k i n q ; t sample tricking and logging
system is used to assure that no samples art
last (stc section [ - A ) .
3. 3at a S t a r a 3 e : 3ata folders consisting at ill
hard copy output is maintained for each sample.
In addition, all raw GC/MS data is stored on
magnetic tape.
4 . o a t a »ev i ew : GC/MS data is initially reviewed
during sample set acquisition by the GC/MS operator
to assure that all instrumental QA parameters are being
met. Final review and release of the data is the
responsibility of the Project Manager. Once the quality
assurance criteria have been met, the quantification
information is entered into the database. Quality
assured data is then transferred to I 1 0ACC/STOK IT
for availability ta the EPA Regions. lefore release
to the public, all transferred data it verified for
completeness by the database manager.
General Procedures o f Analytical Quality Assurance:
1 . G a l C'lrairiatoaraohy-xass Soee t rome t r v System;
a. instrument *ai ntenance: The GC/HJ system
is maintained according to the manufacturer's
suggested schedule. The maintenance schedule
is indicated on a calendar located near each
instrument. Log books will be kept for: Daily
instrument settings; Samples analyzed;
Maintenance; and Data Storagt. Instrumental
problems resulting in more than two days of down
time are to be reported to the EPA Mass
Spectrometry facility Supervisor to discuss
solutions to the problems.
b. Cas Chrematoaraphy; The performance of the
GC is evaluated by determination of the
number of theoretical plattt of resolution, and by
relative retention of the Surrogate Standards.
12/89 QA/QC Xenobiotics 16
-------
1 . Column Resolution; The number of
theoretical plates of resolution, N, i$
determined it the tint the calibration curve
il generated using C h r ys ene • d , g and monitored
• i t h each sample set. The value of M s n a I i not
decrease by more than 20X. The equation far H
is given as follows:
M . 16 ( • r / u ) 2
•nere, •. T > Retention Tint of
Chrysene-d^g in seconds
w • Peak width of
Chrysene-d13 in seconds.
*• 9 e i 1 1 t ve Retention Time; Relative
retention times of the internal standards
shall not deviate by more than •/- 3 X from
the values calculated at the time the
calibration curve was generated.
e. Mass Soec t r ome t ry ; The pe r f or mane* of th«
mass spectrometer Mill be evaluated for both
sensitivity and spectral quality.
t. Stniitiv'tv! The signal to noise value
must be at least 1.0 or greater for m/i 198
from an injection of 10.0 ng decafluorocri-
ph eny l phospfi i ne (OFTPP).
2 . Spectral Qua I ' t v : The intensity of
ions in the spectru* of BFTPP must meet the
criteria listed below:
1 27 30-60X mass 198
197 < IX mats 198
198 base peak
199 5-vX mass 198
442 >40X mass 198
12/89 OA/OC Xenobiotlcs 17
-------
2 . S t ( Permeation Ch roma t oar aoh v: T ti • GPC i *
maintained when needed •» determined by visual
inspection (column ai«ea I or11ion , leaks, cricks, etc)
measurement of flow rat*, and routint measurement of
cont»•inatton of instrument blanks.
a. SPC Cot umn Mow * 11 e : The flow rate of the
CPC is measured three times during an analysis:
1) before tie CPC rtsolution solution, 2) aftar ill
samples are loaded but before analysis and 1) afttr
all samples have been analyzed. flow rate should not
vary by more than »/• 0.2 mi/i»in.
b. G P C C oIumn Resolution; A J50 ul injection of a
performance solution containing Dacthal (5 mg/mi>,
OEHP (4 mg/ml), and Pyrene (0.2 mg/ML> must be run
daily to evaluate column resolution, and to determine
analyte starting and ending collection volume.
c. Col lection Cvele: Proper operation of the
CPC will also be evaluated by recording the time
during an analysis cycle that the coI Iection/wa 11e
valve is in the collect position. This is
accomplished most easily by recording the valve
position on the second pen of a dual pen recorder.
The start and end of the collect cycle must not
deviate by more than »/- 2 ML.
S. Silica Ce I Ch roma t oa r aohy; The silica gel
column will be evaluated by its ability to resolve
cholesterol from a select model target analyte,
Oieldrin. A solution (1.0 *L ) containing Dieldrin
(2.5 «9/mi) and cholesterol (10 mg/ml) is spiked onto a
silica gel column and eluted with methyttne
chI oride/hexane (15X, v:v, 60 «L>. The eluant,
analyzed by fla«e ioniiation detector/gas chromatography
CMD/CC) oust not contain more than 10X of
the cholesterol while at least 90% of the Oieldrin must
be recovered.
C. Criteria for Quint 1t at i vt Analysis; All of the
following quality assurance criteria must be met before a
quantitative value may be reported for an analyte.
1 . Cat Ch rorna toar aeh i c t e I a t i ve * etent i on Time;
•elative retention times of the target analytes shall
not deviate by «ore than */• 3 X fro* the values
established during the generation of the calibration
curve (see Table 1 for »»T data).
12/89 QA/OC Xenobiotics 18
-------
2. *"al vta 1 dent i M eat i on Cr i taria : Ravarta saarch
identification of an analyte (SIA*) must have in MT
»a t ue of 800 or greater .
3. S i a n | \ j_j_ Hoist; The quantification ion mutt Nave
• tignal to noist valu* of at leatt 3.0.
4. 9 e i a t i v»^ Response factor; The rtlativt rt»pon$a
factor for aacn analyt* quantification ion rtlativ* to
t h * appropriatt inttrnal standard quantification ion
mult not dtviatt By mort than 20X from tha vatua
datarminad on tht pravioua day (within a 24 hour pariod)
and within SOX of tha maan vatua fro* tha calibration
curva. Tht target analytai Endrin, Oicofol, and Oaca-
ch l orobipnanyi nuat not daviata by nora than $01 from
tha pravioua day.
A control chart it maintainad on tha daily rasponsa
factor* for tacn targat analyta.
5. Surroaata Standard »«eovary; Tha parcant racovary
(XR> of aach surrogata ttandard will oa datariainad
for all lamplai, at shown balow:
XRi • 100CCo/Ca]
whara XRi * surrogata pareant racovary
Co • obtarvad cone antration of
surrogata
Ca * actual concantration of
surrogata addad to tha aaiapla.
Tha parcant racovary mutt ba within 25 and 130
parcant for iodonaphthalana and SO and 130 parcant
for 4,4'-diiodobiphtnyl. Tha racovary of iodobaniana
qua IitativaIy indicatat tht axtant of avaporativa
loatat that tha analytat littad in Tabla 7 way axparianca
Total Analyta »acovary: Tha ovarall accuracy of
quantification of all targat analytat it avaluatad
by tha analysis of a tubtat of targat analytat
fortifiad into a matrix blank. Racovary of tha
fortiflad analytas mutt fall within tha ranga of SO to
13 0 X axcapt for thota littad in Tabla 7. Tha analytat
12/89 QA/QC Xanoblotics 19
-------
tablt 7. Tareot Analytts with low recoveries tar
1 ,J,5-Trlehlorobeniene
1,2,4-Trichtorobenitnt
1 ,2,3-Triehtorobeniene
1 ,2,&,5-T«trachlorobenzent
1 ,2,3,5-Tttrachlorobeniene
1 , 2,3,4-Tttrachlorobtnitne
Ptntachlorobtnzeno
H t «ech lorobutaditnt
listed in Tablt 7 thOM rtcoveries that fill in tht
of 20 to JOX for this «tthod. An avtraft analytt
rtcovtry (XA«) for ill ttrgvt »n»lyt«* will b« ctlculittd
•nd mu»t bt grtcttr :h»n JSX but lti< than 1SOX.
A control chtrt for tottl inalytt rtcovvry §nd «n*lytt
r«eov«ry i* ncinttintd for ••ch iplkinf lolution.
To d«t«r«int totil anclytt rteov«ry firtt ctlculttt
tht ptretnt rteoviry (XR) for ««eh fortification inilytt
uiinfl,
XI* • 1 00((Ai•Ii )/TI)
wh«rt XI* « tnilytt ptrctnt rtcov«ry
A1 * mtiturtd tn»lyt« eonc«ntrition in
fortification itnpla cfttr
• naIys < «.
II • natural analyt* concantr•tton in
stuple bafort fortification.
Tl • known trut conetntration of
analyta fortification Itvtl.
Than calcuKta XAR by,
XAI • (Summation of Xla) /N
whtr« N • nuabtr of for11f
-------
C ont i nui l Si as Assessment :
XI » <100(Ca-Cb)/T) • 100
where Ca • determined concentration after analysis
Ca • concentration present before spike added,
T * known value of the spike.
t '
l P r » e i i i a n Assessment ;
Prtcisian of qu in t i f i e a t i on of *ich targtt inalytt
will bt *st«*f*d stparacaly for duplicatt tnv i r onm»n t • I
samplti and duptieatt fortMitd Matrix s**pl*t.
XP • 100 «C1 -C2 )/Ct ]
wn«r« C1 • eonetn t r at i on of analytt in ipik*
t i«p I • 1 .
C2 * concentration of analyta in tpika
samp 1 1 2 .
Ct > Actual cone in t ra t i on of anatyta
for forcifitd matrix tanplt or mtan of
duplicata tn v i r onnan t a I tawplat.
Q u l U t v Control Char 1
OFTPP sanaitivity and/or
ion rat i ot
P11un» MS
c I tan MS
ftalativa Ratfntion Tina
adjust CC paraftatars
ftuah GC cot unn
raplaea GC colu«n
Ralativa Raaponaa factors
ratuna MS
raealibrata
Racovary of Surrogata Standards
Total Analyta Racovary (tAR)
var\ fy MS data
rapaat saaipla attraction
If XR for at laaat SOX of
targat analytat not littad
in Tabt a 1 «aat* cr i tar i a
proeaad with calculations,
.lilt.£SS£i£l£i.ill.iiSBiti.
12/19 QA/OC xanobiotics
21
-------
V I . quantification 0 f _ T tr ae t *"e_l y t as !
A . a^in t I f < ea t I on Procedures
Response factors art determined for each target anatyte and surrogate
compound relative to on« of the three internal standards. The
response factors « r • determined by:
Rf • *xcis'*isc«
A j peak area of quantitation ion for a target analyte
or a surrogate compound,
A., • oe a k i r e a of quantitition ion for aither
8 i phany I • d1 Q , Ph anan t h r ana • d 1 Q , or Ch r y s tna - d , , ,
CjS » injaetad quantity of tha inttrnal standard,
Cg * injaetad quantity of tha targat anaiyta or
surrogate compound.
Public domain software was provided by the EPA Office of
Research and Development, Environmental Monitoring and
Support laboratory for the automated identification and
quantification of the target analytes. The data reduction
software uses the following formula to calculate targat
analyte concentrations:
COMC « «QA • NUN • 0«V) • FBSV) / (VIA • SIZE)
where QA • concentration ts calculated uting the
response factor from the daily standard,
HUM > factor to convert to number of ug/ml,
Q*v > Quan Report volume (0.100 ml),
VIA * Volume Internal Standard added to (0.100 ml),
FESV • Final Effective Sample Volume,
SIZE « sample size (g).
The FESV term accounts for the total lipid present in the
sample and the amount injected on the GPC. The FESV is
calculated by:
FISV • Final Volume (ml) • (Total Lipid (g) / Lipid on CPC (g)}
12/89 QA/QC xenobioties
22
-------
Cilcutttiont for determining surrogate spikes end fortified
amounts use tht following equetion:
COUC • CJA • FfSV) / (F$»V • SIZf)
where SA > tpfke emount,
F$«V » Final Effective Surrogate Volume,
FESV. SIM . ttn« «t above.
