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Office of Science and 

Technology (WH-551) 

Washington, D.C. 20460 

EPA 

United States 

Environmental Protection 

Agency 

EPA 823-R-92-008a 

September 1992 

Water 

NATIONAL STUDY OF 

CHEMICAL RESIDUES 

IN FISH 

Volume I 
EPA 823-R-92-008a 

September 1992 

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 
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. 
Table of Contents 

Chapter Page 

VOLUME I 

1 1 

1 

1 

2 

3 

30 

4 

LIST OF FIGURES 

LIST OF TABLES 

ACKNOWLEDGMENTS 

EXECUTIVE SUMMARY 

INTRODUCTION 

BACKGROUND 

GENERAL APPROACH 

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 

Dioxins/Furans 7 

Other Xenobiotic Chemicals 10 

Mercury 12 

Quality Assurance/Quality Control (QA/QC) 12 

SITE SELECTION 15 

DIOXIN AND FURAN RESULTS AND ANALYSIS 

PREVALENCE AND CONCENTRATION SUMMARY 

Toxicity Equivalency Concentration (TEC) 

Comparison of TCDD and other Dioxin/Furan Compounds 

GEOGRAPHICAL DISTRIBUTION 

SOURCE CORRELATION ANALYSIS 

Sources Located Near Highest Concentrations 

Concentration Comparison Between Site Categories 

21 

21 

24 

30 

30 

30 

39 

OTHER XENOBIOTIC COMPOUND RESULTS AND ANALYSIS 

PREVALENCE AND CONCENTRATION SUMMARY 

COMPOUNDS DETECTED AT MORE THAN 50 PERCENT OF THE SITES 

Total PCBs 

Biphenyl 

Mercury 

Pentacloroanisole 

1, 2, 3 and 1, 2, 4 Trichlorobenzene 

Pesticides/Herbicides 

vii 

xi 

xiii 

xv 

53 

53 

57 

57 

60 

64 

67 

70 

73 

iii 
Table of Contents (Cont.) 

Chapter Page 

COMPOUNDS DETECTED AT BETWEEN 10 AND 50 PERCENT OF THE SITES 

Hexachlorobenzene 

Pentachlorobenzene 

1, 3, 5 Trichlorobenzene 

Tetrachlorobenzenes 

Pesticides/Herbicides 

COMPOUNDS DETECTED AT LESS THAN 10 PERCENT OF THE SITES 

Octachlorostyrene 

Hexachlorobutadiene 

Diphenyl Disulfide 

Pesticides/Herbicides 

COMPARISON WITH NATIONAL CONTAMINANT BIOMONITORING 

PROGRAM 

91 

91 

96 

100 

100 

107 

122 

122 

122 

122 

125 

5 FISH SPECIES SUMMARY AND ANALYSES 

SUMMARY OF FISH SPECIES SAMPLED 

PREVALENCE AND AVERAGE CONCENTRATION OF CHEMICALS 

BY SPECIES 

HABITAT AND FEEDING STRATEGY OF MOST FREQUENTLY 

SAMPLEDSPECIES 

129 

131 

131 

137 

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-1 Analysis of Laboratory QA/QC Data 

A-2 Analytic and Quality Assurance Plan for the Determination of 

PCDD/PDCF in Fish 

A-3 Analytical Procedures and Quality Assurance Plan for the Determination 

of Xenobiotic Chemical Contaminants in Fish 

B ADDITIONAL DATA ANALYSES 

B-1 Nomographs for Estimating Cancer Risks 

B-2 Namographs for Estimating Noncarcinogenic Hazard Indices 

B-3 Site Description (also provided in Volume II, Appendix D) 

B4 Dioxins/Furans: Episode Numbers Used in Statistical Tests (also provided 

in Volume II, Appendix D) 

B-5 Xenobiotics: Episode Numbers Used in Statistical Tests (also provided in 

Volume II, Appendix D) 

iv 
Table of Contents (Cont.) 

VOLUME II 

C PROFILES OF BIOACCUMULATION STUDY CHEMICALS 

Dioxins/Furans: 

Dioxin: 2, 3, 7, 8 Tetratachlorobenzo-p-dioxin 

1, 2, 3, 7, 8 Pentachlorodibenzodioxin 

Hexachlorodibenzodioxins 

Furans 

Other Xenobiotics: 

Biphenyl 

Chlordane 

Chlorpylifos 

p,p'-DDE 

Dicofol 

Dieldrin 

Diphenyl Disulfide 

Endrin 

Heptachlor 

Heptachlor Epoxide 

Hexachlorobenzene 

Alpha-BHC ( a - Hexachlorocyclohexane) 

Isopropalin 

Gamma-BHC ( g -Hexachlorocyclohexane) 

Mercury 

Methoxychlor 

Mirex 

Nitrofen 

Nonachlor 

Octachlorosytrene 

Oxychlordane 

Pentachloroanisole 

Pentrachlorobenzene 

Pentachloronitrobenzene 

Pentachlorophenol 

Perthane 

Polychlorinated Biphenyls (PCBs) 

1, 2, 3, 4 and 1, 2, 3, 5 Tetrachlorobenzene 

1, 2, 4, 5 Tetrachlorobenzene 

1, 2, 3 Trichlorobenzene 

1, 2, 4 Trichlorobenzene 

1, 3, 5 Trichlorobenzene 

Trifluralin 
Table of Contents (Cont.) 

VOLUME II (Cont.) 

D DATA TABLES 

D-1 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 I, Appendix B) 

D-4 Dioxin/Furan Data by Episode Number 

Concentration And Detection Limits 

D-5 Xenobiotic 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 
List of Figures 

Figure Page 

2-1 

2-2 

2-3 

2-4 

2-5 

2-6 

2-7 

3-1 

3-2 

3-3 

3-4 

3-5 

3-6 

3-7 

3-8 

3-9 

3-10 

3-11 

3-12 

3-13 

3-14 

3-15 

3-16 

3-17 

4-1 

4-2 

4-3 

4-4 

4-5 

4-6 

4-1 

Schematic of laboratory procedures for dioxins and furans 

Schematic of laboratory analytical procedure for other xenobiotic chemicals 

Schematic of laboratory analytical procedure for mercury 

Location of bioaccumulation study sampling sites 

Location of targeted sites 

Location of sites representing background conditions 

Location of sites selected from a subset of the USGS NASQAN network 

Summary of dioxins/furans detected in fish tissue 

Cumulative frequency diagrams of concentrations of six dioxin congeners in fish tissue 

Cumulative frequency diagrams of concentrations of six furan congeners in fish tissue 

Cumulative frequency distribution of maximum calculated TEC values in fish tissue by 

percentile of sites 

Toxicity equivalency concentrations (TEC) based on Barnes et al., 1989 method 

Map showing geographical distribution of various concentration ranges of 

2, 3, 7, 8 TCDD in fish tissue 

Map showing geographical distribution of various concentration ranges of 

2, 3, 7, 8 TCDF in fish tissue 

Map showing geographical distribution of various concentration ranges of TEC 

in fish tissue 

Example box plot with explanations of features 

Box and whisker plot for 2, 3, 7, 8 TCDD concentration in fish tissue 

Box and whisker plot for TEC concentrations in fish tissue 

Box and whisker plot for 2, 3, 7, 8 TCDF concentrations in fish tissue 

Box and whisker plot for 1, 2, 3, 7, 8 PeCDD concentrations in fish tissue 

Box and whisker plot for 1, 2, 3, 7, 8 PeCDF concentrations in fish tissue 

Box and whisker plot for 2, 3, 4, 7, 8 PeCDF concentrations in fish tissue 

Box and whisker plot for total HxCDDs concentrations in fish tissue 

Box and whisker plot for total HxCDFs concentrations in fish tissue 

Summary of other xenobiotic compounds detected in fish tissue 

Total PCBs: a) cumulative frequency distribution and b) map of geographical distribution 

of various concentration ranges in fish tissue 

Box and whisker plot for total PCBs in fish tissue 

Biphenyl: a) cumulative frequency distribution and b) map of geographical distribution of 

various concentration ranges in fish tissue 

Box and whisker plot for biphenyl in fish tissue 

Mercury: a) cumulative frequency distribution and b) map geographical distribution of 

various concentration ranges in fish tissue 

Box and whisker plot for mercury in fish tissue 

8 

11 

13 

16 

17 

18 

19 

23 

25 

26 

28 

29 

31 

32 

33 

41 

42 

45 

46 

47 

48 

49 

50 

51 

55 

58 

61 

63 

65 

66 

68 

vii 
List of Figures (Cont.) 

Figure Page 

4-8 

4-9 

4-10 

Pentachloroanisole: a) cumulative frequency distribution and b) map of geographical 

distribution of various concentration ranges in fish tissue 

Box and whisker plot for pentachloroanisole in fish tissue 

Cumulative frequency distribution of a) 1, 2, 3 trichlorobenzene and b) 1, 2, 4 trichlorobenzene in fish tissue 

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 

4-12 

4-13 

4-14 

4-15 

4-16 

Box and whisker plot for 1, 2, trichlorobenzene 3 in fish tissue 

Box and whisker plot for 1, 2, 4 trichlorobenzene in fish tissue 

p.p’ -DDE: a) cumulative frequency distribution and b) map of geographical distribution of 

various concentration ranges in fish tissue 

Box and whisker plot for p,p’ -DDE in fish tissue 

Cumulative frequency distribution of a) total chlordane, b) cis-chlordane, c) trans-chlordane, 

and d) oxychlordane in fish tissue 

4-17 Cumulative frequency distribution of a) trans-nonachlor b) cis-nonachlor and c) total 

nonachlor in fish tissue 

4-18 Map of geographical distribution of various concentration ranges for a) total chlordane 

and b) total nonachlor in fish tissue 

4-19 

4-20 

4-21 

4-22 

4-23 

4-24 

Box and whisker plot for total chlordane in fish tissue 

Box and whisker plot for total nonachlor in fish tissue 

Box and whisker plot for oxychlordane in fish tissue 

Dieldrin: a) cumulative frequency distribution and b) map of geographical distribution of 

various concentrations in fish tissue 

Box and whisker plot for dieldrin in fish tissue 

Cumulative frequency distribution of a) alpha-BHC and b) gamma-BHC (lindane) 

in fish tissue 

4-25 

4-26 

4-27 

4-28 

4-29 

4-30 

Box and whisker plot for alpha-BHC in fish tissue 

Box and whisker plot for gamma-BHC in fish tissue 

Map of geographical distribution of various concentration ranges for a) gamma-BHC 

(lindane) and b) alpha-BHC in fish tissue 

Hexachlorobenzene: a) map of geographical distribution of various concentration ranges 

and b) cumulative frequency distribution in fish tissue 

Box and whisker plot for hexachlorobenzene in fish tissue 

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 

4-31 Box and whisker plot for pentachlorobenzene in fish tissue 

4-32 Box and whisker plot for 1, 3, 5 trichlorobenzene in fish tissue 

69 

71 

72 

74 

75 

76 

77 

79 

81 

82 

83 

85 

87 

88 

89 

90 

92 

93 

94 

95 

97 

98 

99 

101 

102 

viii 
List of Figures (Cont.) 

Figure Page 

4-33 

4-34 

4-35 

4-36 

4-37 

4-38 

4-39 

4-40 

4-41 

4-42 

4-43 

4-44 

4-45 

4-46 

4-47 

4-48 

4-49 

4-50 

4-51 

4-52 

4-53 

6-1 

6-2 

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 

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 

Box and whisker plot for 1,2,3,4 tetrachlorobenzene in fish tissue 

Cumulative frequency distribution of a) mirex and b) chlorpyrifos in fish tissue 

Box and whisker plot for mirex in fish tissue 

Map of geographical distribution of various concentration ranges for chlorpyrifos in 

fish tissue 

Box and whisker plot for chlorpyrifos in fish tissue 

Cumulative frequency distribution of a) dicofol (kelthane), b) methoxychlor, and c) perthane 

in fish tissue 

Map of geographical distribution of various concentration ranges for 

a) dicofol and b) methoxychlor in fish tissue 

Box and whisker plot for dicofol in fish tissue 

Cumulative frequency distribution of a) trifluralin and b) isopropalin in fish tissue 

Map of geographical distribution of various concentration ranges for a) trifluralin and 

b) isopropalin in fish tissue 

Box and whisker plot for trifluralin in fish tissue 

Box and whisker plot for isopropalin in fish tissue 

Endrin: a) cumulative frequency distribution and b) map of geographical distribution of 

various concentration ranges in fish tissue 

Box and whisker plot for endrin in fish tissue 

Cumulative frequency distribution of a) octachlorostyrene, b) hexachlorobutadiene, 

c) dipbenyl disulfide, and d) nitrofen in fish tissue 

Cumulative frequency distribution of a) heptachlor and b) heptachlor epoxide in fish tissue 

Map of geographical distribution of various concentration ranges for a) heptachlor and 

b) heptachlor epoxide in fish tissue 

Box and whisker plot for heptachlor epoxide in fish tissue 

Pentachloronitrobenzene: a) cumulative frequency distribution and b) map of geographical 

distribution of various concentration ranges in fish tissue 

Graphical tool for estimating upper-bound cancer risk of p,p’-DDE or equivalents for 

different fish consumption rates 

Graphical tool for estimating upper-bound noncarcinogenic hazard index of p,p’-DDE 

for different fish consumption rates 

103 

105 

106 

108 

109 

110 

112 

113 

114 

115 

117 

118 

119 

120 

121 

123 

124 

126 

127 

128 

130 

158 

160 

ix 
List of Tables 

Table page 

2-1 

2-2 

3-1 

3-2 

3-3 

3-4 

3-5 

4-1 

4-2 

4-3 

4-4 

4-5 

5-1 

5-2 

5-3 

5-4 

5-5 

6-1 

6-2 

6-3 

6-4 

6-5 

6-6 

6-7 

List of Target Analytes 

Internal Standard Solutions Used for PCDD/PCDF Analyses and Xenobiotic Analyses 

Summary of Dioxins/Furans Detected in Fish Tissue 

1989 Toxicity Equivalency Factors 

Location of Maximum Measured HxCDD and HpCDD Concentrations in Fish Tissue 

Location of Maximum Measured HxCDF and HpCDF Concentrations in Fish Tissue 

Mann-Whitney U Test Results for Dioxins/Furans Comparing Selected Source Categories 

Summary of Xenobiotic Compounds in Fish Tissue 

Summary of PCBs in Fish Tissue 

Results of Statistical Tests for Selected Xenobiotics and Mercury 

Results of Statistical Tests for Selected Xenobiotics (Pesticides/Herbicides) 

Sites with Highest Concentrations of Chlordane-Related Compounds 

Distribution and Fading Strategy for Fish Species Collected 

Average Fish Tissue Concentrations of Dioxins and Furans for Major Species 

Detailed Summary of Occurrence of Prevalent Dioxins/Furans by Fish Species 

Average Fish Tissue Concentrations of Xenobiotics for Major Species 

Detailed Summary of Occurrence of Prevalent Xenobiotics by Fish Species 

Dose-Response Variables Used in Risk Assessment 

Estimates of Potential Upper-Bound Cancer Risks at Targeted Sites Based on Fillet 

Samples 

Estimates of Potential Upper-Bound Cancer Risks at Background Sites Based on Fillet 

Samples 

Fish Tissue Concentrations Used to Estimate Cancer Risks 

Number of Sites with Estimated Upper-Bound Risks 

Estimated Upper-Bound Risks at Three Fish Consumption Rates Based on Fillet 

Samples 

Noncarcinogenic Hazard Index Values at Targeted and Background Sites Based on 

Fillet Samples 

5 

9 

22 

27 

37 

38 

43 

54 

59 

62 

80 

84 

132 

138 

139 

140 

141 

149 

152 

153 

154 

155 

157 

159 

xi 
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 Yender, 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 preparation 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 Buttenworth. 

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 QA/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 

Darvene Adams Region II ESD 

Gary McKenna Region II ESD 

Bob Donaghy Region III ESD 

Jerry Stober Region IV ESD 

Pete Redmon Region V ESD 

Carl Young Region VI ESD 

Bruce Lattell Region VII ESD 

Tim Osag Region VIII ESD 

Doug Eberhardt Region IX WMD 

Bruce Cleland Region X ESD 

Dave Terpening Region X ESD 

Evan Hornig Region X ESD 

Elizabeth Southerland OST/AWPD 

Stephen Kroner OST/AWPD 

Martin Brossman OST/AWPD 

Ruth Yender OST/AWPD 

U.S. EPA 

Brian Butterworth 

Douglas Kuehl 

University of Wisconsin - Superior, 

Center for Lake Superior Environmental Studies 

xiii 
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 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. 

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 frequently 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. 

xv 
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 
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 fur-an 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 tetmchlorodibenzofuran (TCDF). These compounds 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 
1 : .

HAWAII 

PUERTO RICO 

Figure 1. Location of bi oaccumulation study sampling sites. 
TABLE 2 

Summary of Prevalence and Concentration 

for Dioxins and Furans 

Chtmlcal 

Percent of 

Sltcs Detected Mar 

Conccabrdon 

pglg or ppt by wet wcigbt 

Mean Medlan 

Diorins 

I ,2,3,4,6,7.8 HpCDD 89 249 10.5 2.83 

2,3,7,8 TCDD 70 204 6.89 1.38 

1,2,3,6,7,8 HxCDD 69 101 4.30 1.32 

1,2.3,7,8 PeCDD 54 54.0 2.38 0.93 

1,2,3,7,8,9 HxCDD 38 24.8 1.16 0.69 

1,2,3,4,7,8 HxCDD 32 37.6 1.67 1.24 

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* 

89 404 13.6 2.97 

64 56.4 3.06 0.75 

54 58.3 1.91 0.72 

47 120.0 1.71 0.45 

42 45.3 2.35 1.42 

32 19.3 1.24 0.98 

21 30.9 1.74 1.42 

4 2.57 1.24 1.30 

1 O.% 1.22 1.38 

N/A 213 11.1 2.80 

+ TEC represents the sum of toxicity-weighted concentrations of all dioxin3 and furans relative to 2,3,7,8 TCDD. 

xix 
Chemlcrl 

DDE 99 14000 

Mercury 92 1800 

B lphenyl 94 131 

Total PCBs 91 124000 

Nonachlor, trans 77 477 

C hlordane, cis 64 378 

Pentachloroamsole 64 647 

C hlordane, trans 61 310 

Dleldrin 60 450 

Alpha-BHC 55 44.4 

1,2,4 Trichlorobenzene 53 265 

Hesachlorobenzene 46 913 

Gamma-BHC 42 83.3 

1,2,3 Trichlorobenzene 43 69.0 

Mrrex 38 225 

Nonachlor, CIS 35 127 

Oxychlordane 27 243 

C hlorpyrtios 26 344 

Pentachlorobenzene 22 125 

Heptachlor Epoxide 16 63.2 

Dicofol 16 74.3 

I .2,3,4 Tetrachlorobenzene 13 76.7 

Trifluralin 12 458 

I ,3,5 Trichlorobenzene 11 14.9 

En&m 11 162 

1,2,3.5 TECB 9 28.3 

Octachlorostyrene 9 138 

1,2,4,5 TECB 9 28.3 

Methoxychlor 7 393 

ISOpr0pdin 4 37.5 

Niuofen 3 17.9 

Hexachlorobutadiene 3 164 

Heptachlor 2 16.2 

Perrhane 1 5.12 

Pentachloronitrobenzene I 15.5 

Diphenyl Disulfide 1 3.24 

TABLE 3 

Summary of Prevalence and Concentration 

for 45” Other Bioaccumulative Compounds 

Percent of 

Sites Detected 

Coaccntratlon 

ngfgor ppb by wet weight 

Mean Median 

295 58.3 

260 170 

2.7 064 

1890 209 

31.2 9.22 

21.0 3.66 

10.8 0.92 

16.7 2.68 

28.1 4.16 

2.41 0.72 

3.10 0.14 

5.80 ND 

2.70 ND 

1.27 ND 

3.86 ND 

8.77 ND 

4.75 ND 

4.09 ND 

1.18 ND 

2.19 ND 

0.98 ND 

0.47 ND 

5.98 ND 

0.12 ND 

1.69 ND 

0.34 ND 

1.71 ND 

0.33 ND 

1.32 ND 

0.46 ND 

0.17 ND 

0.57 ND 

0.35 ND 

0.03 ND 

0.09 ND 

0.02 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. 

xx 
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 1944 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 

NSCW, 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 poliutants 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 wete selected based on 

probable sources of polWa.nts. Background sites were selected to provide a comparison with areas 
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. 