The FSKV term it equal to th« FESV ttra. Tht eonetntr•tion
of • ttrgtt antlytt i* dtnottd in the Hnel report If it
exceeds the cellbretfon renge, <'C' fltg), or it below the
quentitetion limit, ('0' fltg).
0 eterni net i on o_f_ * < n i mun leve I of Quint 1 f 1 e it i on
The celeuleced Method detection li«it« (HOLD for the inelytei, (determined
•ccording the Federal Regitter 1988, Vol. 40, Appendix I, Pert 136,
Definition end Procedure for the determination of the Method Detection
Limit, Rev. 1.11), are unreeIi$11ca I Iy low in comparison to the analysis at
the xenobiotic calibration solutions over a two month period. lased on tn«
analysis of the calibration solutions a minimum level of quantification wis
determined for eech analyte, as given in the Introduction, which accurately
reflects the instrumental detection limits.
minus orrici iMO/T4*-ttt/oc4)e
12/89 UA/QC XenobUtUs
-------
APPENDIX B
ADDITIONAL DATA ANALYSES
-------
APPENDIX B-l
Nomographs for Estimating Cancer Risks
-------
B-1-1
Q>
U
a
O
«o
m
o
O
X
UJ
10
2
10
-3 _
10
10-
\Q
10
-7
1000 100
CHLORDANE
Consumption Rale (grams/day)
1000 100 10 1
[mr i r ~i --[~r—firrr r T jf i • jir^rrT T ' r • ~]
10
1 — i i i IMI| - T — riii ITT] --- i
0.000001 0.00001 0.0001
0001 0.01 01 1
Fish Tissue Concentration
(mg/kg wet wt)
TI( 1 rTTTTTIf ' T III Tt T I)
10 100 1000
-------
DIELDRIN
JS.
DC
8
O
S
X
HI
2
10
103 d
10'4 J
10'6 J
ID'7 d
Consumption Rale (grams/dayj
1000 100 10 1
1000 100
~l — I I 1 1 1 n I i I I I HM| I i i i 1 ni| I I i i llilj - 1 — r-rrrrnj "i r n rrn i -T rrr ni|
0.0000001 0.000001 0.00001 00001 0001 001 01 1
Fish Tissue Concentration
(mg/kg wet wt)
10
100
B-l-2
-------
B-l-3
§
(0
O
(0
«
0)
O
X
LU
10J
io4 A
10
-7
\tf
1000 100
p,p'-DDE
Consumption Rate (grams/day)
1000 100 10 \
17 r""r T nrrrj~" ~r~ T TTTTTT]— T~"T ~\ T MI if T ~r IT rni] r i i i T nr; ~ • i i i r i n i
o.oooooi 0.00001 0.0001 0001 001
o.i
10
100 1000
Fish Tissue Concentration
(mg/kg wet wt)
-------
HEPTACHLOR
J*
CO
cel
O
CO
CO
8
X
LU
10
-2
10
3 .
10 < J
10'J -
10° -=
10
'7
Consumption Date (grams/day)
1000 100 10 i
1000 too
~i—i i i 11 ii ] 1—i i i 1114 r
0000001 0.00001 00001
rrrnii—
i--i i nrrT)- i
0001 001 01 1
Fish Tissue Concentration
(mg/kg wet wt)
10
\— r— i i IIH,
100
1000
B-l-4
-------
CO
ir
I
10
O
to
u
X
Ul
10
2
10
-3
10
10"
10
-6
10
-7
1000 100
r i 1 1 ni - 1
HEPTACHLOR EPOXIDE
Consumplion Rale (grams/day)
1000 100 10
piu MI ly-jnirny r -pi
1 — r~rnm|
m]
00000001 0000001 000001 00001 0001 0.01
T T-|-TTITT[ i T-T-TTIITJ •— i riT>ni|
01 1 10 100
Fish Tissue Concentration
(mg/kg wet wt)
B-l-S
-------
8
3
(ft
i
x
tu
10
ID'3 J
10'
10
-7
HEXACHLOROBENZENE
Consumption Rate (grams/day)
1000 100
|inr i r
1000
1 — I I I I I ii i - 1 — I I I ini| - 1 — I — rrrnr] I — I I i im] ---- 1 — mTrn| i i rinii] i TTTTIIIJ • -
0.000001 0.00001 0.0001 0001 001 01 1 10
Fish Tissue Concentration
(mg/kg wet wt)
nij i i iiini|
100 1000
B-l-6
-------
3-1-7
(A
s
a
O
CO
to
0)
O
X
LU
10
2
10
3
10"
10
5
10"
10"
000 100
alpha-HEXACHLOROCYCLOHEXANE
Consumption Rale (grams/day)
1000 100 10 i
(irrr r r r
~~i' i 11 fTf] i i ~n 'i ni]" 1—r ~r~r i TTTJ r~r Trrrnp r—i r~i i ITTJ" —r" T r 11 m| T~T i n TTT]" T'^T T r r rn j i i i T rrir|
0.000001 0.00001 0.0001 0001 001 01 1 10 100 1000
Fish Tissue Concentration
(mg/kg wet wt)
-------
gamma-HEXACHLOROCYCLOHEXANE
<0
i
a
O
0)
01
8
X
1U
2
10
10'3 d
10'4 J
10 5 -J
10
Consumption Hale (grams/day)
1000 100 10 i
purii i
1000 100
~i—I I i 11111 1—rr I 11 it| r r-TTTTrq r~r-nrinrj-
0.000001 0.00001 00001 0001 001
01 1
Fish Tissue Concentration
(mg/kg wet wt)
10
100
1000
B-l-8
-------
CO
8
CO
O
(ft
0>
S
X
UJ
10
-2 _
10
3 .
10
10
-5
10
10"
1000 100
MIREX
Consumption Rale (grams/day)
1000 100 10
i 1 1 ill | 1 I i t I n i| I i I i t MI | i T TTTrrrj i r~rrrm] — i — r~rrrm| r r rrrrrrp i — r~rTTni(
0.000001 0.00001 0.0001 0001
001
0.1
1
10
Fish Tissue Concentration
(mg/kg wet wt)
100
1000
B-l-9
-------
PCBs
Consumption Rale (grams/day)
8
CO
O
(0
CO
4)
O
X
UJ
to1
102 -J
10'
10* J
10s J
108 -4
1000
p ITT" I
100
1000
—I — i i i I in I - 1 — i i I ill l| -- 1 — i — i I I ill I - 1 — i — mrnq - 1 — n I i ITT] --- 1 — mniT|
0000001 0.00001 00001 0001 001 01 1
Fish Tissue Concentration
(mg/kg wet wt)
i T-rTrmj --T-I T rmi|
10 100 1000
B-l-IO
-------
TRIFLURALIN
0)
0>
u
c
<0
o
(0
0)
0)
u
X
LU
10'
10s
10'
10
7
10'
10
9
1000 100
Consumption Rate (grams/day)
1000 100
iTrrrvi ' 'X"^T
~T y '' ' i
to
I I II l| -- f I TTTTTT] — "I
0.1 1
0.000001 000001 0.0001 0001 0.01
Fish Tissue Concentration
(mg/kg wet wt)
10
I7TTT-p- I t 7TTin|
100 1000
B-i-n
-------
APPENDIX B-2
Nomographs for Estimating Noncarcinogenic Hazard
Indices
-------
01 -,
.001
X
0)
•o
.0001 -
.00001 4
.000001 -J
.0000001
BIPHENYL NONCARCINOGENIC EFFECTS
1000
100
Consumption Rale (grams/day)
10
1000 100
frrrr r r~ i—ry" prm
.0000001 00001
T
0001
I "T T 1 TTf " 1 T 1 T 1 I H) J " T r" IT TIT
001
01
10
100
Fish Tissue Concentration
(mg/kg wet wt)
5-2-7
-------
CHLORDANE NONCARCINOGENIC EFFECTS
Consumption Rate (grams/day)
IUU -
10 -
X
0) 1 -
£ ;
i
8
(0
I 0.1 -
.
001 -
0.001 -
[TTT
f/
// */
///y
*7/7*
// +7 S/
//////
///
/ / /
\ 1 1 1 1 1 1 1 1 /I 1 1 1 ... L/, 1 , , Jf , , , 1 1
1000 100 10 1
( 1 M 1 f i (| i r r r 4 r f i [ f \ \ i \ w\\ \ t t r ( i M f i f~I T n
0.00001 0.0001 0001 001 01
1000 too
r~t I t JTnTTt
i r i i i
~ r~rr rnrr r
1 10
Fish Tissue Concentration
(mg/kg wet wt)
nil
100
1000
B-2-2
-------
X
0) .01
CO
N
CO
.001 :
.0001
.00001
1000
CHLORPYRIFOS NONCARCINOGENIC EFFECTS
Consumption Rate (grams/day)
1000
firr i
100
100
.0000001
' ' "'I
.00001
-r —i—i i i • l n ir
rij 1~ i~~i TTTirj r—i t i nrrf
T -• r i i T ? rr i
.0001
.001
01
10
Fish Tissue Concentration
(mg/kg wet wt)
100
B-2-3
-------
p,p'-DDE NONCARCINOGENIC EFFECTS
100
10 -
2 ,
•o
i
CO
I 0.1
0.01
Consumption Hale (grams/day)
1000 100 10 1
T i r I i |
1000
10
0.001 -| 1—i r i inn
00001 0.001
TIIII— ii—i i 11 n] r—i~i ITTTTI i
001
0.1 1 10
Fish Tissue Concentration
(mg/kg wet wt)
n]
100
1000 10000
B-2-4
-------
DIELDRIN NONCARCINOGENIC EFFECTS
too -,
10 -
s .
•a
•a
CO
I o.i
0.01
0.001
1000
100
Consumption Rale (grams/day)
"TTTTTTT
i i | i i i "I TT TT | 'i i ~ i i i i "i i
000001
00001
0.001 .001 0.1 1 10
Fish Tissue Concentration
(mg/kg wet wt)
100
ll I,
1000
B-2-5
-------
HEPTACHLOR NONCARCINOGENIC EFFECTS
X
«
•o
.01 -
.001 -
.0001 -
.00001
Consumption Rate (grams/day)
1000 100 10
(Trrrn r
1000
100
TTT
.0000001 .00001
0001
.001 01 1
Fish Tissue Concentration
(mg/kg wet wt)
T i nr ' "i 11 i 1111
10 100
B-2-6
-------
100
10
X
0)
•o
c
(0
N
to
1 -
0.1 -
0.01 -
0.001
HEPTACHLOR EPOXIDE NONCARCINOGENIC EFFECTS
Consumption Rale (grams/day)
1000 100 10 1
1000
100
n riTn i i i r i
0000001 000001 00001
0.001
001
i T i ; m
01
Fish Tissue Concentration
(mg/kg wet wt)
10
100
B-2-7
-------
10 -
1 -
X
0>
•o
CO
N
(0
1 -
.01 -
.001 -
HEXACHLOROBENZENE NONCARCINOGENIC EFFECTS
Consumption Hale (grams/day)
1000
.0001 -1 1— up
.00001 0001
1000
100
|7M I T f
"TTTTTT1 r-1-nTTTTI 1 r TTT1 iq ' ' ' ' ' 1nl
001 01 1 1 10
Fish Tissue Concentration
(mg/kg wet wt)
100
1000
B-2-8
-------
100 -,
10 -
X
0>
•o
1 -
X 0.1
0.01 -
0.001
gamma-HEXACHLOROCYLOHEXANE
NONCARCINOGENIC EFFECTS
Consumption Rale (grams/day)
1000 100
1000
10
n i—n
00001 0001 001
r rTTm7 i—i—n rnn r—n i r inr — i
01
10
Fish Tissue Concentration
(mg/kg wet wt)
TTII r—T i~rn nj- • i • T i i i uii
too 1000 10000
fi-2-9
-------
ISOPROPALIN NONCARCINOGENIC EFFECTS
x
0>
•o
.001 -
.0001
Consumption Rale (grams/day)
1000 100 10
.00001
i 11 M| 1—i—i 11 nil r—i—i i 11 n| 1—m i i ill r ~ i ~r T 1111| r~r~ri TTTTI— r —i—t~i i mi
.00001 .0001
001 01 1 1 10
Fish Tissue Concentration
(mg/kg wet wt)
100 1000
B-2-10
-------
100 -
10 -
X
0>
c
"S
(0
N
<0
.1 -
.01
001
1000
MERCURY NONCARCINOGENIC EFFECTS
Consumption Rate (grams/day)
1000 100
(Trrrrr'T "i
10
— i — i i i i mi - r~~i i i
.001 .01 1
i i i rrrnT --- r — r-rrm?i~ i i r i rrni - r-VTnnii i i i i i r n
1 10 100 1000 10000 100000
Fish Tissue Concentration
(mg/kg wet wt)
B-2-n
-------
MIREX NONCARCINOGENIC EFFECTS
100
10 -
3 '
•o
•o
§
<3 01
0.01 -
0001
000 100
Consumption Hale (grams/day)
tooo
frn i
I I I [ I II] 1 I~I TTTTTl T~ r T~ITTTri r'"T"TTTlllI ~T ~T"n"mTT" 1" '
0.000001 000001 00001
0.001 0 01 0 1 1
Fish Tissue Concentration
(mg/kg wet wt)
i i n i u t;
10 100
B-2-I2
-------
PCB (AROCLOR 1016) NONCARCINOGENIC EFFECTS
100
10
X
Q>
•a
to
N
co
i -
o.i -
001
1000
1000
fTTTTr
Consumption Rale (grams/day)
100
10
0.001 -| r-r-rmrr
.00001 0001
i ii| 1—i—mrrir ' ~! r i i mrr i T-TTI n ITi -~i—r
.001 .01 1 1
Fish Tissue Concentration
(mg/kg wet wt)
r -1—TTTrnr i~ ' i r i 111.
10 100 1000
B-2-13
-------
10 -,
S
<0
.01 -
.001
TRIFLURALIN NONCARCINOGENIC EFFECTS
Consumption Rate (grams/day)
1000
100
1000
100
.0001
.0001
.001
.01 1 I 10
Fish Tissue Concentration
(mg/kg wet wt)
100
I r ~i- r r i
1000
10000
B-2-14
-------
APPENDIX B-3
Site Description Matrix
-------
Key to Table B-3
Matrix of Episodes and Site Descriptions
COLUMN HEADING
DESCRIPTION
2
3.
4.
5.
6.
7.
8.
9.
EPISODE
LATITUDE
LONGITUDE
STATE
WATERBODY
LOCATION
NSQ
B
POINT SOURCES:
EPA REGION The U.S. Environmental Protection Agency Region which includes the
sample location.
The EPA Episode Number which is specific to each sampling location.
The latitude of the sample site in degrees, minutes and seconds.
The longitude of the sample site in degrees, minutes and seconds.
The state where the sample was collected.
Name of the water body where the sample was collected.
The nearest town, road or county to the sample location.
Sample site from the USGS NASQAN monitoring network.
Background site as selected for study.
: Point sources include the following six categories:
10. PPC Site near paper and pulp mill using chlorine for bleaching (includes mills
using the sulfite process).
Site near paper and pulp mill not using chlorine for bleaching.
Site near refinery using the catalytic reforming process.
Site near an EPA National Priority List Site (Superfund site).
Site near industrial facility other than a paper mill, refinery, or wood
preserver.
Site near discharge of a Publicly Owned Treatment Works (POTW).
Site near active or former wood preserving activity.
NQNPOINT: Nonpoint sources include the following two categories:
17. URBAN Site near urban runoff.
18. AGRICULTURE Site near agricultural area.
11.
12.
13.
14.
15.
16.
PPNC
REFINERY
NPL SITE
OTHER INDUSTRY
POTW
WP
NONPOINT:
B-3-1
-------
B-3-2
-------
TABLE B-3
Matrix of Episodes and Site Descriptions
EPA
Bf
i
ii
u
ii
u
u
u
u
u
11
II
II
II
II
II
II
II
P_J ..
t
2376
2375
2369
3151
3150
2356
2721
2725
3026
3028
2358
3022
2355
2722
3027
3023
3024
3025
3152
3426
3429
3430
2651
3427
2653
3428
3433
3434
2654
3304
3296
3296
3301
2326
3309
Lnim* ti.tH.4i
41:2iOON 072:52:40W
41:36:47N 071:58:26W
42:37:25N 071:23:10W
42:35:22N 072:21 :08W
42:35:46N 072:03:27W
44:06: ION 070:13:58W
44:15:20N 070:10:50W
44:30:09N 070: 15:00 W
44:10:20N 070:20:25W
45:04:48N 067:19:25W
44.36-.30N 067:55:30W
44:32:30N 070:07:15W
44:49:20N 068:42:30W
43:34:35N 070:33:45W
43:34:25N 070:33:55W
44:54:30N 069:55:05W
44:54:OON 069: 15: 15 W
44:49:40N 069:24:OOW
44:24:42N 071:1 1:29W
40:35:45N 074:12:20W
39:34:30N 075:31.-OOW
39:18:OON 074:37:30W
39:36:OON 074:35:OOW
40:39:15N 074:09:16W
40:54:30N 074.12:<»W
40:43: 15N 074:07: 15W
40:28:24N 074:0340W
40:27:OON 074.03:OOW
39:57:30N 074:12:30W
43:59:30N 076KM:30W
42:51:45N 078:52:OOW
42:52:OON 078:52:30W
43:20:20N 078:4J:OOW
42:13:OON 078:01:OOW
42:13:30N 078:O2:OOW
Stale W«lciWtfy Lccillu
CT Quinipiac River North Haven
CT Quinnebaug River Jewell Cily
MA Merrimack River Tyngs Island
MA Millers River Erving
MA Oiler River Baldwinvillc
ME Androscoggin R. Lewislon
ME Androscoggin R. Turner Falls
ME Androscoggin R. Riley Dam
ME Androscoggin R. Auburn
ME Bearce Lake Barring
ME Nauaguagus R. Cherryfieto
ME North Pond Cheslerville
ME Penobscot R. Eddington
ME Saco River Union Falls
ME Saco River Union Falls
ME Sandy Pond North Anson
ME Sebasticook E. Br. Newport
ME Sebasticook W. Br. West Palmyra
NH Androscoggin R. Berlin
NJ Arthur Kill Carteret
NJ Delaware River Salem
NJ Great Egg Harbor
NJ Mullica River Green Bank
NJ Newark Bay Elizabeth
NJ Passaic River Paterson
NJ Passaic River Newark
NJ Rarilan Bay
NJ Sandy Hook
NJ Torn* River
NY Black River Delta Dexter
NY Buffalo Harbor Buffalo
NY Buffalo River Buffalo
NY Eighteen Mile Creek Olcott
NY Genessee River Belmonl
NY Genessee River Belmonl
NSQ B
X
X
X
X
X
X
X
X
X
X
POINT SOURCES
NPI. Other
PPC PPNC WP Rlnj Site \ut POTW
XXX
XXX
XXX
X
X
X XX
X
X
XX X
X X
X
X
X X
X X
X
X
XXX
X
X X
X XXX
X
X X X X
X XX
XXX
X XX
X
X
X
X
X
N4M4POJNT
Uifeui Acri
X
X
X
X
X
X
X X
X
X
X
X
X
X
X
X
X
X
IfltllliliiiUHi DticiiyllM
Industry: chemical & pesticides; electronics; plastics; metals; Superfund
site (solvents)
Ind.: organic chem. & pest., textiles; Superfund site (Furans)
Ind.: chem. & pest., industrial WWTP; P&P mill on Nashua R. (Irib.);
Superfund site (solvents)
Erving Paper Mills; wooded area; Ag.: croplands and grazing fields
Erving Paper Mills; wooded area; Ag.: croplands and grazing fieldi
International Paper, Boise Cascade, James River; Ind.: textiles
International Paper Co. in Jay
Boise Cascade in Rumford; rural;wooded area
Ind.: textiles; downstream of paper mills
Two biueberiy processing plants; blueberry Fields (pesticides)
No industry, wooded and swampy area
James River Corporation on Old Town
Same as 3027; POTW on upstream Irib. yet is Background site
Same as 2722; POTW on upstream trib. yet is Background site
Industrial WWTP
Industrial WWTP
James River Corporation
GAP Corp. (chem. manufacturing)
Superfund site (several sites; metals & urg. chemicals)
Background even though has agricultural area and POTW nearby
Wooded area
Landfill
Mucal Paper and P&P mill on Uib ; Ind.'. mculi, chem. & pest/.
Superfund site (solvents)
80 Lister Ave.: chem. manufacturing
P&P mill effluent into bay, Exxon Co.; Ind.: chem.; Superfund sKe (several
sites; metals & org. chem.)
Exxon Co.
Ind.: chemical; Superfund site (chlorobcnzcnc; Hg)
Five paper mills (PPNC); Air Brake Co , hydro-power; dairy field*
Ind.: chemical, Keel, petrochemical; landfills
Allied Chemical (manufacturer of HCB); landfills
Ind.: Harrison Radiator; chem. (HCB), Ag.: orchards and croptaadi
Same as 3309. Sampled below Belmont Dam. Superfund site is
approximately 10 mites upstream (heavy metals, hydrocarbons)
Same as 2326
B-3-3
-------
TABLE B-3 (coot.)