PuIp 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 MannWhitney 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 Super-fund 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 observations 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 industrial/urban sites, paper mills using chlorine, refinery/other industry sites, nonchlorine paper mills. 

and Superfund sites. 

HUMAN HEALTH RISK JXllMATES 

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 consumption rates of 6.5,30, and 140 g/day were used. 
The highest estimated lifetime human cancer risk levels are associated with total PCBs. The 

cancer risk exceeded 1 O-” at 42 sites for total PCBs for a fish consumption rate of 6.5 giday (Table 

4). The second highest cancer risk was associated with dieldrin where six sites had estimated cancer 

risks greater than 1 O-” for a 6.5g/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 PC%, 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 of fish 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 dioxin’furan concentrations 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 dioxinsjfurans or the other study compounds. 
TABLE 4 

Number of Sites with Estimated Upper-Bound Risks 

Cllellll~l 

No. of Sites 

with Fillet 

Data 

RISK LEVEL (Cumulative) 

10-6 lo-5 10-4 10-3 

(>l in l,ooo,ooo) (>I in 100,000) (>l in 10,ooo) (rl in 1,ooo) 

PCBs 106 89 79 42 10 

Dieldrin 106 53 31 6 0 

Combined Chlordane 106 44 10 0 0 

DDE 106 40 10 0 0 

Heptachlor Epoxide 106 9 2 0 0 

Alpha-BHC 106 11 1 0 0 

Mirex 106 8 2 0 0 

HCB 106 5 0 0 0 

Gamma-BHC 106 0 0 0 0 

Heptachlor 106 0 0 0 0 

Dicofol 106 0 0 0 0 

Hexachlorobutadiene 106 0 0 0 0 

Pentachloroanisole 106 0 0 0 0 

Tlifhdill 106 0 0 0 0 

Chemical 

No. d Sitea 

with Filkt 

Data 

10-6 10-S 10.4 10-3 

(>l in l,o4lo,ooo) (>I in loo, ooo) (>l in 10,ooo) (>l in 1,ooo) 

PCBS 4 1 1 0 0 

DDE 4 1 0 0 0 

Basis: 1) 

2) 

3) 

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. 

Combined chlonhne is the sum of cis- and trans-chlordane isomers, cis- and &ins-nonachlor isomers, and oxychlordane. 
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. Additionally, 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 of fish 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) 

1 
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 

Study sites were reanalyzed as part of thisstudy 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-feeding 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 polychlorinated 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. 

2 
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 gamed 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).1 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). 

3 
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 ( 10-6 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 

4 
TABLE 2-1 

List of Target Analytes 

DIOXINS 

2,3,7,8 Tetrachiorodibenzodioxin (TCDD) 

1,2,3,7,8 Pentachlorodibenzodioxin (PeCDD) 

1,2,3,6,7,8 Hexachlorodibeuzodioxin (HxCDD) 

1,2,3,7,8,9 Hexachlorodibenzodiox.in(HxCDD) 

1,2,3,4,7,8 Hexachlorodibenzodioxin(HxCDD) 

1,2,3,4,6,7,8 Heptachlorodibenzodioxin(HpCDD) 

FIJRANS 

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 Heptachiorodibenzofuran (HpCDF) 

OTHER XENOBIOTICS 

Biphenyl 

Chlordane, cis 

Chlordane, trans 

Chlorpyrifos 

y;;gy” 

Dieldrin 

Diphenyl Disulfide 

Endrin 

Heptachlor 

Heptachlor epoxide 

Hexachlorobenzene 

Hexachlorobutadiene 

alpha-BHC 

gamma-BHC (lindane) 

Isopropalin 

Mercury 

Methoxychlor 

Mirex 

Nitrofen 

Nonachlor, cis 

Nonachlor, tram 

Octachlorostyrene 

Oxychlordane 

Pentachloroanisole 

Pentachlorobenzene 

Pentachloronitrobenzene 

Perthane 

Polychlorinated Biphenyls 

1 YYKzY:~:~~::~ , , , 

1,2,3,4 Tetrachlorobenzene 

1,2,3,5 Te trachlorobenzene 

1,2,3 Ttichlorobenzene 

1,2,4 Trichlorobeuzene 

1,3,5 Trichlorobenzene 

Trifluralin 

5 
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 HandlinelPreparation 

After collection, the fish were individually wrapped in aluminum foil, labeled, dry-iced, and 

shipped frozen to Duluth. 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 sampIe collection a.re 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 reIationships. 

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 that 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, 1990b. EPA/600/3- 

90/022 (PCDD/PCDF); U.S. EPA, 1990~. EPA/600/3-90/023 (xenobiotic chemical contaminants); 

and U.S. EPA, 1989a (mercurv). 
Dioxinsff urans 

A schematic of the analytical procedures used for the tissue extraction of polychlorinated 

dibenzodioxins and polychlorinated dibenzoiurans (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 13C 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-ceiite 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 florisilkodium 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 PCDDIPCDF 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 specuometry (W/MS) analysis. 

During the course of this study, changes were made to the PCDDrPCDF methodology. ln 

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. Ln 

addition, the procedure for determining the minimum level of detection wasmodified to betterreflect 

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 (DB5 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 flL with tridecane. Sample analyses were done in sets of hvetve 

consisting of: 
FLDRISIL 

CHROMATO4 GRAPHY 

soxHEr csKNJND TISSUE 

EXTRACTION NW 

13C LABELED 

SlJflROGATE ANALYTES 

SOLVENT 

REMOVAL 

CARBON 

KtRERNA DANSH CHROMATOAPPARATUS GRAPHY 

\ 

SIAFUUC ACDICEUTE 

POTASSW SUCATE 

SUCAOEL 

ELUTION 

1. lwERFrnT REMOVAL 

2044. OF 2% 

cH,cL, I I-EXM 

2. ANALYTE f RAWION 

s CH 2ch 

1. NTERFERENT REMOVAL 

2OM. OF 25% 

BENZPQ: I C&CL2 

2. ANACY lE FRACTION 

29&m TOLUENZ 

AM) SECOH) NTERNAL STAPDARD 

” cl21 ,2,3,4-TCW N TRDEC AIS 

mGc/l-RMS 

PCDD/PCDF OUANTITATION 

Figure 2-l. Schematic of laboratory procedures for dioxins and furans. 
TABLE 2-2. Internal Standard Solutions Used for PCDD/PCDF Analyses 

Compound 

Concentration 

wi Solution (pg/pL) 

Concentration 

in tlssue ( pg/g*) 

37~~42.3.7.8TCDD 

13~12 2.3.7.8 TCDD 

13~12 2.3.7.8 TCDF 

13~12 1,23,7.8 PeCDD 

13~12 1,2,3.7,8 PeCDF 

13~12 1.2,3,4.7,8 HxCDD 

13~12 1,2,3,4,7.8 HxCDF 

13~12 1.2.3.4.6.7,8 HpCDD 

13~12 1.2.3,4.6.7.8 HpCDF 

13~12 OCDD 

37~~ 2,3,7,8 TCDF 

1.2.3-4 TCDD 

1.2,4,7,8 PeCDD 

1.2.3.4 TCDF 

1,2.3,6,7 PeCDF 

13~121.2.3.4 TCDD 

*Assumes a 20-g sample. 

Reference: U.S. EPA, 199Ob. 

10.0 

25.0 

25.0 

25.0 

25.0 

62.5 

62.5 

62.5 

62.5 

125.0 

10.0 

5.0 

5.0 

5.0 

5.0 

50.0 

Compound Concentration (cLg/mL) 

Iodobenzene 125 

1 Aodonaphthalene 125 

4,4’-Diiodobiphenyl 125 

Biphenyl-Dlo 

Phenanthrene-Dlo 

Chrysene-D12 

Solution f 1QlLl 

50 

75 

75 

Surrogate Standard and Internal Standard Solutions 

Used for Other Xenobiotic Compound Analyses 
1. One method blank; 

9 i. 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 anaiytes 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 Ptig 

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 II). The actual detection limits achieved were 

often lower than the above targeted values. 

Other Xeno bio tic 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, 199Oc, 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 GUMS 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 .O g to 0.8 g. These changes were made to obtain better recovery of the target 

anaiytes and to decrease interferences. The quantitative results (concentrations) obtained with the 

two methods were comparable. 
-SAWPLES A)E(ETCouECnoN 

I 

t B) SJWCK CoLLTCTloN k 

1-AP4,4--L 

I 

A00 SuiBotMTE ANALYTES 

I 

TOTAL LESS 1 aRAM 

MEPnsH 

A)GBN3FLLEfOtl 

8) mm WHOLE 

AjBLENI2OglSStE 

wmNtP% 

B) EXTRACT WITH 

tEXAtWcyct, 

A) KWEMA-OANSti 

APPARATUS 

8) FLTEBED AR 

C) DRaulM TOTAL 

c 

2.1gSUCAGEL 

A) ACTWAlE 13Ob:. 0VERNM-l 

8) DEACllVATE 1% t&O 

C) ELUTE ANALYTES WTTH 

m 15xDcmoBoc(ETHAN/ 

HEXANt 

A) ADO Id lOUmE 

8) COfdCENlRAlE TO 5OOd 

,I, ,,I ,j ELEC~~~~WACT~~~~~ATK)N 

IIll,l *I POSITIVE CHEMICAL ICMZAl-KIN 

I 

= PER8EAllCN CH3OMATOQRAPY 

NECiAllVE C-CAL MATKIN 

COLLECTFRACTION 1.7TMSlHi 

DiSTANCEFROMAPEXOFDap UJMllJsl 

TOnEAFEXOFPYFIEN -- -- -- 

- 

-= 

-- 

-- 

Y- -- 

-- 

-- -- 

-- -- 

-- -- 

- 

-- -- 

-- -- 

-- 

COLLECT AHI REWCE 

Figure 2-2. Schematic of laboratory analytical procedure for other xenobiotic chemicals. 
Samples were analyzed by GUMS as referenced in U.S. EPA, 1990~. 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 @g/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 Anaiytes (except PCBs) 

Polychlorinated Biphenyls 

Level of Chlorination: 

2.5 rig/g 

1-3 1.25 rig/g 

4-6 2.50 rig/g 

7-8 3.75 rig/g 

9-10 6.25 rig/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; Hotwitz, 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 @g/g)(ppm wet weight). 

The detection limit for mercury was 0.05 pg/g for samples analyzed prior to 1990 and 0.00 13 pg/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 (QAIQC) 

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 
250 ml Flask to Laboratory 

vacuum tfne 

2 L Flask 

(SolutiOn Of HNOs, H2=4, 

KMn04, and k(so4)2) 

Figure 2-3. Schematic of laboratory analytical procedure for mercury. 

13 
nagged 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 arc listed in Appendix A. Table A-4 and 

Appendix A, Table A-7. If more than 20% 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. Hush/replace CC 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 flagged with “QR” in the database (Vol. II, 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. 

2. 

3. 

4. 

Standardized written sampling and analytical procedures, 

Standardized handling and shipping procedures, 

The use of blanks (reagent and field), 

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. 
Procedures for documentation, data reduction and validation. and reporting were specified 

in the Analytical ProceduresandQuality Assurance Plan Manuals (U.S. EPA, 1990b. 199Oc, 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 

TvDe of Site Sampled 

Targeted Sites 313 

Background Sites 35 

USGS NASQAN Sites (Subset) 

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 dioxitifuran congencrs 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 phenols 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 othercompound 

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 
PUERTO RICO 

Figure 2-4. Location of bioaccumulation study sampling sites. 

16 
/- 

. 

PUERTO RICO 

Figure 2-5. Location of targeted sites. 

17 
c 

4 

& a 

PUERTO RICO 

Figure 26. Location of sites representing bdqyound conditions. 
PUERTO RICO 

f@ure 2-7. Lmatbn of sites selected from a subset of the USGS NASQAN Network. 

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 chlorothalonil (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 sires 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 the Toxicity 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-4 (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 HxCDD) to 89 

percent (1,2,3,4,6,7,8 HpCDD) 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 

2,3,7,8 TCDF 

2,3,7,8 TCDD 

1,2,3,6,7,8 HxCDD 

2,3,4,7,8 PeCDF 

1,2,3,4,6,7,8 HpCDF 

1,2,3,7,8 PeCDD 

89 

89 

70 

69 

64 

54 

54 

21 
TABLE 3-1 

Summary of Dioxins/Furans Detected in Fish Tissue 

Percent of 

Sites Where Standard Total Number 

Chemical 

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 

1234789 HpCDF 

123789 HxCDF 

TEC 

Detected Max* Mean* Deviation Median* of Sites D 

89.4 403.9 13.61 40.11 2.97 388 7 

89.0 249.1 10.52 25.30 2.83 354 6 

70.3 203.6 6.89 19.41 1.38 388 1 

68.8 100.9 4.30 9.25 1.32 375 4 

64.3 56.37 3.06 6.47 0.75 387 9 

53.8 58.3 1.91 4.41 0.72 353 14 

53.5 53.95 2.38 4.34 0.93 385 2 

47.3 120.3 1.71 7.69 0.45 387 8 

42.0 45.33 2.35 4.53 1.42 379 10 

37.9 24.76 1.16 1.74 0.69 375 5 

32.3 37.56 1.67 2.39 1.24 375 3 

31.7 19.30 1.24 1.51 0.98 379 13 

20.8 30.86 1.74 2.34 1.42 379 11 

4.0 2.57** 1.24 0.33 1.3 353 15 

1.3 0.96** 1.22 0.41 1.38 379 12 

N/A 213.05 11.08 23.77 2.8 358 

* Concentrations are picograms gram (pg/g) per or parts per 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 - Toxicity equivalency concentration based on method of Barnes et al., 1989. 

Note: 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 

2373 TCDF 

1234678 HpCDD 

2378 TCDD 

123678 HxCDD 

23478 PeCDF 

1234678 HpCDF 

12378 PeCDD 

12378 PeCDF 

123478 HxCDF 

123789 HxCDD 

123478 HxCDD 

:!34678 HxCDF 

123678 HxCDF 

1:!34789 HpCDF 

123789 HxCDF 

i 

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 cumuIative 

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 duphcate 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. 

Toxicitv 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 

123478 HxCDD t 

I 

. 

I 

a 

1 

2a 40 60 50 100 

PercentlIe of sites 

, 

123789 HxCDD 

i’ 

i 

!2 c ‘0 

B 

; 

1 ?Srn~~ 

_ _ _. _ __ - - _. 

I I 

0 XI so 

PezBntJl. d Skw 

m loo 

12378 PeC DD 

, 

123678 HxCDD 

I 

I . . . - ., . _ _ I 

0 20 a M 0 loa 

Percentile of Silo8 

1234678 HpCDD 

. i 

1 il 

t Js4Lk 

.-....-..-.- _.---. -.---.--.- ” .-._._. I 

0 20 

PZLO 0%” 

I la0 

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. 

2.5 
2378 TCDF 

i 

l 

: 

- ____._....^._,_. ._.__... .._ _... . . . . . . . _.. .._ . ..I 

0 20 40 60 30 100 

Porceme Of SItor 

23476 PeCDF 

1 ,I 

0 20 iI sb 43 IOQ 

PercenttIe of Sates 

234678 HxCDF 

mpmnl 

7m- 

.._.. .-..._ ..-. - -..... - - ..-.-.-...-.... 

37ssim 

20 

PeGtlde o& 

W 100 

Figure 3-3. 

12378 PeCDF 

I I 

0 20 40 60 w 100 

Percennle 01 Sdes 

--j 

123478 HxCDF 

‘1 i 

I 

‘i I.... PO”?-z ..,. 

?Shcucmwb 

1: 

f 

/ 379 .sm# 

1 I 

0 20 40 60 so loo 

Percenrle 01 Sites 

1234678 HpCDF 

. 8 . I 

20 

Pezefltil. o&e 

iJ . do 

Cumulative fkequewy diagrams of conenbations of six fkan umgeners in fish 

tissue. Points display vahcs 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 

Mono-, Di-, and Tri-CDDs 

2,3,7,8 TCDD 1 

Other TCDDs 0 

2,3,7,8 PeCDD 0.5 

Other PeCDDs 0 

2,3,7,8 HxCDDs 0.1 

Other HxCDDS 0 

2,3,7,8 HpCDD 

Other HpCDDs 

OCDD 

Mono-, Di-, and Tri-CDFs 

2,3,7,8 TCDF 0.1 

0 ther TCDFs 0 

1,2,3,7,8 PeCDF 0.05 

2,3,4,7,8 PeCDF 0.5 

Other PeCDFs 0 

2,3,7,8 HxCDFs 0.1 

0 ther HxCDFs 0 

2,3,7,8 HpCDFs 0.01 

Other HpCDFs 0 

Reference: Barnes et al., 1989. 

27 
TEC 

4 

25th percentile 

10thpercentile 

: 

6 388sites 

0 20 40 80 80 loo 

Percentile of Sites 

Figure 3-4. Cumulative frequency distribution of maximum calculated TEC values in fish 

tissuebypercentile ofsites. Bar on x-axis indicates sites where concentrations 

of PDCCYPCDF congenen were below detection for ail samples from those sites. 

28 

Comoarison of TCDD and Other Dioxin/Furan Comnounds 

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 dioxitifuran 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. j 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. I pg/g, 2,3,7,8 TCDD of 0.5 1 pg/g. and ?EC 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 IO 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 TCDO (p@g}: 

n - a10 13’ 

A - >ltolO 42 

O- oto1 45 

‘Percent of sibs in categaty 

TOM Sites: 388 

Fibt Only Sites: 31 

Maximum was Fillet: 18 

Figure 3-6. Map showing geographical distribution of various cmxntration ranges of 2,3,7,8 

TCDD in fish tissue. 