DA
•n
11
11
II
11
11
II
n
11
n
it
n
n
n
n
n
II
n
n
n
n
u
II
n
n
u
n
n
u
n
in
in
Hi
in
HI
in
in
in
M»*
*
3306
3319
3320
2709
3259
3409
3321
3322
3260
2328
2329
3323
3324
3325
3326
3300
3297
3299
3302
3303
3412
3305
2322
3308
3411
3307
3327
3432
3431
2210
3147
3099
3098
3097
3149
3100
lartl»a» LM^MC
44:57:30N 074:4ftOOW
4ft40:OON 073:20OOW
4ft40:45N 073:I9:OOW
41:16:30N 073:57:00*
43.-08.-OON 073:36:30W
41:20K»N 073:57:30W
40:38:40N 073:50:40W
40-.37:4SN 073:47:OOW
43:51:30N 073:22.-OOW
43:20:25N 078:43: 14W
43.14«5N 077:32.-03W
4ft48:OON 073:45.00W
4ft47:OON 073:45.-OOW
40-.49AON 073:404»W
40:SO.10N 073:40:15W
43:15:30N 079*B:4SW
43:03:OON 07&58:S5W
43KHOON 07&S3:45W
43:IO:30N 079:03: IOW
44: 12 JON 075.-00*»W
43:28K»N 076:31:OOW
44:58:30N 074:44flOW
44:59.00N 073:2 1:OOW
454ftOON 073:21:OOW
43:1I:I8N 077:31:30W
44:42:30N 075.28.30W
40:38:20N 074:02: 15W
17:59:40N 066:46:25W
18:26:40N 066:06:30W
T8:52:20N O77KG:15W
38:52:30N 077O2:30W
38.-35.OON 075:12.-OOW
3*48:08N 01 5: 39:44 W
39:35:40N 075:37:50W
39;43:58N 075:45:37W
39:1S:36N 076:31:30W
3317 (39i28«ON 079fll:OOW
VM> WMntWr LtcmO*m
NY Grass River Massena
NY Great South Bay Babylon
NY Great South Bay Babylon
NY Hudson River PeekskiU
NY Hudson River Fort Miller
NY Hudson River Pcekskill
NY Jamaica Bay New York
NY Jamaica Bay New York
NY Lake ChampUin Ticonderoga
NY Lake Ontario Olcotl
NY Lake Ontario Rochester
NY Little Neck Bay Long Is. Sound
NY LktleNeckBay Long l«. Sound
NY Manhassett Bay Long Is. Sound
NY Manhasselt Bay Long Is. Sound
NY Niagara R. Delta Porter
NY Niagara River Niagara Palls
NY Niagara River N. Tonawanda
NY Niagara River Lewistoo
NY Oswegatchie River Newton Falls
NY Oswego Harbor Oswego
NY Raquettc River Massena
NY Richelieu River Rouses Pt.
NY Richelieu River Rouses Pt.
NY Rochester Embay. Rochester
NY St. Lawrence River Ogdensburg
NY Upper Bay New York
PR Guayanilla Bay
PR San Juan Harbor San Juan
DC E. Potomac River DC
DC Polemic River Park N. of Wilson Br
DB Indian River Rosedale Bead
DE Red Clay Creek Ashland
DE Red Lion Creek Tybouls Corner
DE White Clay Creek Thompson
MD Baltimore Harbor Baltimore
MD Potomac R.N. Br. Weslernport
N8Q •
X
X
X
X
FtMMTBMJBX.lt
NPL (Mm
rPC PFNC NT Uqr Mb In* PUTM*
X
X
X
XXX
X X
XXX
X X
X X
X
X
X
X X
X X
X X
X X
X X
X X
X X
X X
X
X
X XX
X
X
X
X
X X
X X
X XX
X X
X X
X X
X
X
X X
X X
NONtOtNT
IlitM /t«rt
X
X
X
X
X
X
x x
X X
X X
X X
X X
X
X
X X
X
X X
X X
X
X
X
AMUlMMl StU UncritUMi
(t'xUWo In <*• TlchOt, •! Ike imatftlmt ttUf
Sampled below ALCOA'S outfall ( PCB concern); (JM & Reynolds (2
miles below mouth of river)
Same as 3320
Same as 3319
Same as 3409; Iml: them., P&P mill 150 river miles upstream; Supcrfund
site (PCB)
Fort Miller Pulp and Paper (Finch, Pyruvn * Co.)
Same a& 2709; Ind.: chcm , P&P mill 150 river miles upstream; Supcrfuml
site (PCB)
Ind.: chem.; airport; landfill
Ind.: chem.; airport; landfill
International Paper Co.
Ag.: apple orchards and croplands
Ind.: chem (Kodak); Site al the mouth of (jenesee River
Same as 3324
Same as 3323
Same as 3326
Same ai 3325
Ind.: chem.; Olin, Duponl, Oxidenlal (HCB); Ag.: orchards; landfill
Ind.: chem.; Olin, Dupont, Oxidenlal Chem. (Ml 8), (companies
downstream of site)
Ind.: chemical
Ind.: chem.; Olin, Duponl, Oxidenlal (HCB); Ag.: orchards
Newton Falls Paper Mill (defunct since October 1984)
Ind.: Chemical
Potsdam Paper and Norfolk Paper (PPNC); ALCOA, CM, Reynolds
(upstream of mouth)
Ind.: chemical
Ponderosa Fibers (out of business more than 4 years); Dow chemical in
Canada
Sampled al 69th Street Pier
Caribbean Gulf Refining Corp ; landfill
Estuary
Ind.: metal plating, mining; illegal dump (land/ill); Ag.: mushroom f*rmin|
Chemical spill (HCB concern); Superfund site (HCB)
Weslvaco (indirect); rural
B-3-4
-------
TABLE B-3 («•*.)
ETA
Rt|
III
III
III
111
III
111
III
111
III
111
111
III
111
III
III
III
III
III
III
III
III
III
III
III
111
III
III
III
III
III
III
III
111
III
III
IV
IV
CrMt
t
2231
3103
3316
3161
3420
3094
3095
3096
3318
3419
3310
3101
2215
2212
3104
341S
2211
3414
3315
2216
3422
3421
2225
2228
2227
2220
3423
3424
3193
3258
2500
3314
3311
3312
3313
2304
2309
UIM>* I im&uti
39:39:31N 076:lft28W
39:38:OON 076: HMO W
41:25:20N 078:44: 10W
39:56:30N 075:14:35W
39:53:42N 076:4ft09W
40:02:24N 074:59:20W
39:53:OON 075:1 1:46W
39:51:36N 075:18:40W
40:23:20N 078:24:20W
42:09:25N 08ft02:57W
40:39:40N 07S:14:35W
40:03:40N 075:28:23W
40:17:30N 079:52:33W
39-.5&OON 075:11:20W
39-.5&22N 075:1 1:33W
41:23:30N (T75:48:OOW
40:03:OON 076:3ftOOW
41:18:50N 075:48:45W
40:21:OON 076:23:OOW
41:33:22N 077:41:28W
36:33: ION 076:54:57W
37:47: 15N 08ftOO:06W
37:35:OON 079-.25.-OOW
37:40: 15N 078*5: 10W
36:46:13N 077fl9:59W
37:46:03N OT7:19:57W
37:31 :55N 076:48:40W
37:32:0 IN 076:50:38W
37:01 :45N 078:55:40W
36:49;48N 076:17:30W
38:27:OON 081:4*OOW
38:31:30N 081:54:37W
3*40tf)N 080-.51:52W
40:09: ION 08ft42:25W
39:31: ION 077:52:30W
31:32:48N 089:30:45W
32:24:41N 086:24:30W
MD Susquehanna River Conowingo
MD Susquebanna River Conowugo
PA Clarion River Ridgeway
PA Cobbs Creek Philadelphia
PA Codorus Creek Spring Grove
PA Delaware River Torresdafe
PA Delaware River SchuyUiH Jnct.
PA Delaware River Eddyitooe
PA Frankslowo Branch Kladder Slalioa
PA Uke Erie Erie
PA Lehigh River Eatton
PA Lillle Valley Creek Paoli
PA Mooongahela River Qairton
PA Schuylkill River Philadelphia
PA Schuylkill River Philadelphia
PA Susquehanna N.Br. Raason
Pl* $i>H]»*h*nn* Piurr Pnlumhi*
Pl» t0.iiLitmn
tr--mt"i HI flu -irmtttTf •*---- rrrHmimi
Same as 3103
Same as 2231
Penlech Papers in Johnsooburg; iiiral; acid nine drainage
Old PCP plant (defunct for more than 5 years), landfill
P.H. Gladtfelder in Spring Grove
Coastal Eagle Point Oil Co. in NJ; Inorganic chem.
Mobil Oil in NJ; Ind.: chem; multiple sources; Ag.: croplands (trucking of
vegetables)
Appleton Paper on the Juniala River (Holler Creek)
Hammernill Paper (indirect); rviryard; food processing plant
Steel industry
Paoli Railyard (historic PCB problems)
Ind.: inorganic chem. and pest.
Same as 3104; two refineries; Ind.: org. cnem. & pest.; ftf mill;
Superfund site (PCP)
Same as 2212; two refineries; Ind.: org. cnem. A pest.; ftP null;
Superfund site (PCP)
Superfund site (heavy metals)
Gladtfelder (bleachki aft) 20 miles upstream on tributary
Superfund site (heavy metals); acid mine drainage
Pesticide concern
Union Camp Corporation in Franklin
Weslvaco Corporation
Light agriculture; rural
Westvaco (PPC); Virginia Fibers and Nekoosa Edwards (PPNC)
Union Camp is 20 miles downstream of iimpling site
Upstream from the Cheasepeake Corporation
Chf asf pf akr CorpuratKMi (upslrcam nf site)
OK awpf akt CorporalH"1 (''lMmf4r|Mi|M o' ****)
Rural
Ind.: pesticides, trichlorophenol, and nrg>nir chemicah (Dow and
Monsanto); rural
Ind.: pesticides (Monsanto); rural
Quaker Stale Oil Refining; steel industries; urban runoff
Ag.: orchards; rural
Alabama River Pulp Company
Ind.: organic cnem. tt pest.; Fence-post company; Ag.: croplands
B-3-5
-------
TABLE B-3 (coot)
ETA
•*!
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
t
3360
3170
2302
3172
3328
3171
3169
3168
3331
3332
2151
3329
3334
3174
2148
3333
2142
3173
2132
3330
3337
3177
3375
3376
3377
3378
3178
3179
2294
3176
3336
2290
3175
3338
3180
3335
UUU* LMtMiMl*
32:07:55N 085:03:43W
31:29:40N 085.-22.06W
31:04:01N 087:O2:40W
31:25:07N Og8:26:4SW
33:17:24N 086:21:42W
31-01-02N OB5:13:24W
33:50: 15N 086.31 :46W
3ft52:30N 087:57:48W
30:30*.OON 087:20: 15W
30.38:52N OS 1:29. 28 W
30:23:04N 085:33:24W
30:01.-OON 083:46:OOW
2*50:31N 085:17:S9W
27:12:18N 080:47:28W
27:38:54N 080:24: 10 W
30:07:38N 085:39:25W
29:38:48N 081:37:32W
3ftOO:OON OB1:40-OOW
3ft21:30N 082.-04.-54W
30-.28:OON 083:15:OOW
31:39:10N 081:49tiOW
34:26:OON 083:40:30W
33:39:24N 084:40:25W
33:28:37N 084:54:04W
33:16:45N 085.O6.-OOW
31-08.DON 085«4:OOW
34:55:OON 083:10*OOW
34:27:OON 083:57:30W
32:01:20N 083:56:30W
3ft52:OON 084:36:OOW
30:43:37N 001:3100 W
33:22:25N 081:56:35W
321ft30N 081-08.50W
33:22:OON 081:56:OOW
31:18.-OON 084:45O>W
31:08:15N 081:31:35W
Sim* W-M*Wr [MtiM
AL Chaltahoochee Cotlonton
AL Choclawhatchee R. Henry Co.
AL Cooecuh River E. Brcwton
AL Coosa River AL/GA Stale L
AL Coo-sa River Coota Pines
AL Co-warts Creek Houston Co.
AL Inland Lake Blount Co.
AL Mobile River near Cold Cr.
FL 1 1 Mile rrr tk r^^mtimrmi
FL Amelia River Fernandina Bel
FL Econfina Creek Panama City
FL Fcnholloway River Perry
FL Gulf Co. Canal Si. Joe
FL Lake Okeechobee Okeechobee
FL Main Canal Vero Beach
FL St. Andrew Bay Panama Cky
FL St. Johns River Palalka
FL St. Johns River Green Cv. Spr
FL St. Mary's River Macelenny
FL Withlacooche River Blue Spring
GA Altamaha River Jesup
GA Chatlaboocbee R. Gainesville
GA Challahoochee R. Austell
GA Chattahoochee R. Whilesburg
GA Chattahoochee R. Franklin
GA Cnattahoochee R. DonakUonville
GA Challooga River Clayton
GA Chestatee River above L Lanier
GA Rint River L. Blackshear
GA Lake Seminole
GA North River (motMh) St. Marys
GA Savannah River Augusta
GA Savannah River Savannah
GA Savannah River Augusta
GA Spring Creek Early County
GA Turtle R. (mouth) S. Brunswick R.