3I 
2.3,7.8 TCDF @g/g): 

n - >lO 23’ 

A - >ltolO 40 

o- 010 1 29 

Total Sites: 388 

Filler Only Sites: 32 

Mhnum was Wet: 30 

- 

‘Percent of sites in category 

Figure 3-7. Map showing geographical distribution of various concentration ranges of 2,3,7,8 

TCDF in fish tissue. 
_. _ -- ._- - - 

.____. -..--. 

__------ 

m =>50 5' 

A = > 1 to 50 65 

0 - oto1 30 

‘Percent of sites in cabgory 

Total Sites: 388 

Fillet Only Sites: 33 

Maximum was Fillet: 23 

Figure 3-8. Map showing geographical distribution of various concentration ranges of TEC 

in fish tissue. 

33 
Tetra-Dioxh/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 

bIeaching 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 vicinily. The top five sites for both compounds are shown 

below: 

2,3,7,8 TCDD 

Cont. Episode 

P& (PP[) Number Type of Sample Location 

203.6 3078 WB Sm Buffalo Bayou Meto, Jacksonville, AR 

160.4 3425 WB Carp Wham Brake, Swartz, LA 

143.3 3346 WB Creek Chubsucker Roanoke R., Plymouth, NC 

104.1 3348 WB Blue Catfish Sampit R., Georgetown, SC 

98.9 3340 WB Channel Catfish Leaf R., New Augusta, MS 

2,3,7,8 TCDF 

Cont. 

PgMPPtl 

Episode 

Number Type of Sample Location 

403.9 3162 Hepatopancreas crab 

320.7 3221 WB Carp 

273.8 3395 WB Redhorse Sucker 

261.3 3087 WB Carp 

207.5 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 contamination, chemical manufacturing plants, automobile manufacturing, a refinery, and an incinerator. 

34 
Penta-DiodndFurans 

The sites with the highest 10 percentile concentrations for 1.2,3,7,8 PeCDD were near a 

variety of 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 

Cont. Episode 

pg/g (ppt) Number Type of Sample Location 

53.9 3355 WB Carp 

27.2 3098 WB White Sucker 

22.4 3141 WB Carp 

15.9 3162 Hepatopancreas Crab 

14.3 2290 WB Spotted Sucker 

Old Mormon Slough, Stockton, CA 

Red Clay Cr., Ashland, DE 

Milwaukee R., Milwaukee, WI 

Hylebos Waterway, Tacoma, WA 

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 Super-fund 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). 
I ,2,3,7,8 PeCDF 

Con. Episode 

pg/g(ppt) Number Type of Sample Location 

120.3 3162 Hepatopancreas Crab 

68.4 3163 Hepatopancreas Crab 

54.3 3206 Craytish 

20.3 3085 PF Back Drum 

17.2 2290 WB Spotted Sucker 

Hylebos Waterway, Tacoma, WA 

Commencement Bay, Tacoma, WA 

Willamette R., Portland, OR 

Brazos R. Freeport., TX 

Savannah R., Augusta, GA 

2,3,4,7,8 PeCDF 

Cont. 

ptig (ppt) 

Episode 

Number Type of Sample Location 

56.37 3 162 Hepatopancreas Crab 

45.5 1 3085 WB Sea Catfish 

42.58 3299 WB White Sucker 

34.48 3163 Hepatopancreas Crab 

33.25 3086 WB Catfish 

Hylebos Waterway, Tacoma. WA 

Brazes 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-Dioxinshrans 

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 

P&Z Number Type of Fish Location 

123478 HxCDD 

(375 sites)* 37.6 3355 WB Carp 

14.3 3167 WP Bluegilt 

11.6 2304 WB Carp 

9.9 3092 WB Carp 

8.7 3444 WB Carp 

123678 HxCDD 

(375 sites) loo.9 

89.1 

50.8 

47.3 

41.9 

123789 HxCDD 

(375 sites) 24.8 

9.5 

8.5 

7.8 

6.8 

1234678 HpCDD 

(354 sites) 249.1 3355 WB Carp 

171.0 3377 WB Carp 

150.8 3444 WB Carp 

141.2 2290 WB Spotted Sucker 

138.1 3376 WB Carp 

2290 WB Spotted Sucker 

3355 WB Carp 

3185 WB Channel Catfish 

3377 WB Carp 

3376 WB Carp 

3355 WB Carp 

3185 WB Channel Catfish 

3167 WP Bluegill 

3377 WB Carp 

3098 WB White Sucker 

Old Mormon Slough, Stockton, CA 

Medlins Pond, Morrisviile, NC 

Alabama R., Claibome. AL 

Dugdemona R.. Hodge. LA 

Nonconnab Creek, Memphis, TN 

Savannah R., Augusta GA 

Old Mormon Slough, Stockton, CA 

Bernard Bayou, Gulfport MS 

Chauahoochee R., Franklin, GA 

Chattahoochee R., Whitesburg, GA 

Old Mormon Slough. Stockton, CA 

Bernard Bayou, Gulfport, MS 

Medlins Fond, Morrisville. NC 

Chattahoochee R., Franklin, GA 

Red Clay Cr., Ashland, DE 

Old Mormon Slough, Stockton, CA 

Chattahcochee R., Franklin, GA 

Nonconnab 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 
TABLE34 

Location of Maximum Measured HxCDF and HpCDF Concentrations in Fish Tissue 

Marhum 

c-tion Eptodt 

COUlpOWld P&l Number TypcorFkb LAXXtlOIl 

123478 HxCDF 

(379 sites)* 

123678 HxCDF 

(379 sites) 

123789 H.xCDF 

(377 sitar) 

234678HxCDF 

(379 sitea) 

1234678HpCDF 

(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 

257 

1.76 

1.26 

0.97 

0.91 

3162 

3297 

2410 

3299 

3162 

3301 

3297 

3355 

3150 

3112 

3107 

3206 

3167 

3185 

3167 

3185 

3355 

3377 

3377 

3376 

WB 

Blugill Mcdllns Pond. Morrisvilk, NC 

CbmdCdXl Bcmard Bayou, GulfpMt, MS 

spDttedsu&er - R., Augus@ GA 

ShorthaulRcdborsc James R., Glasgow, VA 

carp Da PIaims R., Ldqmt, IL 

Bluegill 

cllamclcatfish 

Hyltbos Waterway, Taama, WA 

Niagara R., Niagara Falls, NY 

Rouge R., River Rouge, Ml 

Niagara R.. N. Tonawan@ NY 

Bayou D’hde, Sulfur, IA 

Hylcbos Waterway, Tacoma, WA 

Braax R., Freeport, -IX 

Eighteen Mile Cr., Olcott, NY 

Niagara R., Niagara Falls, NY 

old hfolmon Slough, stockton, CA 

Brame R., Freeport, TX 

Otta R., BaAdwinvillc, MA 

Mississippi R., Little Falls, MN 

Wisamsin R, Eruhw, WI 

Willamettc R., Podand, OR 

Mcdlhs Pond, Morrisvilk, NC 

Bernard Bayou, Gulfport, MS 

Bayou D’hdc, Sulfur, LA 

Old Mormon Slough, Smckton, CA 

tZba- R., Franklin, GA 

old Momonslough, sto&tw, CA 

Willmdtc R., Portland, OR 

Brenvr R, Freqxxt, TX 

-R-F&GA 

Chattgboochct R., Whitcsburg, GA 

“Numbershownistotalnuahbaofsitcs. 

WB = whole-hlxly botmal-feeding amlpositc sampk. 

PF = prcdatm tilkt cmposite sampk. 

WP = whole-body prdator ampodb sample. 

38 
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); Super-fund 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 (INDAJRB); sites near industrial areas that include refineries with catalytic reforming 

operations (R/I); sites that could be intluenced by runoff from agricultural areas (AGRI); and sites 

near publicly owned treatment works (POTWs). The two broad categories, industry/urban and 

refineriesiother 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 statisticaI 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/fura.ns and other xenobiotics. Two categories (POTWs and agricultural areas) would not, 

as data on these sites confii. 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 anaiysis 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. 

Categorv 

Background 

USGS NASQAN 

Paper MilIs using Chlorine 

Other Types of Pulp and Paper Mills 

Wood Preserving Plants 

Refineries/Other Industries 

NPL (Super-fund Sites) 

Industry/Urban 

Agriculture 

Publicly Owned Treatment Works (POTW) 

Abbreviation 

B 34 

NSQ 40 

PPC 78 

PPNC 27 

WP 11 

Rn 20 

NPL 7 

INDAJRB 106 

AGRl 19 

POTW 11 

Number 

of Sites 

39 
Statistical Comparison Tests 

To compare observed concentrations between site categories, box and whisker plots were 

prepared for the terra- and penta-dioxins individually and for total hexa-dioxinsand 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 percentile. 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 

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 comparisons 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, 

Supetfund sites, industry/urban sites, or refineries/other industries. As would be expected, the box 

40 
300 

280 

2 3 260 

zi 5 240 

g 220 

.s 200 

E = 180 

8 E 160 

8 140 

120 

100 

Box Plots for Column X, 

hiist 10% 

of d&a 

- 75th pewoentile 

,-median 

I 

- 25th percentile 

IWWtloK 

ofdra 

. 

Column 

Figure 3-9. Example box plot with explanation of features. 

41 
125. 

0 so* P 

0 

25. 

8 I 

+ 

o* f- h1 ’ t I 

NSQ B PPC PPNC R/I NPL WP IND/lJRB POTW AGRI 

Summary Table for 2,3,7,8 TCDD Box Plot 

Site Category n 

Concentration 

Range 

PC&l 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 (WI) 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 

lndustriaVUrban 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 

Agricuftural (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-halt 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 ‘XCDD cmcumtims in fish tissue. 

42 
Mann-Whitney U ‘rest Results for Dioxins Furan Comparing Selected Scrurce Categories 

K ruskal- Wdlis 

INL)/UHI$H/I, 

All Groups NI’L, WC, 

Chemical Except NSQ YI’NC, WI’ 

2,3.7,8-‘KDD .oool .0(x)1 

2,3,7&TCDF .0001 .OOOl 

2,3,4,7,&PcCDF .oool BOO3 

I , 2 * 3 I 7 , 8-PeCDF 0001 .0352 

I ,2,3,7&PcCDD .oool .0871 

HxCDDs .OOol .34% 

HxCDFs a013 .49x1 

I-EC .OOOl .OOUl 

I’I’C’, I( 

.(WW)l 

.UJol 

.wol 

.OOOl 

.ux)1 

.oool 

.mO7 

.oool 

Mann-Whitney 

WC INLW I’I’C 

I’I’C, w 1’ WC, I’I’NC WC, WI I’I’C , NI’I A AtI5 POT W I’I’C, A<; 

.oool .ooOl .@I32 .O348 .0(X) I .ooo I mo1 

.wo t .oOUI .oool .053 1 .uxl1 .tnlo I .0001 

.ou4 mY9 mu I .353x .4OY6 .ooO2 .cml 

.0252 .0779 .3733 .5650 .2Y48 .0065 a005 

.0274 .I021 .48YO .YH09 .138Y ,022s .OO25 

.12YY .6Y76 .7377 .731 I 0493 .0()03 m44 

.7553 .1166 .2724 x479 .9612 .0220 .024Y 

.0003 .ocal .o400 .I692 .oool .ou)I .WOl 

Mann-Whitney 

Chemical WI’,R 

2,3,7&TCDD 

2,3,7,8-TCDF 

2 * 3 , 4 I 7 . LI-PeCDF 

12 9 9 3 7 I v 8-PeCDF 

12 , v 3 * 7 t 8-PeCDD 

HxCDDs 

HxCDFs 

TEC 

.096 1 .1567 .0132 .0515 .0102 

.1956 .002 1 .0118 St098 .Om2 

.1780 .I303 .ooo2 II032 .0053 

.3485 .2337 .0036 .0236 a077 

.7760 .2337 .02 19 .I473 .0846 

Ml7 .3424 .2477 .2976 .5406 

.I115 .53O2 .4090 .8919 .7808 

.I696 0974 .0287 .0774 .0215 

WI’, I’PNC WI’, WI1 WI’, NPI, 

WI’, I NW w I’, 

UHR POT W 

X365 .8878 

.4090 .I263 

.4328 .63Hl 

.283 I .4517 

.283 1 .9250 

.0265 .5885 

.I604 .2690 

.5633 .9250 

WI’, AC 

Valuer shown are ~wtxlai.l pmbabiiities that groups arc different. ‘lhe critical kvel was SCI at 0.05. If p~O.05, the catrgoncs weir: conskkrsd to Ik: signifiwntly difkrcnl 

INDKJRB = lnduslry a&or Urban NStJ = National ambient stnwn momloring nc~wotk. (‘lhis dcsign&on 15: indcpcndcnt 01 SOUICC calrgoncs.) 

AG = Agriculture WI’ = Wood presswing rclatcd aclivlties 

B = Ba&gKMd WC = Paper and pulp mills using chlonnc for blrachmg 

NPL = National priority List (Supcrfund SIIC) I’I’NC = Olhcr papxr and pulp nulls including dcrnking pldnls 

POIW = hblicly owned ‘l‘reulmznl works (sewage) 

WI = Refines UsirQ calalyllc reforming prwxss and other indurlry 

43 
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 other 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. 

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; refmery/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 Super-fund 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 confumed 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). 

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-ftuan fish contamination. 

44 
Summary Table for TEC Box Plot 

Site Category n 

Concentration 

Range 

w/g Mean Stan. Dev. Median 

NASQAN (NSQ) 

Background (B) 

Paper Mills Using Cl (PPC) 

Other Paper Mills (PPNC) 

Refinery/Other Industry(R/I) 

Superfund Sites (NPL) 

Wood Preservers (WP) 

;~riaUUrhan Sites (IND/URB) 

Agricutural (AGRI) 

40 ND- 7.18 1.12 1.87 0.16 

34 ND- 3.02 0.59 0.9 0.21 

78 0.4- 184.24 25.84 36.90 10.62 

27 ND- 28.9 5.70 7.50 2.39 

20 ND- 30.22 8.89 8.64 6.81 

7 0.13- 213.05 33.86 79.06 4.36 

11 0.01-24.64 4.34 8.36 0.43 

105 ND- 61.07 7.79 12.54 3.26 

8 0.03- 2.24 0.70 0.92 0.12 

17 ND- 4.44 1.02 1.19 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 ‘EC concentrations in fish tissue. 

45 
350 

300 

100 

!a 

cl 

0 

0 

0 

0 

0 

0 

0 

0 

8 

0 

0 

0 

0 

0 

* * 

NSQ B PPC PPNC RI NPL WP IND/URB POTW AGRI 

Summary Table for 2,3,7,8 TCDF Box Plot 

Site CategoN 

NASQAN (NSQ) 40 0.19 - 16.61 2.11 3.66 0.68 

Background (B) 34 0.10 - 13.73 1.61 2.51 0.90 

Paper Mills Using Cl (PFC) 78 0.26 - 320.69 39.20 66.18 14.04 

Other Paper Mills (PPNC) 27 0.25 - 55.75 6.42 10.72 3.61 

Refinery/Other Industry (WI) 20 0.24 - 23.36 3.62 5.16 1.91 

superfund sites (Nfx) 7 0.56 - 21.23 7.23 8.62 3.48 

wood Preservers (WP) 10 0.18 - 8.04 1.31 2.54 0.39 

IndustriaWrban Sites (IND/URB) 105 0.24 - 61.58 5.93 9.49 2.90 

POTW 8 0.24 - 2.00 0.94 0.72 0.79 

Agricuftural (AGRI) 17 0.19 - 19.28 2.21 4.52 0.84 

n 

Concentration 

Range 

Mean Stan. Dev. Median 

n = number of sites in category. Maximum value at eech site was used. One-half the d&&ion limit 

was used for values b&w detection. Sites were assigned to only one category. 

Figure 3-12. Box and whisker plot for 2,3,7,8 TCDF concentrations in fSsh tissue. 
30 

25 

a0 

b0’ 

cu: Y 10 

5 

0 

0 

0 n O 

0 

0 

0 

0 

0 

T 0 

8 

+ LIL I 0 

0 

+I + [;I 

1 

=$a 

NSQ a PPC PPNC R/I NPL WP IND/URB POTW AGRI 

Summary Table for 1,2,3,7,8 PeCDD Box Plot 

Concentration 

Site Category n 

Range 

P&J - Mean Stan. Dev. Median 

NASQAN (NSQ) 39 0.36-5.41 1.53 1.24 0.90 

Background (B) 33 0.15-2.67 0.77 0.54 0.54 

Paper Mills Using Cl (PPC) 78 0.25-12.48 2.37 2.72 1.52 

Other Paper Mills (PPNC) 27 0.45-12.38 2.22 3.19 0.68 

Refinery/Other fndustry (R/I) 20 0.46-16.80 3.28 4.17 1.35 

Superfund Sites (NPL) 7 0.46-l 2.62 3.01 4.34 1 .oo 

Wood Preservers (WP) 11 0.28-l 1.50 2.01 3.51 0.52 

IndustriaVUrban Sites (INDIURB) 105 0.20-27.56 2.32 3.93 1.09 

PQTW a 0.46-0.88 0.75 0.18 0.84 

Agricultural (AGRI) 17 0.46-3.54 0.92 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 
54.3 

t 

25. 

0 

0 

a 

0-J 

J&&a, s 4 

L 

NSQ B PPC PPNC RI NPl WP INDNRB POTW AGRI 

Summary Table for 1,2,3,7,8 P&OF l3ox Plot 

Site Cateqory 

NASQAN (NSQ) 

Background (8) 

Paper Mills Using Cl (PPC) 

Other Paper Mills (PPNC) 

Refinery/Other Industry (FUI) 

Superfund Sites (NPL) 

Wood Preservers (V/P) 

IndustrWUrban Sites (INDIURB) 

POTW 

Agricultural (AGRi) 

n 

40 

34 

78 

27 

20 

7 

1: 

a 

7 

Concentration 

tinge 

-- Mean Stan. Dev. Median 

0.16 - 1.69 0.48 0.33 0.39 

0.10 - 1.90 0.43 0.31 0.39 

0.30 - 9.08 1.43 1.88 0.58 

0.22 - 3.09 0.80 0.83 0.40 

0.38 - 4.47 1.18 1.07 0.66 

0.39 - 2.96 I.18 0.97 0.71 

0.39 - 1.3 0.51 0.28 0.39 

0.13 - 54.32 1.73 5.74 0.50 

0.16 - 0.51 0.38 0.10 0.38 

0.20 - 0.89 0.43 0.18 0.38 

n = number of sites in catqpry. Maximum value at each site was used. One-half the detedion 

limit was used for values below detection. Sites were awigned to onty one categoty, 

Figure 3-14. Box and whisker plot for 1,2,3,7,8 PeCDF concentrations on fish tissue. 
0 

0 

0 

8 

8 + * .w 

* 

r 

NSQ 8 PPC PPNC RI NPL WP lNDAJRB POTW AGRI 

Summary Table for 2,3,4,7,8 PeCDF Box Pbt 

Site Cateoorv n Mean Stan. Dev. Median 

NASQAN (NSQ) 40 0.16 - 4.11 0.78 0.79 0.46 

Background (B) 34 0.10 - 1.39 0.50 0.36 0.42 

Paper Mills Using Cl (PPC) 70 0.25 - 20.14 2.92 4.04 t -37 

Other Paper Mills (PPNC) 27 0.40 - 10.21 1.71 2.55 0.59 

Refinery/Other Industty (WI) 20 0.42 - 33.25 5.44 7.86 2.32 

Superfund Sites (NPL) 7 0.48 - 7.53 2.93 2.37 2.73 

Wood Preservers @VP) 10 0.42 - 1.43 0.63 0.40 0.42 

IndustviaMltin Sites (INDIURB) 104 0.13 - 45.51 4.09 8.27 0.98 

POTW a 0.16 - 0.59 0.42 0.13 0.44 

Agricukural (AGAI) 17 0.15 - t.02 0.53 0.26 0.42 

Concentration 

Range 

n = number of sites in category. Maximum value at each site was used. OnMaW the detectbn 

limit was used for values below detection. 

Figure 3-15. Box and whisker plot for 2,3,4,7,8 PtCDF concentrations in fish tissue. 

49 
0 

0 

0 

0 

0 

0 

7 0 P 

0 f I 

NSO B PPC PPNC R/I NPL WP INDNRB POTW AGRI 

0 

0 

Summary Table for Total HxCDDs Box Plot 

Site Category 

NASQAN (NSQ) 

Background (6) 

Paper Mills Using Cl (PPC) 

Other Paper Mills (PPNC) 

Refinery/Other Industry(R/I) 

Superfund Sites (NPL) 

Wood Preservers (WP) 

Industrial/Urban Sites (INDIURB) 

POTW 

Agricultural (AGRI) 

n 

37 

30 

78 

27 

20 

7 

11 

100 

7 

17 

Concentration 

Range 

Ps/e - 

Mean 

ND -13.91 1.73 

ND - 3.57 0.39 

ND - 42.98 4.68 

ND - 63.35 9.23 

ND - 35.17 5.54 

ND - 9.07 2.96 

ND -60.10 7.04 

ND - 28.4 3.60 

ND ND 

ND - 13.79 1.63 

Stan. Dev. Median 

2.94 0.51 

0.80 NO 

6.66 3.19 

16.77 1.25 

9.75 1.97 

2.99 1.94 

17.90 0.71 

5.49 1.14 

ND ND 

3.38 0.44 

n = number of kites 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 corrc~ntrhms in fish tissue. 
60 

50 

40 

30 

20 

10 

0 

0 

0 

0 

0 0 

0 

0 

0 

0 

T 0 

0 

1 

0 

T T 

0 

8 s 0 T 8 I 

8 

A A 7 $ ,'I L 

0 

J 4 4 f , 

NSQ B PPC PPNC R/l NPL WP IND/URB POTVV AGRI 

Summary Table for Total HxCDFs Box Plot 

Concentration 

Site Cateooty 

Range 

nw/s- Mean Stan. Dev. Median 

NASQAN (NSQ) 39 ND - 5.11 0.58 1.21 ND 

Background (6) 29 ND - 2.59 0.22 0.66 ND 

Paper Mills Using Cl (PPC) 78 ND - 16.75 1.74 3.11 0.34 

Other Paper Mills (PPNC) 27 ND - 12.93 1.94 4.16 ND 

Refinery/Other Industry(R/I) 20 ND - 22.46 3.69 5.76 1 .Q5 

Superfund Sites (NPL) 7 ND - 6.08 1.22 2.22 0.41 

Wood Preservers (WP) 11 ND - 40.1 4.42 11.92 ND 

Industrial/Urban Sites (INOIURB) 103 ND - 51.76 3.67 9.49 0.48 

POTW a ND -0.35 0.04 0.12 ND 

Agricuttural (AGRI) 17 ND - 3.01 0.31 0.78 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 infish tkw. 

51 
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: 

53 
TABLE 4-1 

summary of Xenobiotic Compounds in Fish Tissue 

In cases where multiple samples were analyzed per site, the value used represents the highest concentration. 

54 
p,p DDE 

I3 iphenyl 

MeCUi-y 

Total PCBs 

Nonachlor, trans 

L. n Pentachloroanisole 

5 Chlordane, cis 

P A Chlordane, trans 

. Dieldrin 

E 3 

Alpha-BHC 

3 124 Trichlorobenzene 

s HCB 

s I23 Trichlorobenzene 

p 

Gamma-BHC 

MiRX 

5 Nonachlor, cis 

8. 

E. 

Oxychlordane 

Chlorpyrifos 

g 

Pentachlorobenzene 

B Heptachlor Epoxide 

2 Dicofol 

e 

e 

1234 Tetrachlorobenzene 

a 

Trifluralin 

E ‘. 35 Trichlorobenzene 

L. 3 Endrin 

t?, 

9 

12 3 5 Tetrachlorobenzene 

5 Octachlorostyrene 

2 1245 Tetrachlorobenzene 

” Methoxychlor 

Isopropalin 

Ni trofen 

Hexachlorobutadiene 

Heptachlor 

Perthane 

PCNB 

Diphenyl Disulfide 

Percent of Sites with Detected Leve IS 

s 

55 
More than 50 Percent 

of the Sites 

Total PCBs 

Biphenyl 

Mercury 

Pentachloroanisole 

1,2,3 Trichlorobenzene 

Pesticides: 

DDE 

uans-Nonachlor 

cis-Chlordane 

trans-Chlordane 

Dieldrin 

alpha-BHC’ 

10 to 50 Percent 

of the Sites 

Hexachlorobenzene 

I ,2,3 Trichlorobenzene 

Pentachlorobenzene 

1,2.3,4 Teuachlorobenzene 

1.3.5 Trichlorobenzene 

Pesticides/Herbicides: 

gamma-BHC1 

Mirex 

cis-Nonachlor 

Oxychlordane 

Chlorpyrifos 

Heptachlor Epoxide 

Trifluralin 

Dicofol 

Endrin 

Less Than 10 Percent 

of the Sites 

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 

rig/g,, respectively (Table 4- 1). These two compounds were aiso detected at over 90 percent of the 

sampled sites. Mean concentrations of trans-nonachior and dieldrin were the next highest at 3 1 and 

28 rig/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/g). 

As previously discussed in Chapter 3 for dioxins/fura.ns, 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. 

’ Alpha-BHC and gamma-BHC (or Lindaa) arc focmally known as a-hcxachlorocyclobexane and 

y-bexachlorocyclobex, respectively. The former chemical dcsignatiorrs arc used in this document. 
Number 

Category 

Background 

USGS NASQAN 

Paper Mills using Chlorine 

Other types of Pulp and Paper Mills 

Wood Preserving Plants 

Refineries/Other Industries 

NPL (Superfund Sites) 

Industry/Urban 

Agriculture 

POTW 

Abbreviation 

Number 

of Sites 

B 22 

NSQ 40 

PPC 42 

PPNC 17 

WP 11 

Rn 5 

NPL 6 

INDfuRB 35 

AGRI 19 

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 rig/g (Figure 4-2a). Twenty-six percent of the sites had fish tissue concentrations greater 

than 1000 rig/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/seepage from disposal sites containing PCBcontaminated 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 pentachlorobiphenyl (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 Arocior 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: 

2 Four chemicals found at less than 50 percent of the sites am presented in this section to facilitate their discussion. 

These are gamma-BHC; 1.2.3 trichlorobcnzene; cis-nonachlor; and oxychlordane. 
Total PCES 

8 

4 

wm1 

,__._.__..... ---.. - . . . - -..-..-._............. 

H7 / 

2-m 

. . . . ..t..-. -... 

, 

‘mm t 

TOTAL PC6 (tlg@): 

mm .looo 2r 

A I >&26Io1ooo 62 

O- Ota62s 12 

‘Pm d $688 in c8tqoty cumul8tiuo 

u 

TomI Sitw: 374 

mwoniy sit88: 26 

Maximum ~88 WhoIf 0ody: 7 

Figure 4-z. TotalPCBsza)cum~vcfraquencydirtributionradb)ampof~ 

distribution of various cmcaitmtim mqu in tisb thaw. 
TABLE 4-2 

Summary of PCBs in Fish Tissue 

Total Dichbrobiphenyl 30.7 5072 21.43 267.74 ND 362 

Total Monochbrobiphqi 13.6 235 1.22 12.56 ND 362 

Total Lkachbrcb@henyi 3.3 29.5 0.44 3.06 NO 362 

Total Nonachbrubiphenyi 9.7 413 3.04 25 ND 362 

Total PCBs 91 .4 1897.66 7557.6 206.76 362 

‘COrwxtk~bflS are nanograms per gram (rig/g) or parts per bikn ( ppb) by wet weight. In ~8~8s tire multiple Samples were analyzed per St@, the value US& represents the 

htghesl concentration. 
PCBs 

Episode 

ber Type of Fish LQC&QIl 

124192 3259 WI3 Sucker 

29130 2429 mcarp 

25240 3134 WB Sucker 

24118 3182 wcarp 

23809 3142 wcarp 

Hudson R., Fort Miller, NY 

Fox R., Depere Dam, WI 

Manitowoc R., Chilton, WI 

Mud R., Russellville, KY 

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 rig/g for Superfund sites and 

349 rig/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 rig/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: 
6 oool 0 

4 A 0 

2000 

0 0 t 

0 

0 - v 

NSQ B PPC PPNC RI NPL WF’ INDNRB POTW AGRI 

Summary Table for Total PCBs Box Plot 

Site Cateoorv 

NASQAN (NSQ) 

Background (B) 

Paper Mills Using Cl (PPC) 

Other Paper Mills (PPNC) 

Refinery/Other Industry (R/I) 

Supetfund Sites (NPL) 

Wood Preservers (WP) 

IndustrMUrtm Sites (INDIURB) 

POTW 

Agricuttural (AGRI) 

n - 

39 

20 

39 

17 

5 

6 

10 

31 

6 

15 

Concentration 

Range 

Dda Mean Stan. Dev. Median 

ND - 7977 449.1 1408.9 24.8 

ND-460 46.9 106.7 ND 

ND - 17723 1247.0 3147.5 293.2 

ND-6061 1225.1 1739.5 483.7 

ND - 2974 833.5 1230.5 349.3 

2.51 - 1075 491 .o 390.5 525.2 

ND-1804 260.6 561.4 38.6 

2.54 - 12027 1277.9 2374.9 213.2 

ND - 1677 302.4 674.3 22.2 

ND-1064 97.4 274.1 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. 
TABLE 4.3 

Results of Statistical Tests for Selected Xenobiotics and Mercury 

Kruskal-Wallis 

All Groupa Au Groups 

Excepi NPL, 

NSQ, B IN0 

Excepi 

Chemical NSQ 

Pentachloobenzene .7614 

1,2,3,4-T8trachlorob8nz8ne.6567 

1,3,5-Trichlorob8nr8ne .9600 

Total PCBs .a301 

Biphenyl .6338 

Mercury .O222 

1.2,4-Trichloroben28n8 .0645 

Hexachlorobenr8n8 0970 

f.2,3-TtiChkXCb8IlZ8n8 .3530 

Pentachloranlsole XI473 

PPC. 

IND 

.6393 II529 .1954 

.7660 .7417 .6672 

.9283 .9160 .3206 

.0012 .6368 .3646 

.a390 .7417 .6685 

.0203 .3706 .5909 

.0550 9016 .0228 

.1176 .4636 .0164 

.2611 .3127 .4214 

.1979 .6356 .4079 

Kruskal-Wallis 

PPC, PPNC WP, WP, 

PPNC, 

IN0 

WP, 

IND 

.6821 -2246 

.3214 .9516 

.8866 .3624 

.9914 .0099 

II716 .3164 

.8297 .0177 

.7676 .0709 

.1996 .0210 

.OSll .4036 

.1036 .2466 

PPC, 

B, 

IND 

AG, 

IND 

POW, 

IND 

.1995 .4121 3227 

.7723 .5980 .7106 

.5243 .2917 .4583 

.OOOl .OOol .0210 

.oa42 .2275 .5640 

.0489 .0975 0017 

.1590 .2759 7262 

.0167 .4968 .0560 

.8094 3697 .2840 

.0613 .2321 .7262 

Mann-Whitney 

POTW, POTW, POTW, 

RI, 

RI,B AG 

WI, 

POTW 

R/l 

IND 

.2066 .2949 .2733 .4368 

.2923 .1904 .2733 .2254 

.6636 .5127 .5839 .9816 

.0324 .0667 .2012 .9453 

.945&J .0273 .6461 .2723 

.6256 .5705 .0828 .0470 

.2623 .3627 .7150 .8369 

.0632 .4561 .I207 .a014 

.6836 .7600 .2733 .7837 

.1968 .2752 .8551 .6974 

POTW, 

PPNC PPNC PPC NPL WI WP 

-.___ .- _-.___ ~__--. -__- ____ 

- - - - - - 

Chemical 

Total PCE3s 

WI,NPL,IND 

3058 

PPC 

- 

Pentach!oranisole - -1181 .0350 .2256 - - - - 

Mercury - - - - .0158 .1093 .0828 .0562 

Values shown are two-tail probabilities that groups al8 different. The critical level was set at 0.05. If ~~0.05, the categories were considered to be significantly diffef8nl 

INDAJRB = Industry and/or Urban NSQ = National ambient slream quality monitoring network. (Thts designation IS 

AG = Agdculture independent of source categories.) 

I 

EPL = 

Background WP = Wood preserving related activities 

National Priority List (Supertund site) PPC = Paper and pulp miHs using chlorine for bleaching 

POTW = Pubtlcty Owned Treatment Works (sewage) PPNC = Other paper and pulp mills including deinking plants 

Ftn = Refineries using catalytic reforming process and Other industry 

62 
I a) Biphenyl 

0 20 40 00 

Percentile of Sites 

00 100 

Biphenyl (ng/g): 

n = >50 

A - > 2.5 to50 

09 0 to 2.5 

1’ 

11 

88 

*Percent of sites in category 

Total Sites: 362 

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 

Cont. Episode 

131.7 2654 

75.6 3042 

70.6 3403 

70.2 3038 

53.8 3115 

WB Carp Toms River, NI 

WB Carp Missouri R., Omaha, NE 

WB River Carpsucker Holston R.. S. Fork, Kingsport, TN 

WB Carp Des Moines R., Des Moines, IA 

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 rig/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 rig/g.. A Kmskal-Wallis test for a.lI 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 contaminated sediment ingested during feeding), and other variables. 

The measured concentrations ranged up to 1.77 @g with 2 percent of the sites greater than 

1 pg/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: 
NSQ B PPC PPNC WI NPL WP INDRJRB POTW AGRI 

Summary Table for Blphenyl Box Plot 

Site Category 

NASQAN (NSQ) 

Background (8) 

Paper Mills Using Cl (PPC) 

Other Paper Mills (PPNC) 

Refineries/Other Industry (R/I) 

Superfund Sites (NPL) 

Wood Preservers (WP) 

Industrialllltian Sites (lND/URB) 

POTW 

Agricultural (AGRI) 

n 

39 ND-75.6 2.51 

20 ND-l .04 0.42 

39 ND-70.6 3.18 

17 ND-3.35 0.87 

5 ND-O.98 0.44 

6 ND-2.7 0.97 

10 ND-l .5 0.60 

31 ND-32.8 2.56 

6 0.1 -0.79 0.55 

15 ND-l .ll 0.48 

n = number of sites in category. ND’s set at 0. 

Maximum concentratbns at sites were used. 

Concentration 

Range 

WQ Mean Stan. Dev. Median 

12.04 0.49 

0.30 0.38 

11.36 0.54 

0.87 0.61 

0.40 0.43 

1.09 0.76 

0.60 0.45 

6.38 0.68 

0.24 0.63 

0.31 0.53 

Figure 4-5. Box and whisker plot for biphenyl in fish tissue. 
a) MERCURY 

A = z 0.5 to 1 

0 - 0.5 

- 

13 

85 

Total Sites : 374 

Fillat fhlv 

. . ..-- -“‘I Sites: 128 

‘Percent of sites in category cumulative Maximum was Whole Body: 15 

Figure 4-6. Mercury: a) cumulative fkapcncy distribution and b) map of geographical 

distribution of various concentration ranges in fish tissue. 

64 
Mercury 

Cont. Episode 

Drnl Number Type of SW Location 

1.77 2397 PF Walleye 

1.66 3259 PF Lm Bass 

1.63 2027 PF Lm Bass 

1.40 3122 mcatp 

1.13 2290 PF Lm Bass 

Wise. R/Boom Bay, Rhinelander, WI 

Hudson R., Fort Miller, NY 

Kiamichi R., Big Cedar, OK 

Menominee R., Quinnesac, MI 

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 pg/g) was for 

POTWs (Figure 4-7). The remaining median values had a relatively small range with the lowest 

being background at 0.09 ug/g and the highest being refinery/other industry at 0.24 l.tg/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 rig/g (Figure 4-8a). The majority of the higher concentration 

sites (greater than 2.5 q/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 
7 

0 

0 

0 

0 

0 0 0 0 

.6 I\ I .4 

-lr .ZJ Iy_J$-yy~. 1 0 

0 

ONSQ 8 PPC PPNC R/I NPL WP INO/URB POTW AGRI 

j o T 1 T ‘BT 

Summary Table for Mercury Box Plot 

Concentration 

Site Catewnr 

NASQAN (NSQ) 

Background (H) 

Paper Mills Using Cl (PPC) 

Other Paper Mills (PPNC) 

Refinery/Other Industry (R/I) 

Superfund Sites (NPL) 

Wood Preservers (WP) 

IndustriaVUrban Sites (INDIURB) 

POTW 

Agricultural (AGRI) 

n 

Range 

Me - 

Mean Stan. Dev. Median 

39 

21 

40 

17 

5 

6 

ii 

6 

15 

ND - 0.98 0.29 0.25 0.23 

ND- 1.77 0.34 0.40 0.16 

ND- 1.4 0.26 0.33 0.12 

ND - 0.46 0.16 0.15 0.09 

0.08 - 0.49 0.29 0.16 0.24 

ND - 0.89 0.28 0.32 0.22 

0.06 - 0.68 0.31 0.24 0.21 

ND - 0.72 0.15 0.14 0.12 

0.12 - 0.98 0.59 0.30 0.61 

ND - 0.82 0.27 0.24 0.17 

n = number of sites in category. ND’s set at 0. 

Maxinum concentrations at sites were used. 

Figure 4-7. Box and whisker plot for mercury in fish tissue. 