NSQ *
X
X
X
X
X
X
X
roiNTnoukcu
NPt (Mktf
rrc true wr ftm, SM, tmt run*
X
X
X
X
X X
x
X
X
X X
X
X X
X X
X
X
X
X
X X
X X
X
X
X X
X
X
X X
X
X X
X XXX
X XX
X
NONPOINT
UifcM Atri
X
X
X
X X
x
X
X
X
X
X
X
X
X
X
X
X
X
X
1 ittmi nltitlf Omolft**
(FirtHlln>«lfa^ctotOWIfctli»fll«t»t»«>
Alabama Kraft in AL (goes into ( jA water but on AL side)
Container Corporation
Kimberly Clark; wooded area; Ag.: croplands and grazing fields
Several chem. & pest, plants; Hydro-power
Champion International Corp. in Cantonment* rural; swampland* Ag.:
croplands
ITT Rayonier, Inc.
Buckeye Cellulose; rural; swampland; Ag.: grazing fields
Si. Joe Paper (indirect)
Collected below saUnky structure
Southwest Forest Ind., Inc. (indirect) (Stone Container Corp.)
Georgia Pacific Corporation
Wood treatment plant
(IT Rayonier, Inc.: swampland; Ag.: croplands
Town of Schoville: heavy metals, wood products; Ag.: chicken farms and
orchards
Box Board on Hwy 92
Great Southern Pacific Paper Company
Mining: gold, sand, and gravel; Ag.: orchards, dairy farms •& chicken
houses
Procter & Gamble (Buckeye Cellulose)
Great Southern Pacific Paper Company
Oilman Paper Company
Federal Paperboard in Pond, Georgia Pacific; Ind.: pen.
Fort Howard Paper (PPC), Union Quap awl Stow; Container Corp.
(PPNC); Nuclear power
Ponderosa Fibers (indirect)
Brunswick Paper & Pulp on the Turtle R.; marshland; wooded area; Ag.:
grazing fields
fl-3-6
-------
TABLE B-3 (coot.)
ETA
**!
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
IV
*
3183
3339
3182
2056
2341
3181
3446
3185
2126
3445
3341
3340
3435
2133
3184
3344
2139
3165
3345
3164
3342
L«ttM* Lwc*.*
38:24:22N 082:35:52W
36:55:41N 089:05:52W
36:55:27N 086:52:47W
38:00:30N 085:56:30W
38:46:29N 084:57:52W
38:00:30N 083:S6:30W
3&24:22N 082:35:52W
3ft25:OON 089:04:OOW
32:20:41N 090:51:48W
30:19:32N 088:31:OOW
30:25:20N 088:31:10W
31:13:28N 089:02:50W
31:25:OON 091:30:OOW
32:29:14N 090:49fl2W
32;28:OON 090:49:OOW
34:23:50N 078:10:30W
35:40:02N 093O4:23W
34:43:50N 079:39:24W
35:15:06N 082:40:45W
35:56:45N 079:19:20W
34:36:30N 078:59:OOW
3167 J35:50:35N 078:50:20W
3166 J35:08:OON 083:38: 15W
2138
3395
3343
3346
3385
3347
3186
3348
35:15:29N 077:35.fl9W
35:U:S6N 077«6:4SW
35:32:05N 082:54:40W
35:51:55N 076:45:40W
35:59:25N 081:31:32W
34:42:30N 080:S1:50W
32:45:50N 079:53: 10W
33:21:24N 079-.18:34W
3187 :32:29:46N 080:31:33W
3349
2301
3189
2298
3350
2297
33:51:08N 08ft37:32W
35:29:45N 087:49:58W
35:55:37N 084:58:18W
35:16:31N 088:58:36W
35:19:08N OB4:48:13W
36.00-.56N 083-.49-.54W
State Vr«Ultl<] 1 mrmltmm
KY Big Sandy R. Catllelsburg
K Y Musiuippi River Wickliffe
KY Mud River Russellvillc
KY Ohio River West Point
KY Ohio River Markland
KY Ohio River Westpoint
KY Bif Sandy R. Catlettsburg
MS Bernard Bayou GuUport
MS Big Black River Bovina
MS Chevron Effluent Pascagoula
MS Escatawpa River Moss Point
MS Leaf River New Augusta
MS Mississippi River Natchez
MS Yazoo River Redwood
MS Yazoo River Redwood
NC Cape Fear River Riegchvood
NC Caltaloochee Creek Catlaloochee
NC Deep River Ramseur Dam
NC French Broad River Pisgih Forest
NC Haw River Saxapahaw
NC Lumber River Lumberton
NC Medlins Pood Morrisville
NC Nanthalia River Macon Co.
NC Neuse River Kinston
NC Neuse River New Bern
NC Pigeon River Clyde
NC Roanoke River Plymouth
NC Yadkin River Patterson
SC Catawba River Calawba
SC Charleston Harbor Charleston
SC Sampil River Georgetown
SC St. Helena Sound
SC Wateree River Eatiover
TN Buffalo River FUrwoodi
TN Ft. Loudon Res.
TN Halchie River Bolivar
TN Hiwaiee River Calhoun
NSQ •
X
X
X
X
X
X
TN HoUton River Knomille ,
POINT SOU BCKS
NPL OtWr
PPC rpNC wr Rh? sn> M POTW
X XX
X
X X
XXX
X X
XXX
XXX
X X
X
X XX
X
X
X
X
X
X X
X
X X
X X
X
X
X
X
X X
X
X X
X
XX X
X
X
X
X
X XX
NONPOINT
U*M Ac*
X
X
X X
X X
X X
X
X
X
X
X
X
X X
X
X
X
X
X
X
X
X
X
X
X
JU4UIMMI SM. DMcrlvttM
^•clmiMlalfctikfrHiummmjymtHt)
Ashland Oil IDC.; Ind.: chem,. iron and steel; coal mining, timber
Westvaco Corporation; Ag.: croplands
Ind.: metal plating; rendering plant; Ag.: croplands
Same as 3181; Ind.: chem. & pest., refinery, Ag.: crops; Superfund site
(PCB's; solvents; dioiuns & furans)
WUliamelte Industries; multiple sources; rural
Same as 2056; Ind.: chem. & pest., refinery, Ag.: crops; Superfund site
(PCB's; solvents; diorins & furans)
Ashland Oil refinery, coal mining
Ind.: chem.; wood treatment; (gas recovery) refinery, rural; Superfund site
(solvents)
Ag.: soybeans and cotton
Chevron refinery. International Paper; shipyard; fertilizer company
International Paper Company
Leaf River Forest Products
International Paper Company
Same at 3184; Ind.: paper; fertilizer plant
Same as 2133; Ind.: paper; fertilizer plant
Federal Paper Board; rural; swampland; wooded area; Ag.: croplands
Champion Paper (PPC-indirect source); wooded area
Ecusta (sulfile mill using chlorine) ; rural; wooded area; Ag.: cropland!
Ind.: textiles; rural; Ag.: croplands
Alpha Cellulose (sulfile mill using chlorine)
Koppers Company (wood treat.); Superfund site - wood (real. (PCP)
Weyerhaeuser Company
Weyerhaeuser Company
Champion International in Canton; rural; wooded area; Ag.: croplands
Weyerhaeuser Company on Welch Creek; runt; wooded area; Ag.:
croplands
Sealed Air Corporation (makes absorbanl paper for meat trays)
Bowater Carolina; rural; wooded area; Ag.: croplands
Westvaco Paper and Pulp; Amoco chemical plant
International Paper Company; rural; wooded area; Ag.: croplands
Union Camp Corporation; rural; wooded area; Ag.: croplaodi
Ind.: aluminum
Bowaler South Paper Company, rural; wooded area; Ag.; croplands
Industry, metals
B-3-7
-------
TABLE kV3 (C«rt.)
•TA
**
IV
IV
IV
IV
IV
IV
IV
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
EpMt
1
3403
3444
3188
340*
3351
3190
3401
2379
2383
3113
2380
3114
31 IS
3117
2039
33S6
2060
2057
3119
3118
1994
3120
3122
1998
3148
2432
2410
2431
2430
2435
2387
2437
3112
3125
2385
3001
2416
2394
2439
LtflMk Li»j)fc
-------
TABLE B-3 (coot)
f.T
**I
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
EpfcW.
#
2618
3132
3135
3136
3137
2429
3138
3140
3143
3144
2422
3134
3141
2427
3142
3110
2.197
2608
3106
3107
3108
3109
3145
3146
2023
3060
3062
3061
3078
3443
2015
2018
3073
2016
3452
3077
2017
.*K8
mi
LmlUmtt Lnmt/Hmt,
39:24:40N 084:33: 14W
39:17:36N 082:55:4«W
44:49:39N 091:30:38W
45:24:05N 091:13:18W
45:55:OON 090-.26:4IW
44:27:39N 088:03:30W
44: 16: ION 088:22: 18W
44:13:24N 088:27:34W
44:00:43N 08H:3I:OOW
43:32: 17N 089:27:36W
46:36:2 IN 090:52:30*
44fll:58N 088:08:45W
43:03:26N 087:53:54*
45:03: 16N 087:44:50W
43:43:51N 087:47fl4W
44:58:OON 092:46.-OOW
45:37:27N 089:25: 14 W
44:16.00N 089:53K»W
44.16:OON 089:53:OOW
45:01 :20N 089-.39:09W
45:10:31N 089:40tfOW
44:56:57N 089:37:4SW
45:26: 17N 089:43:56W
44:52:57N 089:38: 17W
35:20:56N 094:17:54W
34:26:41 N 092:06:38W
34:lfc09N 091:43:56W
33 10 UN 092:39:OOW
J45039N 092:07 20W
34:09:OON 09I:31:OOW
33:33:27N 091:14:15W
35:59:43N 092:1 2:45W
35:56:33N 092.O7fl5W
33:33fl7N 094fl2:28W
3.34 I5N 094:0&:OOW
33:57:17N 094:21:49W
33:14:32N 093:59:58W
3fl:53:OON 093:25:OOW
32:40:«)N 091:43:OOW
State WMtiMy UollMi
OH HunihonCual Himilloo
OH Sciofo River Chillicotbe
Wl Chippcwa River Eau Cliire
Wl Flambeau River E. Ladyunitb
Wl Flambeau River Park Falls
Wl Fox River DePere Dam
Wl Fox River Appleton
Wl FoxRivei Lk ButteD.Morts
Wl FoxRivei Osbkosh
Wl Fox River, upper Portage
Wl Uke Superior Ashland
Wl Maailowoc River ChiHon
Wl Milwaukee River Milwaukee
Wl Peshfigo R. Harbor Peshtigo
Wl Sheboygan River Kohler
Wl SI Croix River Hudson
Wl Wise. R/Boom Lake Rhinelander
Wl Wisconsin River U. Pentenwell FI
Wl Wisconsin River U. PenCenwell FI
Wl Wisconsin River Brokaw
Wl Wisconsin River Merrill
Wl Wisconsin River Wausau
Wl Wisconsin River Mohawskin
Wl Wisconsin River Rothschild
AR Arkansas River Van Buren
AR Arkansas River Little Rock
AR Arkansas River Pine Bluff
AR Bayou DeLoutre El Dorado
AR Bayou Melo Jacksonville
AR Bayou Melo ReydeU
AR Mississippi River Arkansas City
AR N. Sylamore Creek Fifty Six
AR N. Sylaraore Creek Fifty Six
AR Red River Index
AR Red River Index
AR Rolling Pork River De Queen
AR Sulphur River Texarkana
.A Anacoco Bayou Deridder
LA Bayou Bonne Idee Oak Ridge
NSQ •
X
X
X
X
X
X
X
POINT SOtmCU
NPL Olbtr
rrc PPNC WP Rhq m> imt rorw
X X
X XX
X
X
X X
X XX
X X
X
X
X X
X
X X
X X
X X
X X
X XX
X XX
X
X
X
X
X
X X
X X
X X
X X
X
X X
X
X X
X X
X
X
NONPOIOT
Urkwi feri
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
AMMlMMi SHt DmtpUM
(F«dim» t» U» .fctBjft ml Bit li»p»«t rifc)
Canal off G. Miami R.; Appleton Paper; Aviation plant; sleel;
hydro-power; Superfund site
Mead Corporation on Paint Creek; Ind.: inorg. chent. & pest.; Superfund
site
Pope and Talbot (deinking)
Pope and Talbot (deinking)
Flambeau Paper; Ag.: croplands ami grazing fields
Fort Howard, James River, Green Bay Pkg., Nicdct Paper, Champion
Kerwin Paper Company (deinking), Gladtfelder, Wl Tissue, Kimberly Clark
Gladllekier, Wl Tissue Mills, Kerwin Paper (historical PCB contamination)
Ponderosa (deinking)
Historical PCB contamination
James River-Dixie Northern (deinking); rural
Incinerator; H2O softener plant, Ag.: croplands
Ind.: metals (historical PCB contamination); 300-400 Industrial discharges
Badger Paper Mills, (indirect)
Superfund site (historical PCB contamination)
Anderson Windows; wood treatment plant
Upstream of paper mills
Nekooca, Fort Edwards, Consolidated Kraft; Vulcan mat. (rubber &
plastic); same as 3106
Nekoosa,,Fort Edwards, Consolidated Kraft; Vulcan mat. (rubber &
plastic); same as 2608
Wausau Paper (sulfite mill)
Ward Paper (deinking)
Wood treatment plant she is between paper mills.