68 

Pentachloroanisole 

Episode 

. . ot Frsh 

647 3375 WB Carp Chattahoochee R.. Austell. GA 

570 3185 WB Channel Catfish Bernard Bayou, Gulfport. MS 

334 3376 WB Carp Chattahoochee R., Whitesburg, GA 

240 2618 WB Quill back Hamilton Canal, Hamilton. OH 

187 3377 WB Carp 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 

rig/g for nonchlorine paper milts (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 L2.4 Trichlorobenzene 

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 concentrations, however, were low (below detection for 1.2.3 TCB and 0.14 rig/g for 1,2,4 TCB) (Figure 4- 

10a.b). The two compounds are used in a variety of industrial applications including l-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 rig/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: 

1,293 TCB 

Cont. Episode 

NW Tvpe of Fish 

69.0 2056 WB Carp Ohio R., West Point, KY 

54.9 3097 PF Brown Bullhead Red Lion Cr., Tybouts Comer, DE 

30.2 3164 WB Carp Haw R., Saxapahaw, NC 

26.8 3376 WB Carp Chattahoochee R., Whitesburg, GA 

24.8 2341 WB Carpsucker Ohio R.. Markland, KY 

70 
25. o 

0 

8 , 

T 0 

0,' I 

+ r a-, , t I f 

NSQ 8 PPC PPNC R/I NPL WP IND/URB POTW AGRI 

Summary Table for Pentachloroanisole Box Plot 

Site Category n 

Concentration 

Range 

wg Mean Stan. Dev. Median 

NASQAN (NSQ) 39 ND - 46.8 3.75 a.43 0.33 

Background (B) 20 ND - 3.33 0.59 1.14 ND 

Paper Mills Using Cl (PPC) 39 ND - 85.1 5.46 14.32 0.77 

Other Paper Mills (PPNC) 17 ND - 334 33.10 89.53 1.67 

Refinery/Other Industry (R/I) 5 ND - 13.2 4.21 5.97 0.32 

Superfund Sites (NPL) 6 ND - 2.99 1 .oo 1.39 0.22 

Wood Preservers (WP) 10 ND - 4.47 0.86 1.46 ND 

IndustriaVUrban Sites (INDIURB) 31 ND -13 2.44 3.88 0.42 

POTW 6 ND - 24.20 4.42 9.72 0.16 

Agricuftural (AGRI) 15 ND - 7.31 1.18 2.34 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. 
- r a) 123 Trichlarobenzene l ! i 

4 5 

Peraontlb of Sites 

I W 124 Trichlorobenzene 

% 

: 

. 

s ‘- ; 

E I ’ 

4 -- 

/. 

8 ..1---..,I_ 

1 7-w 

‘0 

a . , . . . . . . . . 

a0 40 0 m 1m 

Percmtib of Sites 

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 

Cont. Episode 

Number . . Tvpe ot Ftsh l,oc&n 

264.8 2654 WB Carp Toms R., NJ 

191 2056 WB Carp Ohio R., West Point, KY 

104 2290 WB Spotted Sucker Savannah R., Augusta, GA 

103.8 3097 PF Brown Bullhead Red Lion Cr., Tybouts Comer, DE 

80.4 3411 WE3 Redhorse Sucker 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 Super-fund sites with chlorobenzene contamination (3 18 1.3097.2654). 

Two sites are near paper mills (3376.2290). one is near achemical 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 Super-fund 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 rig/g from nonchlorine paper mills and for 1.2,4 

TCB is 3.2 ngg for sites in the industrial/urban category (Figures 4- 12 and 4- 13). 

Pesticides/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: 

p,p’ -DDE 

Cont. Episode 

r Tvoe of Fish Lo&on 

14028 3315 WB Carp 

8708 3282 WB Carp 

3221 3084 WB Channel Catfish 

3214 3212 WB Carp 

2493 323 1 WB Carp 

Union Canal, Lebanon, PA 

Alamo R., Cahpatria, CA 

Arroyo Colorado, Harlingen, TX 

Owyhee R., Owyhee, OR 

Yakima R., Richland, WA 

73 

5 l 

0 

0 

l 

t, 

t 0 

et I t 1 

NSQ 8 PPC PPNC RI NPC VVP INDNRB POTW AGRI 

Summary Table for l-2,3-Trichbrobenzene Box Plot 

Site Catewrv n 

NASQAN (NSQ) 39 

Background (6) 20 

Paper Mills Using Cl (PPC) 39 

Other Paper Mills (PPNC) 17 

Refinery/Other Industry (R/I) 5 

Superfund Sites (NPL) 6 

Wood Preservers (WP) 10 

IndustriaVUrban Sites (IND/URB) 31 

POTW 6 

Agricultural (AGRI) 15 

Concentration 

Range 

-- Mean Stan. Dew. Median 

ND - 2.6 0.39 0.67 ND 

ND - 0.69 0.14 0.22 ND 

ND - 3.92 0.42 0.96 ND 

ND - 26.8 2.25 6.46 0.16 

ND - 0.51 0.10 0.23 ND 

ND - 5.34 1.13 2.11 0.16 

ND - 0.29 0.03 0.09 ND 

ND - 4.77 0.43 1.12 ND 

ND - 2.60 0.63 1.05 0.51 

ND - 1.71 0.21 0.45 ND 

n = number of sites in categgr. ND’s set at 0. Maximum concentratbns at sites were used. 

Figure 4-12. Box and whisker plot for 1,2,3 tricholorbenzene in 6sh tissue. 
80.4 

t 

0 

0 

0 0 

0 

f&l 

T 

* 

0-l I ' r I ' 

7 I 1 

t 

a 8 c 

NSQ B PPC PPNC Al NPl. WP IND/lJRB POTW AGRI 

Summary Table for 1,2,4-Trichlorobenzene Box Plot 

Site Cateqorv 

Concentration 

Range 

n -- Mean Stan. Dev. Median 

NASQAN (NSQ) 39 

Background (8) 20 

Paper Mills Using Cl (PPC) 39 

Other Paper Mills (PPNC) 17 

Refinery/Other Industry (WI) 5 

Supetfund Sites (NPL) 6 

Wood Preservers (WP) 10 

IndustriaVUrban Sites (IND/URB) 31 

POTW 6 

Agricuttural (AGAI) 15 

ND - 1.97 0.36 

ND - 0.47 0.17 

ND - 7.58 0.33 

ND - 16.1 1.44 

ND-l.36 0.44 

ND - 3.12 0.70 

ND - 0.42 0.07 

ND - 80.4 3.24 

ND - 1.97 0.64 

ND - 2.46 0.26 

0.55 ND 

0.19 0.08 

1.26 ND 

3.86 0.24 

0.56 0.22 

1.23 0.12 

0.14 ND 

14.36 0.20 

0.73 0.54 

0.62 0.09 

n = number of sites in category. ND’s set at 0. Maximum concentrations at sites were usd. 

Figure 4-13. Box and whisker plot for 1,2,4 trichlorobenzene in fish tissue. 

76 
1 

: a) P,P DDE 

b) 

c. 

0 20 40 60 a0 100 

Percentile of Sites 

r 

mA 

: 

. 

DDE (rig/g): 

m - >320 

A = > 2.5to 320 

O- 0 to 2.5 

*Percent of sites in category 

362 

. 

Fillet Only Sites: 29 

Maximum was Fillet: 8 YJ s 

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 Super-fund 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 rig/g for agricultural areas. Kruskal-Wallis tests (Table 4-3) comparing 

agricultural sites with Super-fund 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 (&U-IS 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 bioaccumulation, while oxychlordane has a lower potential. The total chlordane and total nonachlor concentra; 

tions were compared for the same sample and found to be$orrelated based on a linear function (Y 

= 0.7) but not as strongly as cis- versus trans-chlordane (f = 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 nonachlor. 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 rig/g)) also 

have a high level of chiordane. 

The maximum concentrations at the top five sites for each of these compounds were detected 

near industrial areas and Super-fund sites (Table 4-S). 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 concentrations 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). Super-fund 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 Super-fund sites and industry/urban areas (Figure 4-19). For total nonachlor 

78 
Summary Table for p,p’DDE Box Plot 

14028 

t 

Site Cateoorv 

Concentration 

Range 

n w/s - Mean Stan. Oev. Median 

NASQAN (NSQ) 39 

Background (6) 20 

Paper Mills Using Cl (PPC) 39 

Other Paper Mills (PPNC) 17 

Refinery/Other industry (WI) 5 

Superfund Sites (NPL) 6 

Wood Preservers (WP) 10 

Industrial/Urban Sites (IND/URB) 31 

POTW 6 

Agricultural (AGRI) 15 

1.09 - 1223 136.18 226.21 46.90 

ND-384 56.28 93.42 11.66 

1 .o - 895 87.27 167.67 22.20 

0.9 - 1157 161.94 306.58 42.50 

5.9 - 2329 506.07 1000.14 41.50 

1.5 - 805 200.17 300.35 97.95 

1.65 - 91.5 33.13 32.7 t6.85 

7.23 - 14028 602.34 2499.49 78.80 

2.49 - 516 98.16 204.84 17.40 

13.1 - 8708 1526.89 2313.13 201 .oo 

n = number of sites in category. ND’s set at 0. Maximum concentrations at sites were used. 

Figure Q-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) 

Kruskal-Wllis Mann-Whitney 

Chemical 

All Groups 

Except NSQ 

IndNRB B,PPC,PPNC AG 

NPL, AG WP,POTW IND, URB AG, NPL AG, B INO, B 

Total Nonachlor 

Trifluralin 

Mirex 

Heptachlor Epoxide 

Dieldtin 

Endrin 

Chlcrpyrifos 

Alpha-BHC 

lsopropalin 

Total C hlordane 

P>P’ DDE 

Gamma BHC 

Dicofol 

Oxychiordane 

.0071 .7565 .1946 .5346 .5593 .0113 .0013 

.4822 .1363 .9870 .0809 .1021 .0956 .8926 

.6451 .8643 .3180 6477 .6128 .4334 .7212 

.9599 .7704 .9899 .6144 .8153 .8415 .7576 

.0891 .6856 .4053 .5269 .4835 .3861 .0176 

.8983 .5777 .7063 .6732 .5858 .8415 .8020 

.4019 .5426 .4757 .6990 .4835 .5938 .2242 

.0905 .4388 .I437 .3989 .2129 .1880 .0087 

.9951 .7358 .9920 .4821 1 .ooo 1 .ooo .4403 

.004? .6774 .2289 6144 .3115 .0164 .0036 

.OOOl .I074 .5430 .0403 .1857 .0002 .0017 

.0417 .3614 .0184 .2657 .6404 .1615 .0056 

.6233 .2085 .8068 .0893 .2429 .2861 .4635 

.2994 .7081 .9567 .4748 1 .ooo .6892 .1708 

V&a8 bhown ate two-tail probabilii~es that groups are different The crltical level was set at 0 05. If p<O.OS, the categories were considered to be stgnificantly different. 

INDlURB = Industry and/or uban 

AG 

B 5 Agricukurc Background 

NPL = National Priorlty hst (Superfund sate) 

POTW = Publicly Owned Treatment Works (sewage) 

R/l = Refines using catalytic reforming process and 

other industry 

NSQ = Natmnal Ambient Stream Quahty monitormg network. (This desrgnation IS independen( 

of source categones.) 

WP = Wobd preservmg related activhes 

PPC = Paper and pulp mills using cthrine for bleachng 

PPNC = Other paper and pulp mills incluhg demklng plants 
a) Total-CHLOROANE ’ 

Wh prcanab 

d 

! 

. 362siln 

. 

__.__,__.__(__._,_,,..~.,........ (_....._..._..........,...................... 

20 40 60 80 11 

Percentile of Sites 

I 

4 Vans-CHLORDANE 

; 

‘+ 20 . . . . . .._..._....................._..........” . . . . . . . ..-............ 

0 Y) 60 00 100 

Percentile of Sites 

b) cis-CHLORDANE , 

/ 

1 

. 

b 362sh8 

. 

1 . . . , . 

0 20 ra 60 'G '- lie 

Percentile of Sites 

1 

d) Oxychlordane 

mm- . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..~...... 

1, : 

. 

. 

0 10 40 m m IQ0 

Percontib of Sites 

Figure 4-16. Cumulative frequency distribution of a) total chlorda~~e, b) cis-chlordane, c) 

trans-chlordane and d) oxychlordane. (Maximum awcentration at each site was 

used. The bar along the x-axis indicated values below the detection.) 

31 
Vans-NONACHLOR 

1. ,-._._ ._._.-........-.-._.- - . . ..*.........v...................., . . . . . . . . .._. 1 

0 20 Y) 60 80 100 

Percentile of Sites 

1 

% 

a 

Z 

B 

s 

OoDT,, cis-NONACHLOR ! 

looI 

90U1 pranM0 

I7 ; y9w

0 20 40 60 '30 100 

Pefcemie of Sites 

Total-NONACHLOR 

0 20 a 60 0 100 

Percentile of Sites 

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): 

n = >lOO 

A = >2.5to100 

01 oto 1 

‘Percent of sties in category 

Total Sites: 362 i 

Fillet Only Sites: 29 J . 

Maximum was Fillet: 15 

Total Nonachlor (ng/g): 

n - z-100 

A - >2.5to100 

O- 0 to 2.5 

‘Percent of sites in category 

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-S 

Sites With Highest Concentrations Of 

Chlordane Related Compounds 

Maximum 

Concentration Episode 

Chemical nn/a Number lbe of Fish Location 

Total Chiordane 

688 

384 

379 

376 

369 

cis-Chlordane 

378 

200 

1% 

185 

179 

trans-Chlordane 

310 

206 

191 

188 

182 

Oxychlordane 

243 

%.2 

91.4 

87.2 

77 

Total Nonachlor 

601 

521 

477 

340.9 

299 

cis-Nonachior 

127 

124 

123 

83.2 

65.7 

trans-Nonachlor 

477 

398 

350 

279 

242 

2215 

3045 

3435 

3376 

WB carp Monongahela, Clairton, PA 

WB carp Missouri R., Kansas City, MO 

WB Bigmouth Buffalo Mississippi R., Natchez, MS 

WB carp Chattahoochee R., Whitesburg, GA 

WB carp Mississippi R., West Alton, MO 

2215 WB carp Monongahela R., Clairton, PA 

3048 WB carp Mississippi R., West Alton, MO 

3045 WB carp Missouri R., Kansas City, MO 

3376 WB carp Chattahoochee R., Whitesburg, GA 

2383 WB carp Des Plaines R., Lockport, IL 

2215 WB carp Monongahela R., Clairton, PA 

3435 WE Bigmouth BuffaIo Mississippi R., Natchez, MS 

3376 WB carp Chattahoochee R., Whitesburg, GA 

3045 W-B carp Missouri R., Kansas City, MO 

2190 WB Carp Nishnabotna R., Hamburg, IA 

2427 WB carp Peshtigo R. Harbor, Peshtigo, WI 

2618 WCarp Hamilton Canal, Hamilton, OH 

2215 WB carp Monongahela R., Clairton, PA 

3117 PF Lake Trout Lake Michigan, Waukegan, IL 

2439 WB Carp Great Miami R., New Baltimore, OH 

2215 WB Carp Monongahela R., Clairton, PA 

3377 WB Carp Chattahoochee R., FrankJin, GA 

3117 PF Lake Trout Lake Michigan, Waukegan, IL 

2394 WB carp Great Miami R., Franklin, OH 

3181 W-B carp Ohio R., West Point, KY 

3117 

2215 

3377 

3285 

2383 

2215 

3377 

3117 

2394 

3181 

PF Lake Trout Lake Michigan, Waukegan, IL 

WI3 carp Monongahela R., Clairton, PA 

WB carp Chattahoochee R., Fra&lin,GA 

Stingray Colorado Lagoon, Long Beach, CA 

WB carp Des Moines R., Lockport, IL 

WCarp Monongahela R., Clairton, PA 

WB carp Chattahoochee R., Franklin, GA 

PF Lake Trout Lake Michigan, Waukegan., IL 

wcarp Great Miami R., Fra&in, OH 

WB Carp Ohio R., West Point, KY 

Total number of sites for each chemical was 362. 

&a 
I - 1_1 

NSQ B PPC PPNC RI NPL WP INDNRB POTW AGRI 

0 0 

0 

0 

T t 

Summary Table for Total Chlordane 60x Plot 

Site Cateqow 

NASQAN (NSQ) 

Background (6) 

Paper Mills Using Cl (PPC) 

Other Paper Mills (PPNC) 

Refinery/Other lndustty (WI) 

Superfund Sites (NPL) 

Wood Preservers (WP) 

IndustriallUrban Sites (INDIURB) 

POlw 

Agricuttural (AGRI) 

n - 

39 

20 

39 

17 

5 

6 

10 

31 

6 

15 

Concentration 

Range 

w/a Mean Stan. Dev. Median 

ND - 251.7 31.60 

ND - 36.3 5.20 

ND - 379 20.54 

ND - 376 46.73 

ND - 131.5 35.45 

ND - 76.60 23.25 

ND - 14.23 3.0 

ND-364 32.80 

ND - 4.66 1.42 

ND - 120.4 17.20 

64.97 3.66 

10.30 ND 

63.90 ND 

116.27 4.52 

55.00 11.2 

27.53 13.42 

4.69 0.62 

73.25 11.29 

1.95 0.63 

30.66 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 ffsh 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 4-2 1). A single dominant source was not observed 

for either compound based on Kruskal-WaIlis 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 rig/g (Figure 4-22b). The top 5 out of 362 sites for dieldrin are listed 

below: 

Dieldrin 

Cont. Episode 

450 3161 WB Sucker Cobbs Cr., Philadelphia, PA 

405 3117 PF Lake Trout Lake Michigan, Waukegan, IL 

323 3036 WB Carp 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 rig/g)) was for locations near Super-fund sites and the 

next highest for sites near industrial/urban areas (9.9 rig/g)) (Figure 4-23). 

alpha/gamma-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 
521 

t 

0 

0 

0 

NSQ 8 PPC PPNC RI NPL WP INDiURB POTW AGRI 

Summary Table for Total Nonachlor Box Plot 

Site Cateqorv 

NASQAN (NSQ) 

Background (B) 

Paper Mills Using Cl (PPC) 

Other Paper Mills (PPNC) 

Refinery/Other Industry (R/I) 

Superfund Sites (NPL) 

Wood Preservers (WP) 

IndustriiVUrban Sites (IND/URB) 

POTW 

Agricultural (AGRI) 

n - 

39 

20 

39 

17 

5 

6 

10 

31 

6 

15 

Concentration 

Range 

cm Mean Stan. Oev. Median 

ND - 221.3 26.26 49.28 7.07 

ND - 30.4 5.68 9.84 ND 

ND - 159.3 17.70 36.10 2.29 

ND - 521 54.00 130.03 6.59 

ND-166.6 46.48 68.47 28.76 

ND - 132.9 32.35 49.92 14.7 

NC - 22.52 5.07 7.15 2.01 

ND-245 32.45 50.08 11.3 

ND - 78.2 16.49 30.77 2.72 

ND-105.0 19.88 27.75 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 5sh tissue. 

87 
0 

I 0 

e 8 

T 0 

01 I 9 I ,Ti 

NSQ B PPC PPNC R/I NPL WP INDAJRB POTW AGRI 

Summary Table for Oxychbrdane Box Plot 

Site Category 

NASQAN (NSQ) 

Background (B) 

Paper Mills Using Cl (PPC) 

Other Paper Mills (PPNC) 

Refinery/Other Industry (R/I) 

Superfund Sites (NPL) 

Wood Preservers (W P) 

IndustriaUUrban Sites (INDIURB) 

POTW 

Agricultural (AGRI) 

n 

39 

20 

39 

17 

5 

6 

10 

31 

6 

15 

n = number 01 sites in category. ND’s set at 0. 

Maximum concentrations at sites were used. 

Concentration 

Range 

w-9 

ND - 77.0 4.67 14.11 ND 

ND- 4.64 0.50 1.34 ND 

ND - 14.4 0.73 2.59 ND 

ND- 3.48 0.34 0.92 ND 

ND- 11.7 3.87 4.52 2.62 

ND - 14.3 2.38 5.84 ND 

ND ND ND ND 

ND - 42.3 3.34 8.25 ND 

ND - 17.9 2.98 7.31 ND 

ND - 6.75 2.62 0.68 ND 

Mean Sfan. Dev. Median 

Figure 4-21. Box and whisker plot for oxychlordane in fish tissue. 

88 
DIELDRIN 

: 

. 

1. 

0 

. . . . . . . . ..~........................................................ 1 

20 a 8D w 100 

Percentile of Sites 

Dieldrin @g/g): 

m - >loo 

A - >2.5to loo 

O- 0 to 2.5 45 Total Sites: 362 

Fillet Only: 30 

‘Percent of sites in category Maximum was Fillet: 11 

Figure 4-22. Dieldrin: a) cumulative fitquency distribution and b) map of geographical 

distribution of various concentrations in fish tissue. 
0 

NSQ B 

4 

PPC PPNC RI NPL WP INDAJRB POTW AGRI 

Summary Table for Dieldrin Box Pbt 

Site Catwow n 

Concentration 

Range 

w/a Mean Stan. Dev. Median 

NASQAN (NSQ) 39 ND - 323 35.48 71.16 ND 

Background (8) 20 ND- 136 14 .31 35.45 ND 

Paper Mills Using Cl (PPC) 39 ND-236 14.86 41.18 1.40 

Other Paper Mills (PPNC) 17 ND - 41.5 4.90 9.94 1.84 

Ref inevK)ther Industry (WI) 5 ND - 64.9 16.64 27.40 4.18 

Superfund Sites (NPL) 6 ND-260 54.55 101.77 13.05 

Wood Preservers (WP) 10 ND - 7.73 0.97 2.45 ND 

IndustriaVUrban Sites (INDIURB) 31 ND - 116 18.46 29.71 9.96 

POlw 6 ND - 38.2 7.86 15.16 0.64 

Agricuttural (AGRI) 15 ND-188 43.94 69.37 ND 

n = number of sites in category. ND’s set at 0. Maximum cwcentmtions at sites warn used. 

Figure 4-23. Box and whisker plot for dieldrin in fish tissue. 

90 
alpha-BHC 

Cont. 

noJo 

Episode 

Number _ . Ty?e ot Frsh 

44.4 3098 WB White Sucker 

29.0 2427 WB carp 

20.8 2410 WB Carp 

19.3 2383 WB Carp 

18.6 2056 wx carp 

Red Clay Cr., Ashland, DE 

Peshtigo R. Harbor, Peshtigo, WI 

Rouge R., River Rouge, MI 

Des Plaines R., Lockport, IL 

Ohio R., West Point, KY 

gamma-BHC (Lindane) 

Cont. 

n_p/g 

Episode 

Number Type of Fish Location 

83.3 3042 WB Carp 

44.5 2416 WB Carp 

38.8 3098 PF American Eel 

27.4 2439 WB Carp 

25.7 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 

3 18 1). 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 piots 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; metboxychlor; isopropalin; and perthane. One chemical, beptachlor epoxide, 

found at 16 percent of the sites, is presented in the next section with heptachlor. 

91 
ia 

f 

f ’ 

8 

ALPHA-BHC 

# 

i 3asii 

i ._,___......._...,..,....~..........,.......~..~. . . . . 

0 20 

F&Mile of&M 

eo loo 

1 

"04 b) GAMMA-BHC (LINDANE) 

0 20 ul 60 a loo 

Percentile of Site8 

Figure 4-24. Cumulative frequency distribution of a) alpha-BHC and b) gamma-BHC (lindane) 

in fish tissue. 

92 
Ei 20 

9 

P 

m 15 

0 

I , 

T 1 Q”” 

f I I ,11 

NSQ 6 PPC PPNC RI NPL WP INDNRB POlW AGRI 

Summary Table for Alpha-BHC Box Plot 

Site Catwow 

NASQAN (MU) 

Background (B) 

Paper Mills Using Cl (PPC) 

Other Paper Mills (PPNC) 

RefinerylOther Industry (R/I) 

Superfund Sites (NPL) 

Wood Preservers (WP) 

Industrial/Urban Sites (INOAJRB) 

POlw 

Agricuttural (AGRI) 

n - 

39 

20 

39 

17 

5 

6 

10 

31 

6 

15 

Concentration 

Range 

D&a Mean 

ND - 12.30 1.98 

ND - 9.08 0.72 

ND - 11.30 1.74 

ND - 2.77 0.99 

ND - 4.97 1.92 

ND - 8.43 2.49 

ND - 1.08 0.21 

ND - 17.48 2.20 

ND - 3.98 1.41 

ND - 7.58 1.32 

Stan. Dev. Median 

2.98 0.93 

2.09 ND 

2.75 ND 

0.99 0.85 

2.11 0.96 

3.18 1.26 

0.44 ND 

4.11 0.91 

1.82 0.56 

2.19 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 fJsh tissue. 

93 
0 

0 

0 

0 

0 1 -r 

8 

0 

0 

, 

Q 0 I 

I T 

0 I _ 

O* I 1 ~I 1 * 

NSCI B 

I , I 

PPC PPNC R/I NPL WP IND/URB POTW AGRI 

Summary Table for Gamma-BHC Box Plot 

Site Category 

Concentration 

Range 

n wa Mean Stan. Dev. Median 

NASQAN (NSQ) 39 ND - 83.3 3.25 13.91 ND 

Background (B) 20 ND - 2.97 0.15 0.66 ND 

Paper Mills Using Cl (PPC) 39 ND - 25.7 2.66 5.85 ND 

Other Paper Milk (PPNC) 17 ND-21.9 3.33 6.60 0.63 

Refinery/Other Industry (R/I) 5 ND - 3.1 1.49 1.21 1.41 

Superfund Siles (NPL) 6 ND - 7.8 1.30 3.18 ND 

Wood Preservers (WP) 10 ND - 3.3 0.57 1.09 ND 

IndustriaVUrban Sites (INDIURB) 31 ND - 10.5 1.99 2.97 0.37 

POTW 6 ND - 0.58 0.10 0.24 ND 

Agricuftural (AGRI) 15 ND- 9.8 1.15 2.52 ND 

n - number of sites in category. ND’s set at 0. 

Maximum concentrations at sites were used. 

94 

Figure 4-26. Box and whisker plot for gamma-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 all 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 

Cont. Episode 

n p/g N&I Tm J.oa 

913 3085 W B 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 
Hexachlorobentene (nglg): 

8 = >50 1’ 

A - >2.5 to50 20 

0 = 0 to 2.5 79 

Fillet Only: 27 

l Percenl of sites m category Maxlrnum was Fillet: 8 

b) Hexachlorobenzene t 

a ) 

1 t j 

l , 

Figure 4-28. Hexachlorobenzene: a) map of geographical distribution of various concentration 

ranges and b) cumulative frequency distribution in fish tissue. 

97 
120 

60 

20 

0 

0 

913 

t 

0 

0 0 If 

I I 9 

I 

t 9 I , 

NSQ B PPC PPNC WI NPL WP IND/URB POTW AGRI 

Summary Table for Hexachforobentene Box Plot 

Site Category n 

Concentration 

Range 

wg Mean Stan. Dev. 

NASQAN (NSQ) 

Background (0) 

Paper Mitts Using Cl (PPC) 

Other Paper Mills (PPNC) 

Refinery/Other Industry (R/I) 

Super-fund Sites (NPL) 

Wood Preservers (WP) 

Industrial/Urban Sites (INDIURB) 

POTW 

Agricultural (AGRI) 

39 ND - 6.49 0.83 1.35 

20 ND - 6.88 0.60 1.59 

39 ND - 93.7 3.90 16.35 

17 ND - 2.7 0.54 0.77 

5 ND-75 15.39 33.33 

6 ND - 12.5 2.89 5.09 

10 ND - 1.89 0.24 0.60 

31 ND-913 31.56 163.6 

6 ND -1.76 0.29 0.72 

15 ND - 15.6 2.08 4.26 

n = number of sites in category. ND’s set at 0. 

Maximum concentrations at sites were used. 

Median 

ND 

ND 

ND 

ND 

0.73 

ND 

ND 

0.33 

ND 

0.09 

98 

Figure 4-29. Box and whisker plot for hexachlombenzene in fish tissue. 
Pentachlorobenzene (ng!g): \ 

n I >lO 1' 

A I >2sto10 6 \ 1 oral 3w35. . 

0 I oto2.5 93 Fillet P-l-.. q 

‘Percent of sites in category 

Max? num was Fillet: 6 

I b) Pentachlorobenzene 

‘I I 

I. , , . _ I 

0 P 40 00 00 loo 

Pamantilr d Sites 

135 Trichlorobenzene 

Figure 4-30. Pentachlorobenzene: a) map of geographical distribution of various concentrative 

ranges and b) cumulative frequency distribution in fish tissue. c) Cumulative 

frequency distribution of 1,3,5 trichlorobenzene in fish tissue. 
Pentachlorobenzene 

Cont. Episode 

Nwber Tvpe of Smle Lo@” 

125 3086 W B Catfish Bayou D’Inde. Sulfur, LA 

5 1.4 3063 PF Spotted Sea Trout Calcasieu R., Moss Lake, LA 

36.3 3097 WB carp Red Lion Cr.. Tybouts Comer, DE 

32.6 3085 W B Sea Catfish Brazos R., Freeport, TX 

9.6 2532 WB Carp Mississippi R., St. Francisville, LA 

Four of these sites are near chemical manufacturing pJants 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 4-3 1) 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 1 J percent of the sites, the 

compound 1,3,5 trichlorobenzene was detected above the quantitation limit at only three sites 

(Figure 4-30~). These sites are listed below: 

1.3.5 TCB 

Cont. Episode 

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 WB Carp Ohio River. West Point, KY 

Sites 3403 and 2290 are near paper mills. The latter site also has other industriaJ/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 4-33ab.c). The tetrachloroknzenes are moderately to highly volatile and, as a result, may be higher than reported because the 

anaJytical 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 ttichlorophenoxyacetic acid), a 
6C ‘T 

0 

0 

0 

I 8 T 

01 f 0 1 I I I P L 

NSQ 6 PPC PPNC R/I NPL WP lNDlURI3 POTW AGRI 

Summary Table for Pentachlorobenzene Box Plot 

Site Category 

Concentration 

Range 

n w&i Mean Stan. Dev. Median 

NASQAN (NSQ) 39 ND - 1.26 0.03 0.20 ND 

Background (0) 20 ND - 0.6 0.03 0.13 ND 

Paper Mills Using Cl (PPC) 39 ND - 9.61 0.38 1.71 ND 

Other Paper Mills (PPNC) 17 ND - 0.57 0.08 0.17 ND 

Refinery/Other Industry (R/I) 5 ND- 51.4 11.36 22.50 ND 

Supetfund Sites (NPL) 6 ND - 46.3 7.72 18.90 ND 

Wood Preservers (WP) 10 ND ND ND ND 

Industrial/Urban Sites [INDIURB) 31 ND - 42.6 1.84 7.68 ND 

POTW 6 ND ND ND ND 

Agricultural (AGRI) 15 ND - 0.75 0.07 0.20 NT: 

n = number of sites in category. ND’s set at 0. 

Maximum concentrations at sites were used. 

Figure 4-3 1. Box and whisker plot for pentachlorobenzene in fish tissue. 

101 
0 

0 

I 

0 

0 9 f T 

NSQ B PPC PPNC R/i NPL WP IND/URB POTW AGRI 

Summary Table for 1,3,5-Triihbrobenzene Box Plot 

Site Category 

NASQAN (NSQ) 39 ND - 0.06 0.002 

8ackground (B) 20 ND - 0.24 0.02 

Paper Mills Using Cl (PPC) 39 ND - 14.9 0.40 

Other Paper Mills (PPNC) 17 ND - 2.35 0.16 

Refineries (RFNY) 5 NO - 0.54 0.11 

Superfund Sites (NPL) 6 ND- 0.55 0.09 

Wood Preservers (WP) 10 ND ND 

Industriallllrban Sites (INDIURB) 31 ND - 1.20 0.13 

POTW 6 ND ND 

Agricuttural (AGRI) 15 ND ND 

n 

Concentration 

RarQ8 

nglg Mean Stan. Dev. Median 

0.01 

0.06 

2.36 

0.57 

0.24 

0.22 

ND 

0.32 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

ND 

n = number Of Sit8S in Category. ND’s S8t at 0. 

Maximum tX!K8ntrationS at Sites W8r8 used. 

Figure 4-32. Box and whisker plot for 1,3,5 trichlm in fish tissue. 
1 a) 1234-TETRACHLOROBENZENE 

j 3@siti 11 

0 20 40 60 80 1OO 

Percentile of Sites 

I b) 1235TETRACHLOROBENZENE 

1 “F,) 1245TETRACHLOROBENZENE 

1 

lool 1 1 

. 

PercentlIe of Sites 

0 20 40 60 80 loo 

Percentile of Sites 

Figure 4-33. Cumulative fkqucncy distribution of a) 1,2,3,4 tetrachlorob~~~~, b) 1,2,3,5 

tetrachlorobenzene and c) 1,2,4,5 tctnchloroba~~~ 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: 

1,2,3,5 and L2.4.5 TECB 

Cont. Episode 

ngfg Number Type of Sample Location 

28.3 3097 PF Brown Bullhead 

15.3 2056 WB Carp 

12.9 2341 WB Carpsucker 

12.0 2290 WB Spotted Sucker 

10.7 3086 PF Red Drum 

Red Lion Creek, Tybouts Comer, 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 Super-fund 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). 

1,2,3,4 TECB 

Cont. 

rig/g 

Episode 

Number Type of Sample Location 

76.65 3097 PF Brown Bullhead 

11.50 2056 WB Carp 

11.3 2341 WB Carpsucker 

10.6 3096 WB Channel Catfish 

10.4 3094 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 
a) 

‘ECB @g/g): 

B5 

2.5 to 5 

0 to 2.5 

‘Percent of sites in category 

Sites: 

Chlly: 

LA u Maximumw ‘as Fillet: 

1235 TECB (t-q&): 

8 =>5 

= 2.5to5 

I 0 to 2.5 

Total Sites: 

Fillet only: 

Maximumwas 

‘Percent of sites in category 

c) 

1245 TECB (ng/g): 

8 -A 

ii 

= 2.5 to 5 Maximum was 

- oto2.5 97 

‘Percent of rites in category 

Fillet: 

Fillet: 

352 

30 

9 

352 

30 

3 

362 

30 

2 

Figure 4-34. Map of geographical distribution of various conmtration ranges for a) 1,2,3,4 

tetrachlorobenzene, b) 1,2,3,5 tetrachlorobemene, and c) 1,2,4,5 

tetrachlombenzene in fish tissue. 
Summary Table for 1,2,3,+Tetrachlorobenzene Box Plot 

Concentration 

Site Category n 

NASQAN (NSQ) 39 

8ackground (6) 20 

Paper Mills Using Cl (PPC) 39 

Other Paper Milfs (PPNC) 17 

Refinery/Other Industry (R/I) 5 

Superlund Sites (NPL) 6 

Wood Preservers (WP) 10 

IndustriaUUtban Sites (IND/URB) 31 

PQTW 6 

Agricuhural (AGRI) 15 

Range 

Wg Mean Stan. Dev. Median 

ND ND ND 

ND - 0.25 0.03 0.08 

ND- 0.66 0.03 0.14 

ND- 0.11 0.02 0.03 

ND - 5.21 1.74 2.46 

ND -20.92 3.49 8.64 

ND - 1.01 0.10 0.32 

ND - 0.76 0.04 0.14 

ND ND ND 

ND 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 tebachlorolmzene in fish tissue. 

Ah5 
Pesticides/Herbicides 

Mirex, Chlorpyrifos, Dicofol, Methoxychlor, and Perthane 

Mirex was used primarily tocontrol fire ants in the Southeast between 1962 and 1975 (NAS, 

1978). Mirex has also been used on pineapple mealy bugs in Hawaii and asa 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 4-36aJ. The chemical was produced at plants located along the Niagara 

River, and it occurred at high levels in this area as shown below: 

Mirex 

Cont. Episode 

er 

225 2328 PF Chinook Salmon 

137 3305 WB Channel Catfish 

131 2329 PF Brown Trout 

85.4 3412 WB Carp 

73.7 3301 WB Carp 

Lake Ontario, Olcott. NY 

Racquette R., Massena. NY 

Lake Ontario, Rochester, NY 

Oswego Harbor, Oswego, NY 

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 organochforine pesticides such as DDT. It is used oncotton, 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 

rig/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: 

107 
CHLORPYRIFOS 

1oQ 

;: 

. 

1 

1 : . . . . . . . . . "".? . . . . . . . . . . . . . . . . ..__............................... J. . . ..__............._....... j 

: 

l 

I 

0 20 40 60 80 lit0 

Percentile of sites 

Figure 4-36. Cumulative frequency distribution of a) mirex and b) chlorpyrifos in fish tissue. 
0 

70. 

0 

0 

0 I 

01 ? 

.a . 

f, 1 

NSQ B PPC PPNC R/I NPL WP INDNRB POTW ACM 

Summary Table for Mirex Box Plot 

Concentration 

Site Category n 

Range 

w&l Mean Stan. Dev. Median 

NASQAN (NSQ) 39 ND-23.1 1.6 5.0 ND 

Background (B) 20 ND-1 1.3 0.7 2.5 ND 

Paper Mills Using Ci (PPC) 39 ND-21.6 1.6 4.0 ND 

Other Paper Mills (PPNC) 17 ND-35.5 4.9 9.6 ND 

Refineries/Other industry (RIO 5 ND-2.0 0.8 0.9 0.7 

Supetfund Sites (NPL) 6 ND-O.6 0.2 0.3 ND 

Wood Preservers (WP) 10 ND-OS 0.1 0.2 ND 

Industrial/Urban Sites (IND/URB) 31 ND-854 3.9 15.6 ND 

POTW 6 ND-2.6 0.6 1.1 ND 

Agricultural (AGRI) 15 ND-l 0.4 1.3 3.0 ND 

n = number of sites in category. ND’s set at 0. Maximum concentrations at each site were used. 

Figure 4-37. Box and whisker plot for mircx in fish tissue. 