Rbinelander Paper Company
Weyerhaeuser, half dozen small mills; Ag.: croplands
International Paper Company, wooded area; Ag.: croplands
Lion Oil Company
Superfund site (dkuuns); rural; wooded area
Downstream about 30 miles of the Jacksonville tile (3078)
Pollalch Corporation; Ag.: croplands
Same as 3073
Same as 2018
Nekoosa Edwards Paper Conpaay
Nekoosa Paper; lime and gravel mines; Ag.: crop awl grazing land*
Wood treatment plant on Bear Creek
International Paper Company in Texas
Boise Southern Co. (Boise Cascade); ruial; Ag.: cropland
HCB use in agriculture
B-3-9
-------
TABLE B-3 (coot)
ET
kg
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VII
VII
VII
VII
»
3086
3442
3353
3063
3092
3352
3064
3082
2532
3065
3066
3418
3416
3080
2544
3087
3425
3074
3105
3090
3079
2027
3076
3091
2026
3089
3084
3085
3068
3069
3081
2280
3075
3093
3070
3072
1071
2283
3035
3037
3038
3034
L«M«4t La^taJt
3ftl2:OON 093: 17:OOW
30:02:36N 090:22:27W
32;3I«ON 09I:54:OOW
SOflb.flON 093:20:OOW
32.05flON 092:47:00*
32:33:OON 091:5100W
30*)2:OuN 09f>02:OOW
32:4I:OON 09I:II09W
»45:30N 09I:23:45W
30;27«ON 0»I:13.OOW
30ti6:OON 09IOIrOOW
»39flON 091:17«OW
33KXMUN 092.-04:OOW
32:27:OON 092:07:OOW
».».23N 090:21 :42W
32:35:OON 091:56.00W
32:33:OON 09I:5SOOW
35:46:38N I05:39:27W
35:I3:42N 098:31:35W
36«4«ON 095:16«W
36:32:OON 096:56.-(MW
34:38:18N 094:36:45W
33:57:OON 094.35.-OOW
33.56:OON 09507.00W
34:l4fl3N 096:58:32W
35.41 OON 095:I4.OOW
26:1I:42N 097:36:06W
28:58:59N 095:23:41W
2*40:4SN 094:58 SOW
27:51:30N 097 ».20W
31:25:5SN 094:33:56W
28:57:35N 096.4 1.13W
2ft09*)ON 096:52:OOW
3l08flON 094:48:39W
» »30N 093.S400W
3HW.-OON 105:36.40W
29:I4:1SN 098:21 :43W
W.5525N 091:02 I2W
42:03:S4N 09I:47:48W
41:4ft57N 093:40:08W
4l:33.fl2N 093:31:29W
4I:34:S3N 09ft23:23W
SMt Wilii*.^ Uc.ll..
LA Bayou Diode Sulfur
LA Bayou Labarcbe Norco
LA Bayuu UFourche Bastrop
LA Calcasicu River Mou Uke
LA DttgdemoM River Hodge
LA Lake Irwia Slart
LA Like FoMcliamiui New Orleaai
LA Lake Providence
LA Mmixapp4 River, Si. Fraacunilc
LA Mutiuippi River Baloa Rouge
LA Miuiuippi River Union
LA Miuiuippi River Zjdurv
LA Ouachka River Slerlingtoa
LA Ouacbila River Monroe
LA TangipaaxK River Robert
LA Wham Brake SwarU
LA Wham Brake Swartz
NM Rio Mora Terrcro
OK Fort Cobb Reiervoir Fort Cobb
OK Fort Gibson Ra Pyrer Creek
OK Kaw Reiervotr
OK Kiamkhi River Big Cedar
OK Liule River Goodwater
OK Red River
OK Washka River Durwood
OK Webbers Falfa Mwkogee
TX Arroyo Colorado Harlingeo
TX Brazoi River Freeport
TX HousloaSJupCbnt Morfu Point
TX Inner Harbor Corpus Chrisli
TX Lake San Rayburn Lufkin
TX Lavaca River Edna
TX Metquite Bay
TX Necfce. River DJbott
TX Necket River (tidal) Port Arthur
TX Rio Graade River El Paao
ry CMM AMtfHftn Diwr T*\m *rm iln.f
i A jwi nvtimu ni^C( ciBcnoon
TX So. Fork Rocky Cr. BiigfS
IA Cedar River Palo
A Dei Moinet River Dei Moines
IA DCS Moines River Des Moines
A Miuiuippi River Le Clake
*sy •
X
X
X
X
X
X
X
X
r»INT SOURCES
NPL fMlwff
rrc rrNC wr um, so* imt POTW
X
X X
X X
X XX
X
X X
X
X XX
X
X
X
X X
X
X
X
X
X
X
X
X X
X X
X
X XXX
X XX
X X
X X
X XX
X X
Xv y
A A
X
X X
X
iwmroiNT
(JAM *«rt
X
X
X
X
X
X
X
X
X
X X
X
X
X
X
X
X
X
XV
A
X X
X
X X
AMMM^Mlf D.iiiljIlM
(VldWta ki MM rtcMr * Iht u«vM*l Ufa)
Cilfo Petrolewn Corporation; Ind.: chen.
SheN Md Norco Refineries; Shell chemical planl
Interim km a) Paper Company, rural
Conoco, Inc.; Ind.: chem.
Above Bayou LaFourcne. This dammed water reeds Wham Brake.
HCB use in agriculture
Crown ZcHertMcn
GeorgHi Pacific Corporation, Crown Zcllerbacb; two rerweries
Ind.: multiple sources; Ag.: cropland and grazing
Georgia Pacific and James Madison Paper; rural; wooded area
Georgia Pacific and Interaatinnal Paper; rural; wooded area
Georgia Pacific in Arkansas; Ag.: crop and gruing lands
Same as 3425; International Paper Co. (dischatges to B. LtFourche)
Same as 3087; International Paper Co. (discharges to B. LaFouf che)
Ag.: croplands; gotf course near the site
RobeHTiiMeMifc
Vulcan Plant in Wichiu, Kansas (chemical processing plant)
Heavily wooded area; Ag.: cattle
Wood treatment: Thompson Lumber, Huffman Preserver, Nixon Bros.
Preserver-
Weyerhaeuser Company
Ken McGee Refining Corporation, Total Petroleum, Inc.
Fort Howard Paper Company
HCB use
At Dow Chemical outfall
Champion International and Simpson Paper; four refineries; Ag.; cropland
Four refineries
Champion International Corporation on 1 he Angelina River
Tempfe-EaMcx, Inc. in Diboll and Borden CliemicaJ (resin)
Tempte-EMex, Inc. in Sibbee, TX; two refineries; Ind.: chem. A pest.
Chevron USA, Inc., El Paso Refining Company
ILjMwl IllljiiJU ••lllkBM
nowcn nywoLni nuns
Background ske
About 50 miles duwulream of Waterloo
Upstream about 10 miles from a POTW
Below POTW (pretreatmenl plant)
U|Klrcim of lock and dam at Davenport (*b»ve Jam)
B-3-10
-------
TABLE B-3(oont)
EPA
R«f
VII
VII
VII
VII
VII
VII
VII
VII
VII
VII
VII
VII
VII
VII
VII
VII
VII
VII
VII
VIII
VIII
VIII
VIII
VIII
VIII
VIII
VIII
VIII
VIII
VIII
VIII
VIII
VIII
VIII
VIII
VIII
IX
IX
IX
IX
»
2191
2190
3036
2194
3039
2201
3040
3047
3048
3049
3045
2199
3044
3046
3050
3042
3043
3041
2205
3197
3198
3200
3236
3237
3235
3234
2122
210S
2100
3111
2109
3199
2110
319S
3196
2098
3266
3282
3288
3285
uui«* IMC*.*.