109 
Chbqyrifos (ngg): 

l - r50 

A - > 2.51050 

0 - 0102.5 

- .-. Totat Sites: 362 

Fillet Only: 30 

‘Percent of rile8 in catagoty Maximum was Fillet: 8 ’ 

Figure 4-38. Map of gcqraphicai distribution of various umcentxation ranges for chlorpyrifos 

in fish tissue. 
Chlorpyrifos 

Episode 

344 3282 WB Carp 

64.5 3375 WB Carp 

63.7 3071 WB Carp 

62.7 3141 PF Northern Pike 

61.7 3283 WB Carp 

Alamo R., Calipatria, CA 

Chanahoochee 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 3 141) 

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 15.5 percent). Dicofol and methoxychlor concentrations 

were greater than the quantification limit of 2.5 rig/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 dicofo1 is shown in Figure 4-42. The 

highest mean concentration of all the categories was for sites near agricultural areas (2.7 ng/g). 

The highest five concentrations of dicofol and methoxychlor are listed below: 

Dicofol 

Cont. Episode 

er Tvpe of- J.aciLtiQa 

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, ID 

South Platte River, Denver, CO 

Malheur River, Ontario, OR 

Lake Michigan, Waukegan, IL 
0 

0 0 

04 T I 1 A 7 I , 1 

NSQ B PPC PPNC WI NPL WP IND/URB POTW AGRI 

Summary Table for Chlorpyrifos Box Plot 

Concentration 

Site Category 

NASQAN (NSQ) 39 ND-40.8 2.34 7.43 ND 

Background (B) 20 ND-5.13 0.40 1.29 ND 

Paper Mills Using Cl (PPC) 39 ND-22.6 1.15 5.02 ND 

Other Paper Mills (PPNC) 17 ND-45.6 4.71 11.98 ND 

Refineries/Other industry (R/l) 5 ND-19.4 4.40 8.43 0.48 

Superfund Sites (NPL) 6 ND ND ND ND 

Wood Preservers (WP) 10 ND-Z.51 0.25 0.79 ND 

IndustriaVUrban Sites (INDIURB) 31 ND-61.7 3.89 11.50 ND 

POTW 6 ND ND ND ND 

Agricultural (AGRI) 15 ND-344 24.46 88.56 ND 

n 

Range 

wg Mean Stan. Dev. Median 

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. 

x12 
I a) DICOFOL (KELTHANE) 

I 

I, I 

a 20 40 60 w . loo 

Percentile of Sites 

b) METHOXYCHLOR . 

4 

b 

. 

d 

l 

& 

362siln 

r’ 

. . . . . . 

20 4a 60 80 10 

Percentile of Sites 

c) PERTHANE 

I 

L I 

. ) 

. ’ 

I 

0 20 

. 

L ) 

362 Silm 

40 60 80 loo 

PercentlIe of Sites 

Figure 4-40. Cumulative frequency distribution of a) dicofol (kelthane), b) methoxychlor, and 

c) perthme in fish tissue. 
Oicofol (ngig): 

m = >lO 2’ 

A I >2.5tolO 5 

o= 0 to 2.5 93 \ 9 Total S \ 

‘Percent of sites u-3 category 

‘ites: 362 ‘. ’ 

‘U xi 

Fillet Only: 29 

Maximum was Fillet: 9 

b) ; - 

9 

A - >2.5to20 

0 I 0 to 2.5 

l Percem of sites in category 

i: 

Fillet Only: 

Maximum was Fillet: 3 

Figure 4-41. Map of geographical distribution of various concentration ranges for a) dicofol 

and b) methoxychfor in fish tissue. 

114 
I 

18. 

16. 

s 12. 

2 

z 10. 

B .- 

0 8. 

6. 

0 

0 

e 0 

0 0 I 

T e 0 

0 

0’ 

NSQ B PPC PPNC R/I NPL WP IND/URB POTW AGRI 

1 

Summary Table for Dicofol Box Plot 

Site Category 

NASQAN (NSQ) 39 ND-5.37 0.54 1.44 ND 

Background (B) 20 ND-2.29 0.27 0.70 ND 

Paper Mills Using Cl (PPC) 39 ND-4.53 0.14 0.74 ND 

Other Paper Mills (PPNC) 17 ND-2.44 0.28 0.65 ND 

Refineries/Other Industry (R/I) 5 ND-3.69 1.02 1.61 ND 

Superfund Sites (NPL) 6 ND ND ND ND 

Wood Preservers (WP) 10 ND ND ND ND 

Industrial/Urban Sites (IND/URB) 31 ND-O.50 0.02 0.09 ND 

POTW 6 ND-4.09 0.68 1.67 ND 

Agricultural (AGRI) 15 ND-18.40 2.66 5.41 ND 

n 

Concentration 

Range 

WS Mean Stan. Dev. Median 

n = number of sites in category. ND’s set at 0. 

Maximum concentrations at sites were used. 

Figure 442. Box and whisker plot for dicofol in fish tissue. 
Methoxychlor 

Cont. Episode 

r TV393. 3195 WB Chub Jordan River, Salt Lake City, UT 

17.9 3375 WB Carp Chattahoochee River, Austell, GA 

8.22 2056 WB Carp Ohio River, West Point, KY 

8.15 3172 WB Carp Coosa River, ALGA State Line 

7.71 3144 WB Carp Fox River, Portage, WI 

The two highest concentrations (3355 and 3195) were found near Superfund 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 manufactured. 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. 

lsopropalin 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 
. . . . , 

20 40 60 80 100 

Percentile of Sites 

loo&- 

W ISOPROPALIN i 

b 20 40 so 

Percentile of sites 

80 . 100 . . ..- 

Figure 4-43. Cumulative frequency distribution of a) trifluralin and b) isopropalin in fish tissue. 

I17 
i 

Trifluralin(n@g): 

m I .lOO 

A I >2.5to100 

0 a 0 to 2.5 

‘Percent of sites in 

2’ 

9 

69 

category 

Fillet Only: 

Maximum was Fillet: 

‘Pofcwl of sites in category Maximum was Fillet: 

Figure 4-44. Map of geographical distribution of various conccntion ranges for a) trifluralin 

and b) isopropalk in fish tissue. 

118 
458 

t 

0 

‘r 

0 

0 

0 

N$Q Ei PPC PPNC d/l NFL \hiP INDiURB PdTW A&l 

Summary Table for Trifluralin Box Plot 

Site Category n 

NASQAN (NSQ) 39 

Background (6) 20 

Paper Mills Using Cl (PPC) 39 

Other Paper Mills (PPNC) 17 

Refineries (RFNY) 5 

Superfund Sites (NPL) 6 

Wood Preservers (WP) 10 

Industrial/Urban Sites (IND/URB) 31 

POTW 6 

Agricultural (AGRI) 15 

Concentration 

Range 

44 

ND-458 20.92 

ND-183 10.80 

ND-23.1 0.59 

ND-3.4 0.20 

ND - 2.9 OS8 

ND ND 

ND ND 

ND-82.8 6.37 

ND ND 

ND-153 23.35 

Mean Stan. Dev. Median 

77.01 ND 

37.73 ND 

3.70 ND 

0.82 ND 

1.30 ND 

ND ND 

ND ND 

18.83 ND 

ND ND 

46.52 ND 

n - number of sites in category. ND’s set at 0. 

Maximum concentrations at sites were used. 

Figure 4-45. Rex and whisker plot for trifluralin in fish tissue!. 

I19 
40 

35 

30 

G 

P 

25 

c .- 

75 

Ef 

20 

'a 

4 15 

10 

0 

0 

0 

0 0 

0 

0 

T T 

NSQ 6 PPC PPNC R/I NPL WP lND/LJRB POTW AGRI 

Summary Table for lsopropalin Box Pbt 

Concentration 

Site Category 

NASQAN (NSQ) 39 ND-25.9 1.27 

Background (B) 20 ND ND 

Paper Mills Using Cl (PPC) 39 ND ND 

Other Paper Mills (PPNC) 17 ND ND 

Refinery/Other tndustry(R/I) 5 ND ND 

SUfMiUnd sit8S (tdptw) 6 ND ND 

Wood Preservers (WP) 10 ND-l 0.2 1.02 

IndustriaVUrban Sites (INDIURB) 31 ND-37.5 1.33 

POT-W 6 ND ND 

Agricuttural (AGRI) 15 ND ND 

n 

RafIg8 

nsls Mean Stan. Dev. Median 

n - number of sites in category. ND’s set at 0. 

Maximum concentrations at siles w8fe used. 

4.89 ND 

ND ND 

ND ND 

ND ND 

ND ND 

ND ND 

3.23 ND 

6.98 ND 

ND ND 

ND ND 

120 

Figure 4-46. Box and whisker plot for iqmpaiin in fish tissue. 
362 Sites 

‘iI , 20 40 60 80 100 , 

Percentile of Sites 

Endrin (ng/g): 

n - 950 

A - >2.5 to 50 

0 - 0 to 2.5 90 

‘Percent of sites it-i category 

Total Sites: 

Fillet Only: 

Maximum was Fillet: 

362 u 

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 SITES” 

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 rig/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 rig/g at only four sites. The top five sites (all 

of which are near organic chemical manufacturing plants) are listed below: 

Hexachlorobutadiene 

Cont. Episode 

164.00 3063 WB Sea Catfish 

23.00 3085 WB Sea Catfish 

10.50 3115 PF Catfish 

2.54 3065 WB Flathead Catfish 

2.37 3086 WB Catfish 

Calcasieu R., Moss Lake, LA 

Brazes R., Freeport, TX 

Mississippi R., E. St. Louis (Sauget), IL 

Mississippi R., Baton Rouge, LA 

Bayou D’Inde, Sulfur, LA 

Diphenyl Disulfide 

Diphenyl disulflde was detected at only two sites (Figure 4-49~). This compound is used in 

small amounts in the pharmaceutical industry, in the vulcanizing of rubber, and as a flavoring agent. 

4 Some cbemicais found at less than 10 percent were presemted elsewhere for ease of discussion. See footnotes 2 

page 57. and 3, page 9 1. 

122 
loo162 

90. 

t 

60. 

20. 

P 

0 

10. 

0 a 0 

OJ ? I , I 0 

NSQ 0 PPC PPNC R/I NPL WP IND/lJRB POTW AGRI 

Summary Table for Endrin Box Plot 

Site Cateaorv n 

NASQAN (NSQ) 39 ND-7.5 0.53 1.65 ND 

Background (B) 20 ND-26.5 2.00 6.50 ND 

Paper Mills Using Cl (PPC) 39 ND-l 62 5.22 25.90 ND 

Other Paper Mills (PPNC) 17 ND ND ND ND 

Refinery/Other lndustry(R/I) 5 ND ND ND ND 

Superfund Sites (NPL) 6 ND-l 6.2 3.64 6.55 ND 

Wood Preservers (WP) 10 ND ND ND ND 

IndustriaHJrban Sites (IND/URB) 31 ND-7.37 0.32 1.38 ND 

POTW 6 ND ND ND ND 

Agricultural (AGRI) 15 ND-45.4 4.23 12.30 ND 

Concentration 

Range 

wcl Mean Stan. Dev. Median 

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 
I 7. 

: a) Octachlorostyrene 1 ’ b) Hexachlorobutadiene I 

. 

. lcq rq), I I 

% 

. 

a 00 m a W 40 00 ‘00 

Pmont~b d Silos Porcmtib of &es 

Oiphenyl Oisulfide 

1 1 

0 W 

PwLtib of Eter 

m rw 

Pwcm?til, ol Sitn 

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 

Cont. Episode 

r TV. 1.w 

17.9 3354 WB Carp 

12.8 3300 WB White Sucker 

10.4 2654 WB Carp 

10.6 3302 WB White Sucker 

3.95 3288 PF Squawfish 

New Mormon Slough, Stockton, CA 

Niagara River Delta, Porter, NY 

Toms River, NJ 

Niagara River, Lewiston, NY 

Blanco Drain, Salinas, CA 

The site with the highest concentration is located near a Supetfund 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 Heptacblor Epoxide 

Heptachlor is an insecticide that has been used to control fire ants in southern States and soil 

insects on corn. 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 bioaccumulates 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-SOa,b). Thirteen percent of the sites had maximum concentrations over 

2.5 rig/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 4-5 1). 

The box plot for heptachlor epoxide shows that median concentrations for all categories were below 

detection (Figure 4-52). 

12s 
HEPTACHLOR t 

. 

. 

1 

f 

t 

. 

362 SitOr 

d 

20 40 60 60 100 

Percentile of Sites 

b) HEPTACHLOR EPOXIDE 

I 362 Sites 

0 20 

PeZentile of Ges 

eo 100 

Figure 4-50. Cumulative fkcquaq distribution of a) heptachlor and b) hcptachlor cpoti& in 

fish tissue. (Maximum concentration at each site was used. Bar on x-axis 

represents sites below detection.) 

126 
Heptachlor (ng/g): 

*Percent of sites in category MaxImum w 

/ 

3 

Heptachlor @oxide @g/g): 

m I >25 3’ 

A I > 2.5 to25 10 

o= 0 to 2.5 07 es: 

v rlller wdy: 

‘Percent ot sites in category Maximum was Fillet: 5 

Figure 4-5 1. Map of geographical distribution of various concentration ranges for a) heptachlor 

and b) heptachlor cpoxide in fish tissue. 

127 
0 

60. 

Summary Table for Heptachlor Epoxide Box Plot 

site CateoorY 

NASQAN (NSQ) 

Background (8) 

Paper Mills Using Cl (PPC) 

Other Paper Mills (PPNC) 

Refinery/Other Industry (R/I) 

Super-fund Sites (NPL) 

Wood Preservers (WP) 

IndustriaVUrban Sites (IND/URB) 

POTW 

Agricuttural (AGRI) 

Concentration 

Range 

n - - Mean Stan. Dev. Median 

39 ND - 63.2 3.3 11.2 ND 

20 ND - 19.9 1.6 5.0 ND 

39 ND - 28.7 1.1 5.0 ND 

17 ND - 2.9 0.2 0.7 ND 

5 ND - 2.3 0.5 1 ND 

6 ND ND ND ND 

iy 

ND ND ND ND 

ND - 24.1 1.3 4.7 ND 

6 ND ND ND ND 

15 ND - 9.3 0.6 2.4 ND 

n = number of sites in category. NO’s set at 0. Maximum concentrations at sites were used. 

Figure 442. Box and whisker plot for heptachlor epoxide in dsh tissue. 

128 
Pentachloronltrobenzene 

Pentachloronitrobenzeene (PCNB) is used as a soil fungicide, a seed dressing agent for 

peanuts, to control stem and root rot on tlowers 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 organochlorine 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 transchlordane, 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 concentrations 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 for p,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 
b) l - %5- 

t 

4 Pentachloronitrobenzene 

I 0 

t-l 

8 O0 

0 0 

Per itachloronitrobenrel le NVg): 

l = >2.5 0.5 

0 = 0 to 2.5 99.5 

\ Total Sites: 362 y 

Fillet Only: 30 

*Percent of sites in category 

Maximum was Fillet: 0 

Figure 4-53. Pentachloronitrobenzene: a) cumulative frequency distribution and b) map of 

geographical distribution of various concentration ranges in fish tissue. 
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 comparisons 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. Freshwater, 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. addition, In 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 Species Collected 

Scientific Name Common Name Range 1 

Feeding No. of 

Strategy 2 sites 3 

Class - Chondrichthyes 

Order - Squaliformes 

Family - Carcharhinidae 

Triakis semifasciata Leopard Shark 

Order - Rajiformes 

Family - Rajidae 

Raja binoculata 

Family - Dasyatidae 

Dasyatis (species unknown) 

Order - Chimaeriformes 

Family - Chimaeridae 

Hydrolagus colliei 

Class - Osteichthyes 

Order - Acipenseriformes 

Family - Acipenseridae 

Acipenser transmontanus 

Order - Semionotiformes 

Family - Lepisosteidae 

Lepisosteus osseus Longnose Gar 

Lepisosteus platostomus Shortnose Gar 

Order - Amiiformes 

Family - Amiidae 

Amia calva 

Order - Anquilliformes 

Family - Anquillidae 

Anguilla rostrata 

Order - Clupeiformes 

Family - Clupeidae 

Big Skate 

Stingray 

Spotted Ratfish 

White Sturgeon 

Bowfin 

American Eel 

Alosa sapidissima American Shad 

Dorosoma cepedianum Gizzard Shad 

M 

M 

M 

M 

P 

B 

P 

P 

Both P 4 

F P 1 

F P 1 

F P (Pisc.) 2 

Both P 1 

Both P 1 

Both P 1 

(Filter Feeder) 

1 estuarine/Marine: M=Marine; F=Freshwater; (I)=Introduced 

2 P=Predator; B=Bottom Feeder 

3 Number of sites where fish were collected and analyzed 

SOURCE: AFS, 1980 

Pisc. = Piscivorpis; Omni. = Omnivorous 

132 
- 

TABLE 5-l (CONT.) 

Scientific Name Common Name Range ’ 

Feeding, No. of 

Strategy - sites 3 

Order - Osteoglosstfomtes 

Family - Hiodonudae 

Order - Sahnomfonnes 

Family - Sahnomdae 

Salvelinus fonunalis 

Family - Osmeridae 

Family - Esocidae 

E 

Order - Cypriniformes 

Family - Cyprinidae 

Family - Catostomidae 

Goldeye F P 1 

Lake Whitefish Both P 1 

Pink Salmon Both P 1 

Coho Salmon Both P Wisc.i 1 

Rainbow Trout Both P (Fish. Insects, Algae) 7 

Chinook Salmon Both P (Pisc.) 1 

Mountam Whitefish F P (Aq. Insects) 1 

Cutthroat Trout Both P 1 

Atlantic Salmon Both P (Pisc.) 2 

Brown Trout BoWI P WiSC.) 10 

Brook Trout Both P 2 

Dolly Varden Both P 2 

Lake Trout F P (Pisc. 1 1 

Surf Smelt 

Northern Pike 

Chain Pickerel 

Pickerel; Pike 

Chiselmouth 

Goldfish 

GrassCarp 

Common Carp 

Chub 

Sacramento Blackfish 

Squawfish 

River Carpsucker 

Quillback 

Longnose Sucker 

Bridgelip Sucker 

White Sucker 

Largescale Sucker 

Sacramento Sucker 

Sucker (unspecified) 

Both 

F 

F 

F 

F 

R-4 

WI 

WI 

F 

F 

F 

F 

F 

F 

F 

F 

F 

F 

B 

P (Pisc.) 

P 

P 

B 

B 

B 

B (Omni.) 

B 

B 

B (Fix.) 

B 

B 

B 

B 

B (Omni.) 

B 

B 

1 

8 

4 

1 

1 

I 

1 

135 

1 

1 

9 

4 

1 

2 

3 

32 

2 

3 

32 

’ EeutineMuine: M = Manne: F = Freshwater: [I] = Introduced 

* P = Predator: B = Bottom Feeda 

’ Number of aicu tiere fiih were collected and analyzed 

SOURCE: AFS. 1980 

Pk. = Pixivorcus: Omai. = Omnivorws 
TABLE S-1 (CONT.) 