41:15:32N 095:S5:20W
40:36:07N 095:38:44W
40:36.fl7N 095:38:44W
37:32:34N 097:16:29W
37:32:35N 097:16:29W
36:02:30N 09ft07:30W
36:02:30N 09O07:30W
39:42:36N 091:2l:06W
38:52:33N 090:10:26W
37:17:46N 089:30:S6W
39:07:52N 094:27:S8W
3*11:14N 093:53:45W
39:44:32N 094:5 1J6W
39:11:14N 093:S3:45W
37:»:15N 093:48:45W
41:15:32N 095:55:20W
41:08:18N 095:52:40W
41:45:42N 103:25:02W
4ft59:48N 096:01:18W
38:33:OON 106:01:OOW
3fc48:10N 104:57:30W
4ftlO;30N 104:59:OOW
46:UkOON 112:46:26W
47:01 flSN 114:21:20W
45:45:35N 11 1:05:04 W
47:56: 14N 114:11.O4W
45:47:48N 10&2&12W
47:35:25N 103:15«5W
49:OftOON 097:1 3:45 W
49:00 DON 097:1 3:45 W
4i4*42N 096:33:45W
42:49:45N 096:33: 15W
44:Oft49N I03:49:48W
40:45: ION 111:55:15W
41.2ft40N W5.35:45W
42:34:27N I06:41:31W
33:OS:OON 113:02.-OOW
33:12.flON 115.3700W
36:41:OON 121:44:OOW
33:46tt>N USOkOOW
sun WM.I*WT i^cMtM
IA Miuouri River Council Bluffs
IA Nishnabotu River Hamburg
IA Nithnabotu River Hamburg
KS Arkansas River Derby
KS Arkansas River Derby
MO Little River Ditch 81 Hornenville
MO Little River Ditch 81 Horaenvilk
MO Miuiuippi River Huaitwl
MO Miuiuippi River WeMAlloa
MO Miuiuippi River CipeGJradeau
MO MiiUMiri River KwuuCky
MO Miuouri River LcxinflM
MO Miuouri River StJoteph
MO Miuouri River Lcxiagloa
MO Oufle River Roscoe
NE Miuouri River Oauh*
NE Miuouri River BeUevue
NE North PUlle River Mcgrew
NE Pbtle River LouiiviUe
CO ArfcMus River S«lida
CO South PUtle River Denver
CO St. Vriao River Loagnonl
MT CUrk Fork River WanaSpriop
MT CUrk Pork River Hutoa
MT But OiJUtin River Bozciun
MT GooieBay Lakeiide
MT YeUowttone River Billings
ND Lklte Miuouri R. Watford City
ND Red River Pcmbuu
ND Red River Pembuu
SD Big Sioux River Akron
SD Big Sioux River Akron
SD Cattle Creek Hill City
UT Jordu River SattUkeOty
WY 1 iriaiir River Lariaue
WY North Platte River Akova
AZ Gib River GiU Bend
CA Alano River Calipalru
CA Blanco Drain Salinai
CA Colorado Lagoon Long Beach
NSQ I
X
X
X
X
X
X
X
X
X
X
X
X
X
roiNTSoimciB
NM. Otker
PTC PPM: WP BI.J Sib imt POTW
X X
X
X
X X
X X
X X
X X
X X
X X
X X
X
X X
X
X X
X X
X
X
X
X X
X
X
X
X
X
X X
X X
X X
X X
X X
X X
X
X
NUN POINT
llri>« Acri
X
X
X
X
X
X
X
X X
X
X X
X
X X
X X
X
X
X
X
X
X
X
X
X X
X X
X X
X X
X
X
X
AiUlU.o.1 StU< Dncripllm
(F«UUI» la UK ofclnlly «( Ibc uunpHnt tlte)
Intl.: them, and pest , mclaU; hydro-power; same as 3042-opputite sidci of
river
Same as 3036
Same as 2190
Same as 3039. Below Wichita
Same as 2194. Below Wichita
Same as 3040. Rice growing region
Same as 2201. Rice growing region; heavy pesticide use
Fish collected near downtown area.
Ind.: cheat. ; heavy metals; heavy shipping traffic
Collected at POTW outfall. Proctor & Gamble paper products, Ag
croplands
Same as 3046
Same as 2 199
Ag.: croplands
Ind.: chem. and pest.; metals; hydro power; same at 2191 - oppoiile sides
of river
Defunct wood treatment plant
Stone Container Corporation
Sugar beet processing plan); croplands; Same as 31 1 1
Sugar beet processing plant; croplands; Same as 2100
Same as 3 199
Same as 2109
Ind.: pesticides; Superfund site (chlorobenzenes)
Railroad tie treating plant (defunct)
Cotton growing region (Near Phoenix)
HCB use in agriculture
Multiple sources
Multiple sources
B-3-11
-------
TABLE B-3 (coot.)
tf
Rt|
IX
IX
IX
IX
IX
IX
IX
IX
IX
IX
IX
IX
IX
IX
IX
f V
IVY
IX
IX
IX
IX
IX
IX
IX
IX
IX
IX
IX
X
X
X
X
X
X
X
X
X
X
X
X
X
X
*
3273
3286
3271
3272
3275
3276
3289
3451
3354
3283
3355
3290
3274
3357
3267
1TM
Ji f\l
3287
2748
3281
3264
3450
3269
3278
2037
3261
3262
2776
3238
3241
3246
2070
3244
3245
3252
3250
3249
3158
2478
32«
3248
3203
iMtuttt LmH.ji
41:45:OON 124:llflOW
3547I5N II8:I7:33W
40:34:OON 1 23:11 OOW
37:55:OON 122:21 flOW
40.54:OON 124OO«)W
40:52:OON 124.0000W
36:48:OON 121:46OOW
34:01 :45N II84045W
37:57:OON 12!:18:OOW
33:Ort:OON 1 1 5:40:00 W
37:56:OON 121:19:OOW
37:57:OON 12I:20:OOW
41:55:OON I24.-07«OW
38:05:OON 1JI:44:OOW
40:27:OON 1 22: 11. 00 W
4n-DQ-f¥1N 1 ft- 1 1 •iWW
^u.i/y.uun i a, i i.uuw
33:46:OON 118:06:OOW
34:24.00N 119:3f rma if—I.. Pli^f D^jl Rliiff
\*r\ kSacraBicnto Kiver itea DIUII
CA San Gahriel River Long Beach
CA Santa Clara River Santa Paula
CA Santa Clara River Santa Paula
CA Santa Monica Bay Lot Angeles
CA Short Bank (Pac. O.) Lot Angelet
CA Stanislaus River Ripon
CA Upper Eel River Potter Valley
HI Honolii Stream Hilo
HI Pearl Harbor Middle Loch
HI WailuaPaelekaaSt. Kauai
NV Colorado River Btw Hoover Dn
AK Bird Creek Bird
AK Ship Creek Anchorage
AK Silver Bay Silka
AK SusKna River Susitna
AK Vamterbilt Creek Juneau
AK Ward Cove Ketchikan
D Boise River Parma
D Coeur d'Alene Lake Coeurd'Aleme
D Coeur d'Alene River Coeur d'AleM
D Rock Creek Twin Falls
D Snake River Kings Hill
D Snake River Lewislon
D St. Joe River St. Marie
)R Columbia River Portland
NSQ •
X
X
X
X
X
X
X
X
rtNNTMMIKCD
NPL OMlvr
rrc rrnc wr itar MM M rurw
X
X
X
X
X
X
X
X
X X
X
X X
X X
X
X X
X
X
X XX
X
X
X
X
X X
X
X
X
X
X
X
X
X
NONroiKT
»•*• Acrt
X
X X
X X
X
X
x
X
X
X X
X
X
X
X
X
X
(r»iHlilM tm •» Hrl^n «tH» i«nii«»i iln)
McNamara A Peepe (historical PCP site)
Multiple sources
Sierra Pacific (historical PCP site)
United Heckalborn: pesticide packaging plant in 60*s (PCB's, DDT, Pb)
MoUala-Arcala
Sierra Pacific
Multiple sources
POTW: Tapia Creek; grazing land (horses)
McCormick and Baxter (wood preservers); Superfund site (solvents)
Multiple sources (HCB we)
McCormick A BaMer (wood preservers); Ag.: croplands A orch.;
Superfund site (solvents)
McCormick A BaMer (wood preservers); Superfund site (solvents)
Arcala Lumber Company (historical PCP tile)
Gaylord Container Corp.; Ind.: diem.; refinery, power plaor, Ag.:
orchards and croplands
Simpson Paper Company; wooded area
Diamond InternatiowH (recycled paper); Ag.: croplands aoo grazing
Simpson Paper Company, Pacific Coast Paper
Same at 3281
Same as 2748
El Segundo Refinery, Hyperion POTW outfall; multiple sources
POTW: Hyperion oMfaB
Multiple sources
Louisiana Pacific (historical PCP site)
Combustion sources; Superfiwd site (tohfcati)
Agent Orange test tile (not a designated superfend site)
Salvage yard with runoff of PCB; Superfund site; landfill
Alaska Pulp Company
Louisiana Pacific Corp. (tulfite mill); Kelcstikan Pulp and Paper
Ind.: silver mining
Iki^M^*
Pollalch Corporation
B-3-12
-------
TABLE B-3 (Conl.)
!
RPA
.?*
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Kptmdr
* l^ttbHk IxngHudr
3216 J45:51:53N I22:47:39W
1218
3219
3201
3208
3212
3205
3115
3206
3217
3213
3437
3226
3438
3220
3221
X ; 1222
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
3439
3440
3441
3163
M91
3192
46:09:2 IN 12324:OOW
45: 39: ION I20.56:OOW
45:36:06N I22:43:57W
44:03:30N lt6.57:OOW
43:46:59N 1I7:03:09W
45:26:33N I23:I4:07W
45:23:40N 122:45:3()W
45:34:53N 122:44:39W
44:23:16N 123 14:03W
45:!7:I7N I225R:93W
45:17:38N I22:46:08W
47:23:30N I22:37:WV
46:15:36N I23:5757W
46:07:50N 122:59:27W
46:06:OON 118:55:OOW
45-..34-.08N 122:24.42W
46:15:06N I23:33:32W
46:00:33N 122:51 :04W
45:5R:05N 122:49 1 thr vk*i»y of hmmpllnf Jttf)
X X X X X Boise Cascade (indirect)
X
X X
X X
X X
X X
X
X X
X
X
X
X
X
X X
X X
X
X
X
X
X
James River Corporation in Clatskanic
Hydro-power (PCB's generated); food processing plant; Ag.: orch. &
croplands
Five paper mills using Cl bleach, (wo paper mills not using Cl bleach;
shipyard
X • Minor industries; Ag.: croplands
X X
X
Ind chem.; smelters; shipyards; timber
Hallsey Pulp Company (Pope and Talbot); Ag.: croplands
X , Deinking plant; other pulp mills upstream; Ag.: croplands
X
Below transformer and scrap melal salvage yard; r>clow Superfund site
(PCB)
X Weyerhaeuser and Uongvicw Rber Company; Ag.: croplands & grazing
X
fields
Boise Cascade; Ag.: croplands & grazing fields
Crown Zelferbach (James River Corporation)
V
X
Boise Cascade and Weyerhaueser, Longview Fiber downstream
Boise Cascade and Weyerhaueser. Longview Fiber downstream
X XX Boise Cascade and Weyerhaueser, l/>ngview Fiber downstream
X X X X X X X Simpson Tacoma Kraft. US Oil and Refining; heavily industrialized;
Superfund sue (Commencement Bay)
X ITT Rayonier. Inc. (sulfite mill, nonchlorine)
46:57:13N 123:5I:I5W WA Grays Harbor Cosmopolis X ; Weyerhaeuser Company (sullilc mill, chlorine)
3162 47:17:05N 122:24:28W WA Hylebos Waterwav Tacoma
3227
3295
3294
2247
2246
3223
47:14:20N 1 23:02 :40W
WA Oakland Bay Shelton
48:08:OON 123:24:45W WA Port Angeles Harbor Pon Angeles i
X XXX Champion Paper Company, heavily indusmaliml: Superfund site
X ; X Simpson Pulp Mill (wixxl overlay products)
X X ; ITT Rayonier, Inc.
48:()6:30N 122:45:30W WA Port Townsend Port Townsend X
47:12:52N 122:20:25W WA Puyallup River Puyallup X XX Simpson Paper Company (downstream)
47:49:52N I22:02:50W WA Snohomish Monroe X
48:01 :52N 122:13:OOW WA Sleamboat Slough tivcrctt
; i
3224
3231
3230
48:45:()1N I22:29:02W WA Whalcom Waterway Bcllmgham
46:22:42N I19.25.29W IWA Yakima River Richland
X X Lighl agriculture, timber
X X
Wej . .laeuscr Company and Scott Paper Company; Superfiind site
(solvents)
X • Georgia Pacific (sulfite process)
X XX
47:1I:10N I20:02:30W WA Yakima River CleF.luni j X
B-3-13
-------
APPENDIX B-4
Dioxins/Furans: Episode Numbers Used in Statistical Tests
(By Category)
-------
TABLE B-4
Dioxins/Furans: Episode Numbers Used in Statistical Tests (By Category)
S;ASQAN (NSQ)
Episode
2015
2016
2017
2023
2026
2070
2098
2105
2122
2126
2148
2151
2152
2191
2205
2220
2228
2246
2247
2280
2298
2309
2322
2358
2430
2431
2432
2437
2439
2478
2544
2776
3036
3041
No data available
State
AR
AR
AR
AR
OK
AK
WY
ND ;
MT
MS
FL
FL
FL
IA
NE
VA
VA
WA
WA
TX
TN
AL
NY
ME
MI
MI
MI
MN
OH
ID
LA
NV
IA
NE
3042
3050
3104
3199
3281
3308
Total
NE
MO !
j
PA
SD ,
CA ;
NY
40
AGRICULTURE (AG) !
Episode
2280
2358
2478
3050
3082
3083
3084
3099*
3105
3158*
3170
3171
3180
3193
3208
3212
3282
3352
3437
Total
SUPERFUND
Episode
3078
3097
3226
State
TX
ME
ID
MO
LA
LA
TX
DE
OK
ID
AL
AL
GA
VA
OR
OR
CA
LA
OR
19
(NPL)
State
AR
DE
WA
for dioxins/furans. Number of data values varies by
3261
3272
3414
3415
Total
POTW
Episode
2122
2152
2322
2432
2544
3308
3450
3451
Total
BACKGROUND
Episode
2027
2037
2110
2139
2216
2283
2301
2379
2387
2397
2435
2651
3001
3022
3023
3027
chemical.
HI
CA
PA
PA
7
State
MT
FL
NY
MI
LA
NY
CA
CA
8
(B)
State
OK
HI
SD
NC
PA
TX
TN
IL
MN
WI
MI
NJ
MN
ME
ME
ME
B-4-1
-------
TABLE B-4 (Cont.)
3028
3037
3073
3074
3075
3166
3169
3178
3179
3187
3200
3205
3238
3248
3309
3320
3430
Total
PULP & PAPER
(Chlorine) (PPQ
Episode
2015
2016
2017
2138
2142
2294
2302
2304
2355
2385
2422
2427
2532
2721
2725
3062
No data available
ME 1 3080
I A 3081
AR 3088
NM 3107
TX 3118
NC 3122
AL 3146
GA 3150
GA 3151
SC 3152
CO ' 3192
OR 3217
AK ! 3218
ID 3220
NY 3221
NY 3222
NJ
33
3224
3237
3245
3246
3256
State i 3260
AR ' 3267
AR 3303
AR 3316
NC 3317
FL
GA
AL
AL
3318
3328
3329
3331
ME 3332
MN 3333
WI
WI
LA
ME
ME
3335
3336
3337
3339
3340
AR
LA 3341
TX ! 3342
LA , 3343
WI 3344
MI 3345
MI
WI
MA
MA
NH
WA
OR
OR
WA
WA
3346
3347
3348
3349
3350
3351
3353
3395
3403
3404
WA 3416
WA
3418
MT 3420
AK 3421
AK
ID
NY
CA
NY
PA
MD
PA
AL
FL
FL
FL
FL
GA
GA
GA
KY
MS
3422
3423
3424
3425
3435
3452
Total
INDUSTRY/URBAN
(IND/URB)
Episode
1994
2023
2057
2060
2191
2210
2215
2220
MS
NC
NC
NC
NC
NC
SC
SC
SC
TN
TN
LA
NC
TN
TN
LA
LA
PA
VA
VA
VA
VA
LA
MS
AR
78
State
MI
AR
IN
IN
IA
DC
PA
VA
for dioxuis/furans. Number of data values varies by chemical.
B-4-2
-------
TABLE B-4 (Cont.)
2220
2225
2227
2309
2328
2329
2410
2416
2500
3024
3025
3034
3035
3038
3039
3040
3042
3043
3044
3045
3046
3047
3048
3049
3060
3064
3066
3079
3085
3094
3100
3101
3103
3111
3113
3115
3120
* No data available
VA
VA
VA
AL
NY
NY
MI
OH
3134
3141
3144
3147
3149
3164
3165
3168
WV 3172
ME 3174
ME
IA
IA
IA
KS
MO
NE
NE
MO
MO
MO
MO
MO
MO
AR
LA
LA
OK
TX
PA
MD
PA
MD
ND
IL
IL
MI
3182
3188
3189
3190
3198
3199
3203
3206
3219
3227
3231
3234
3235
3236
3244
3249
3250
3252
3258
3269
3275
3276
3283
3285
3286
3289
3296
WI 3297
WI
WI
DC
DE
NC
NC
AL
AL
FL
KY
TN
TN
TN
CO
SD
OR
3298
3299
3300
3301
3302
3306
3307
3310
3311
3313
3314
3315
3321
3322
3324
3326
OR 3327
OR 3411
WA 3412
WA 3426
MT
MT
MT
AK
ID
ID
ID
VA
CA
CA
CA
CA
CA
CA
CA
NY
3428
3432
3438
3443 «
Total
NY
NY
NY
NY
NY
NY
NY
NY
PA
WV
WV
WV
PA
NY
NY
NY
NY
NY
NY
NY
NJ
NJ
PR
WA
AR
106
PULP & PAPER
(No Chlorine)
Episode
3089
3090
3091
3092
3093
3108
3112
3114
(PPNQ
State
OK
OK
OK
LA
TX
WI
MN
IL
for dioxins/furans. Number of data values varies by chemical.
B-4-3
-------
TABLE B-4 (Cont.)
3135
3136
3137
3138
3140
3143
3145
3184
3191
3270
3287
3294
3330
3360
3375
3376
3377
3378
3401
Total
WI REFINERY/OTHER
\VI INDUSTRY (R/I)
i
WI Episode State
WI ' 2026 OK
WI 2380
WI 2383
WI 3061
MS 3063
WA . 3069
CA j 3071
CA 3072
WA 3086
FL 3095
AL 3096
GA 3125
GA 3183
GA 3264
GA 3312
TN 3431
27 ' 3434
3442
WOOD PRESERVERS ^444
rvvp)
1 ' 3446
Episode State Total
3076 OK
3077
3110
3167
3173
3196
3197
3271
3273
3274
3278
Total
* No data available
AR
WI
NC
FL
WY
CO
CA
CA
CA
CA
11
IL
IL
AR
LA
TX
TX
TX
LA
PA
PA
MN
KY
CA
WV
PR
NJ
LA
TN
KY
20
r
for dioxins/furans. Number of data values varies by chemical.
B-4-4
-------
APPENDIX B-5
Xenobiotics: Episode Numbers Used in Statistical Tests
(By Category)
-------
TABLE B-S
Other Xenobiotics: Episode Numbers Used in Statistical Tests (By Category)
NASQAN (NSQ)
Episode
2015
2016
2017
2023
2026
2070
2098
±*\j j \j
2105
2122
2126
2148
2151
2152
2191
2205
2220
2228
2246
2247
2280
2298
2309
2322
2358'
2430
2431
2432
2437
2439
2478
2544
2776
3036
* No data available
** Data available for
3041
State
AR
AR
AR
AR
OK
AK
WY
ND
MT
MS
FL
FL
FL
IA
NE
VA
VA
WA
WA
TX
TN
AL
NY
ME
MI
MI
MI
MN
OH
ID
LA
NV
IA
3042
3050
3104
3199
3281
3308
Total
NE
NE
MO
PA
SD
CA
NY
40
AGRICULTURE (AG)
Episode
2280
2358*
2478
3050
3082
3083
3084
3099
3105
3158
3170
3171
3180
3193
3208
3212
3282
3352
3437*
Total
SUPERFUND
Episode
3097
3226
State
TX
3261
3272
3414
3415
Total
POTW
Episode
2122
2152
2322
2432
ME 2544
ID 3308
MO
LA
LA
TX
DE
OK
ID
AL
AL
GA
VA
OR
OR
CA
LA
OR
19
(NPL)
State
DE
3450*
3451*
Total
BACKGROUND
Episode
2110
2139
2216
2283
2397
2435
2651
3022
3023
3028
3037
3073
3074
3075**
3166
WA 3169
HI
CA
PA
PA
6
State
MT
FL
NY
MI
LA
NY
CA
CA
8
(B)
State
SD
NC
PA
TX
WI
MI
NJ
ME
ME
ME
IA
AR
NM
TX
NC
AL
for other xenobiotics. Number of data values varies by chemical.
mercury only.
5-5-7
-------
TABLE B-5 (Cont.)
3178
3200
3205
3238
3248
Total
PULP & PAPER
(Chlorine) (PPC)
Episode
2017
2138**
2294
2302
2422
2532
2721
2725
3107
3118
3122
3151
3152
3192
3222
3224
3237
3245
3246
3260
3267
3303
3316
3318
3332
3335
3336
* No data available
* * Data available for
GA
CO
OR
AK
ID
21
State
AR
NC
GA
AL
WI
LA
ME
ME
WI
MI
MI
MA
NH
WA
WA
WA
MT
AK
AK
NY
CA
NY
PA
PA
FL
GA
GA
3340
3341
3342
3348
3395
3403
3416*
3418*
3420
3421
3422
3423
3424
3425
3435
Total
INDUSTRY/URBAN
(IND/URB)
Episode
3043
3044
3045
3079
3085
3101
3120
3149
3172
3174
3189
3190
3203
3234
3235
3236
3244**
MS
MS
3258
3269*
NC . 3275**
SC
NC
TN
3276
3283
3285
LA 3286
LA
PA
VA
VA
3289
3296
3298
3306
VA ; 3307
VA
LA
MS
42
3315
3411
3412
3426
3428
3438*
Total
State
VA
CA
CA
CA
CA
CA
CA
CA
NY
NY
NY
NY
PA
NY
NY
NJ
NJ
WA
35
NE PULP & PAPER
MQ (No Chlorine )
MO
OK
TX
Episode
3090
3091
PA ' 3108
MI 3112
DE
AL
FL
TN
TN
OR
MT
MT
MT
AK
3135
3136
3140
3143
3145
3191
3287
3294
3330
3360
(PPNQ
State
OK
OK
WI
MN
WI
WI
WI
WI
WI
WA
CA
WA
FL
AL
for other xenobiotics. Number of data values varies by chemical.
mercury only.
B-5-2
-------
TABLE B-5 (Cont.)
3360 AL
3376 GA
3377 GA
3401 TN !
Total 17
WOOD PRESERVERS
(WP)
Episode State
3076 OK
3077 AR
3110 WI
3167 NC
3173 FL
3196 WY
3197** CO
3271 CA
3273 CA
3274 CA
3278 CA
Total 11
REFINERY/OTHER
INDUSTRY (R/l)
Episode State
3061 AR
3063 LA
3072 TX
3095 PA
3446 KY
Total 5
i
* No data available for other xenobiotics. Number of data values varies by chemical.
** Data available for mercury only.
B-5-3
-------
B-5-4
-------
EPA
United States
Environmental Protection Agency
(WH-551)
Washington, DC 20460
Official Business
Penalty for Private Use
$300
* 1 9 9 2 *
THE YEAR OF
CLEAN WATER
------- |