Scientific Name Common Name 

Creek Chubsucker 

Lake Chubsucket 

Northern Hog Sucker 

Sma.ilmouth Buffalo 

Bigmouth Buffalo 

Range ’ 

F 

F 

F 

F 

F 

F 

F 

F 

F 

F 

F 

F 

F 

F 

F 

F 

F 

F 

F 

F 

F 

- 

Both 

M 

Both 

F 

I 

Feeding2 

Strategy 

B 

B 

B 

B 

B 

(Zooplankton % Crust) 

B 

B Uooplankton 

Insect Larvae/Plants) 

B (Aq. Insects) 

B (Aq. Insects) 

B (Aq. Insects) 

B (Aq. Insects) 

B (Aq. Insects) 

B (Aq. Insecrs~ 

B (Aq. Insects) 

No. of 

Sites ’ 

B tack Buffalo 

Spotted Sucker 

1 

10 

Silver Redhorse 

Gray Redhorse 

Black Redhorse 

Golden Redhorse 

Shorthead Redhorse 

Blacktail Redhorse 

Redhorse Sucker 

1 

1 

1 

1 

I 

I 

16 

Order - Siluriformes 

Family - Ictaturidae 

E 

White Catfish 

Blue Catfish 

Black Bullhead 

Ydlow Bullhead 

Brown Bullhead 

channel catf-lsh 

Flatheal Catfish 

Catfish (unspecified) 

B 

B (Omni.) 

B (Omnt.1 

B (Omni.1 

B fOmni.1 

B (Omni.) 

P (Pisc.) 

4 

6 

2 

1 

4 

30 

8 

11 

Family - Ariidae 

Hardhead Catfiih B 

Order - Gadiformes 

Family - Gadidae 

Atlantic Cod P 

Order - Perciformes 

Family - Percichthyidae 

white Perch 

White Bass 

Stri~Bass 

Bass (unspecified) 

P 

P 

(F&h & Insects) 

P 

7 

1 

4 

IO 

1 

3 

’ EstuannelMuine: M = Maine: F = Freshwafer: [I] = IIIUO&XI 

* P = Ptedator: B = Bottom Feeda 

’ Number of silu what fuh were cokxed and analyzed 

SOURCE: AFS. 1980 

Pk. = Pistivwaru: OInoi. = olMivaou 
TABLE 5-l (CONT.) 

Scientific Name 

Family - Cenrrarchidae 

Common Name Range ’ 

Feeding2 

Strategy 

No. of 

Sites 3 

Family - Percidae 

m 

vitrtum 

Family - Pomatomidae 

Family - Carangidae 

Family - Lutjanidae 

Family - Sparidae 

Family - Sciaemidae 

Rock Bass 

Redbreast Sunfish 

Green Sunfish 

Pumpkinseed 

WarmoUth 

Bluegill 

Longear Sunfish 

Redear Suntish 

Redeye Bass 

Smdlmouth Bass 

Suwannee Bass 

Spotted Bass 

Largemoub Bass 

White Crappie 

Black Crapple 

Crappie (unspecified) 

Yellow Perch 

Sauger 

Walleye 

Bluefish M P (pisc.) 

Yellow Jack M P 

Crevalle Jack M P 

Papio M P 

Red Snapper M P 

Freshwater Drum F P (Mollusks & Fish) 

spotted Seatrout Both P 

Weakfish M P 

spotted Drum M P 

SP BOtb P 

F 

F 

F 

F 

F 

F 

F 

F 

F 

F 

F 

F 

F 

F 

F 

F 

F 

F 

M 

P 

P 

P 

P 

P 

P (Insects) 

P 

P (Mollusks~ 

P 

P (Pisc.) 

P 

P 

P 

P (Pisc.) 

P msc.~ 

P 

P 

P (Pi%) 

P 

J 

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 

’ Baurioe/Msrine: M = !&he: F = Freshwwcr: (I] = lnuoduced 

* P = Rcdator: B = Bosom Fccda 

3 Number of sites where fsh were collected and aallyti 

SOURCE: AFS. 1980 

Pk. = Pircivorms: Omni. = Mvarau 

135 
TABLE 5-l (CONT.) 

Scientific Name Common Name 

Atlanuc Croaker 

Black Drum 

Red Drum 

Range ’ 

Both 

M 

Both 

Feeding 

Strategy ’ 

P 

No. of 

sites 3 

3 

P 

P 

3 

3 

1 

1 

1 

3 

1 

1 

1 

I 

I 

4 

1 

2 

2 

1 

5 

1 

4 

Famrly - Cichlidae 

Family - Embiotocidae 

Family - Mugilidae 

Fmlly - Scorpaenidae 

Family - Cottidae 

Cmus. (species utiown) 

Order - Pleufonecuformes 

Family - Bothidae 

Family - Pleuronectidae 

Redbelly Tilapia 

White Surfperch 

Striped Mullet 

Brown Rockfish 

Copper Rockfiib 

C$$b$ Rockfish 

Redstripe Rockfiih 

Sculpin 

Coastrange Sculpin 

Sumf.nerFlomder 

southem FIounder 

Flatheal Sole 

Diamond Turbot 

starry Flounder 

HomyheadTurbot 

Winter Flounder 

- 

WI 

M 

BOtb 

M 

M 

M 

M 

M 

- B 

Both B (Plants & Insects) 

M 

Both 

M 

M 

Both 

M 

M 

B 

B 

B 

P 

’ ~tine: M = Marine: F = Frcsfiwuc (II= iolralwcd 

2P=PtedaxB=BottomFeedcr 

’ Number of sites where fuh W~XC ~lkti ad mdyacd 

SOURCE: AFS. 1980 

pirc. I Piscivorau: OrMi. = Omnivaau 

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 1-t 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 dioxitifuran 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 tillet 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; pentachlorobenzene; 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 Cam 

The common carp I- 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 

Values calculated using whole body samples for bottom feeding species and fillet samples for Game Fish (predators). 

Values below detectbn have been replaced by one-hatl detection limit for the given sample. Asterisk indicates all values below detection. 

Units = w/g. 

-4 TEC 

I 13.06 

138 

TABLE S-4 

Average Fish Tissue Concentrations of Xeoobiotics for Mqjoor Species 

Bottom Feeders 

Valuer calcuhted using wble body samples for bottom leed~ng specms and Met samples for Game Fish (predatws). Values bebw derec~~on have been set at zero. 

Unlu - ngrg. unless noted. 
TABLE 5-5 

Detailed Summary of Occurrence of Prevalent Xenobiotics by Fish Species 

Values wre determvled usq whole body sampbs lot bottorrleeding species and frtlet samples lot pedalor species. 

Fast number indicates number ot samples whete detected; seumd numbec mdtcates total number of samples al dltterent slles lor @ven species analyzed. 

It mofe than 008 fillet or whole t&y sample of the same species at a stta was analyzed. only the highest value was used. 141 
their major food source. Adults consume fish, snails, plants, bottom ooze. insect Iarvae, insects, 

crustaceans, mobsks, and fish eggs. 

White Sucker 

The white sucker !m 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. piants, algae, insects, mollusks, and zooplankton. 

Channel Catfish 

The channel catfish BDunctatus) is found throughout the central part of the country 

and into parts of the western and eastern United States. 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 (Minvtrema 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 (m 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 (m 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 vitrm 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. 
White Bass 

The white bass (&Iorone m 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 > 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 (Pvlod.&s olivw is generally found in the central par@ 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 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 Crappie 

The white crappie (B 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 (Pomatomus 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 crayfuh consumes a smalIer 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 filter 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 filets 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 sitespecific 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 

alpha-BHC 

gamma-BHC (Lindane) 

Chlordane 

Chlorpyrifos 

p,p’-DDE 

Dicofol 

Dieldrin 

Endrin 

Heptachlor 

Heptachlor epoxide 

Hexachlorobenzene 

• 

• 

• 

• 

• 

• 

• 

• 

• 

• 

• 

Hexachlorobutadiene 

Isopropalin 

Mercury 

Mirex 

Pentachloroanisole 

Pentachlorobenzene 

Pentachloronitrobenzene 

Polychlorinated biphenyls (PCBs) 

1,2,4,5 Tetrachlorobenzene 

1,2,4 Trichlorobenzene 

Trifluralin 

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, carcinogenic 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)-1) 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-l 

Dose-Response Variables Used in Risk Assessment 

Analyte 

Cancer Potency 

Factor (CPF) 

(mg/kg/day)-’ 

EPA 

Cancer Reference 

Evidence mm 

Rating a (mg/kg/day) 

Biphenyl 

Chlordane 

Chlorpyrifos 

DDE Cp.p-> 

Dicofol (Kelthane) 

Die&in 

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 

- 

4.50xlooc 

9.10xlock 

;:p;$- 

- 

6.30x 10°c 

1.30x10*’ 

- 

1.80~10~~ 

1.60~10-~~ 

- 

- 

7.70x10°c 

NA 

B2 

NA 

B2 

C 

B2 

D 

B2 

B2 

B2 

C 

NA 

B2 

B2 

D 

R 

D,R 

D 

pending 

B2 

D 

D 

C 

5.00x 10-2b 

6.00x lo-5c 

;:;;;;$ 9 d 

- 

5.00x lo-“c 

3.00x lOA 

5.00x10k 

1.30xlo-5c 

8.00x lo* 

2.00x10-3c 

1.50x10-2c 

- 

3.00x IO& 

3.00x10-4e 

2.00x10-6c 

3.00x10-2e*f 

8.00~10~ 

3.00x10-3c 

l.OOxlO~h 

3.00x lo4 

2.00x 1 o-2c 

7.50x 10-3c 

a Designations are (IRIS, 1989): NA = not evaluated, B2 = probable human carcinogen, C = possible 

human carcinogen, D = not classified, R = under review by EPA. 

b Value from PHRED (1988). 

c Value from IRIS 1989 (data currew as of 9189). 

d Value is for DDT. DDE is assumed to have similar toxic properties. 

e Value from ATSDR (1987). 

f Value from HEAST (U.S. EPA, 1989c). 

g Value from EPA Region X toxicologist 

h RtD for kuochlor 1016. 

149 
l Defining chemical concentrations to be used, 

l Selecting consumption rates for various segments of the population, and 

l Estimating chemical doses. 

The detected fillet concentration at each site was used to estimate risks. If more than one 

fillet sample, exduding 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 estuarme 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 u-r 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 

(U.S. EPA, 1986b, 1989d). Exposure doses were determined using an equation that assumes a 

constant daily fish ingestion rate over a lifetime (70 years). 

D,i=(Ci x Z/)/W 

where: 

Dij = 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: 
Rq= I -t?Xp(-Do X Pi) 

where: 

Rij = Risk associated with chemical i at consumption rate j 

Pi = Carcinogenic potency factor for chemical i (tnU@g/day)m’ 

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: 

where: 

Hij = Hazard index of chemical i at consumption rate j 

Dij = Dose of chemical i at consumption rate j (mg/kg/day) 

RfDi = 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, RfD). 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 background 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 10m6 to 10m3 for each of the chemicals with CPF values. The highest lifetime risk levels are 

associated with total PCBs. The cancer risk exceeded 1OA at 42 of 106 sites for total PCBs, for a 

fish consumption rate of 6.5 g/day. PCBs also exceeded 10e3 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, cisand 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 Samplesa’b 

Chemical Maximumc Meand Mediane 

No. of 

Sites with 

Fillet Data 

PCBs 

DDE 

Combined Chlordanef 

Dieldrin 

or-Hexachloroc yclohexane 

y-Hexachlorocyclohexane 

Hexachlorobenzene 

Heptachlor 

Heptachlor Epoxide 

Mirex 

Trifluralin 

Dicofol 

Hexachlorobutadiene 

Pentachloroanisole 

3.7x w3 

8.9x1O-5 

9.3x1o-5 

6.0x103 

1.ox1o-5 

8.1x1o-6 

8.0~10-~ 

1.2x10-’ 

3.4x 1o-5 

3.8x 1O-5 

8.3x1o-8 

6.1x10-’ 

6.4x10-’ 

7.2~10-~ 

3.4x10A 

4. 1x1o-6 

3.6~10-~ 

2.2x 1o-5 

4.4x10-’ 

3.6x10-* 

2.5x10-’ 

1.1x10-’ 

8.7x 1O-6 

7.4x lo-’ 

1.7x1o-g 

2.8~10-~ 

7.1x1o-g 

2.ox1o-9 

6.0x 1O-5 106 

4.6x10-’ 106 

5.5x10-’ 106 

1.2x1o-6 106 

- 106 

- 106 

- 106 

- 106 

- 106 

- 106 

- 106 

- 106 

- 106 

- 106 

‘Consumption rate of fish set at 6.5 g/day. 

bCancer Potency Factors used are given in Table 6- 1. 

Cd’ Risk shown is associated with maximum, mean, and median fillet concentration at targeted sites. 

Values below quantification set at zero. 

fCombined chlordane is the sum of cis- and uans-chlordane isomers. cis- and trans-nonchlor isomers, and 

oxychlordane. 

*Dash indicates median fillet concentration was below detection. 

152 
TABLE 6-3 

Estimates of Potential Upper-Bound Cancer Risks at Backgroundd Sites 

Based on Fillet Samples 

No. of 

Chemical Maximuma Meanb Median’ 

Sites with 

Fillet Data 

PCBs 

DDE 

3.2x lO-5 8.ox1o-6 - 4 

1.4x1o‘6 4.1x10-’ 1.4x10-’ 4 

Consumption rate of fish set at 6.5 g/day. 

CPF values used are gtven in Table 6- 1. 

Dash indicates median fillet concentrauon was below detection. 

a. b*cRisk shown is associated with maximum, mean, and median fillet concentration at background sites. 

Values below quantification were set at zero. 

d 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 necessarity represent areas completely free from point and nonpoint sources of pollution. 

lbkluz 

All fillet concentrations at background sites were below detection for die&in, chlordane. alpha-BHC, gamma-BHC. 

hexachlorobenzene, heptachlor. heptachlor epoxide, mirex, trifluralin. dicofol. hexachlorobutadiene. and 

pentachlomanisole. 

153 
TABLE 6-4 

Fish Tissue Concentrations Used to Estimate Cancer Risks 

TARGETED SITES 

No. of 

Sites with 

Chemical Maximum Mean Median Fillet Data 

PCBs 5148.1 477.4 84.5 106 

DDE 2820 130.6 14.6 106 

Combined Chlordane 770 29.6 4.6 106 

Dieldrin 405 15.1 0.8 106 

oc-Hexachlorocyclohexane 17.5 0.75 ND 106 

y-Hexachlorocyclohexane 6.68 0.30 ND 106 

Hexachlorobenzene 50.7 1.6 ND 106 

Heptachlor 0.28 0.003 ND 106 

Heptachlor Epoxide 40.7 1.0 ND 106 

Mirex 22s 4.42 ND 106 

Trifluralin 116.0 2.35 ND 106 

Dicofol 14.9 0.68 ND 106 

Hexachlorobutadiene 88.3 0.98 ND 106 

Pentachloroanisole 48.6 1.3 ND 106 

Units are rig/g unless noted. 

BACKGROUND SITES 

Chemical Maximum 

PCBs 44.8 

Mean 

11.2 

Median 

ND 

No. of 

Sites with 

Fillet Data 

4 

DDE 43.0 13.0 4.4 4 

All fillet concentrations at background sites were below detection for dieidrin, chlordane. alpha-BHC. gamma-BHC. 

Hexachlorobenzene. heptachlor. heptachlor epoxide. mirex, trifluralin, dicofol, hexachlorobutadiene. and 

pentachloranisole. 

Combined chlordane is the sum of cis- and trans-chlordane isomers, cis- and trans-nonachlor isomers, and 

oxychlordane. 

154 
TABLE 6-5 

Number of Sites with Estimated Upper-Bound Risks 

Chemical 

No. of Sites 

with Fillet >10-6 >10-5 >lo’J 1o-3 

Data (>I in 1,OOO.OOO) (~1 in 100,OO) (>l in 10,000) (>1 in 1,000~ 

PCBs 106 89 

Dieldrin 106 53 

Combined Chlordane 106 44 

DDE 106 40 

Heptachlor Epoxide 106 9 

Alpha-BHC 106 II 

Mirex 106 8 

HCB 106 5 

Gamma-BHC 106 0 

Heptachlor 106 0 

Dicofol 106 0 

Hexachlorobutadiene 106 0 

Pentachloroanisole 106 0 

Trifluralin 106 0 

79 

31 

10 

10 

2 

1 

2 

0 

0 

0 

0 

0 

0 

0 

BACKGROUND SITES 

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 

Chemical 

VEL (cm 

No. of Sites 

with Fillet >1C6 >lO -5 >10-4 

Data (>I in l.OOO,OOO~ (>l in 100,000) +l in lO,m) (>l in 1,000~ 

PCBS 4 1 1 0 0 

DDE 4 1 0 0 0 

Basis: 1) Used EPA (i.e., upper bound) cancer potency factors. 

2) Used consumption rale 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 uans-nonachlor isomers. and 

oxychlordane. 

1.55 
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 tillet concentrations at targeted sites, estimated 

risks equal or exceed 10m5 for PCBs at 6.5 g/day and 30 g/day. At the higher consumption rate of 

130 g/day, estimated risks due to combined chlordane and dieldrin were also above 10e5. 

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 

low6 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 

(Le., 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 (TabIe 6-7). Based on a fish consumption rate of 

6.5 g/day, the hazard index, defined previously, exceeded I (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 .O. 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 compoundsevaluated. 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 (2,8 19 ng/g), a hazard index value 

of 0.52 was estimated for a 6.5~g/day consumption rate, while 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 MlXll Metli:m 

6.5 30 140 6.5 30 140 6.5 30 14p 

KBS 3.2~10-~ I .5xMs4 6.9x 1O-4 FCBS 8.ox1o-6 3.7x10-* I .7x Id f’CBs 

DDE 1.4x1o-6 6.4x 1O-6 3.oxlo-5 DDE 4.1xlo-7 1.9x w6 8.8x w6 DDE I .4x 1o-7 6.4, lo-’ 3.oxici' 

65 ^ 30 140 Teed 6.5 30 140 . 6.5 30 l@ 

fX1BS 

DIE 

Combined 

chlordane 

Dicofol 

Dieldrin 

3.7x 10-j 

8.9x10-’ 

9.3xlo-5 

6.lxl0-7 

6.0x 1 0-4 

a-Henacbloro- 1.0x 11 

cyctobexane 

y-Hexachlom- 8. lx I 

cyclohexane 

I lexachlow 8.0x I’ 

benzene 

1 fexachlow 6.4x 

butadiene 

I Ieptachlor 1.2x 1 

f ieptachfor 

@oxide 3.4x 1 

Mirex 3.8x 1, 

f’entachloro- 7.2x 10.’ 

anisole 

Triffuralin 8.3x lo-g 

l.7x10YL 

4.lxfo-4 

4.3x lo-4 

2.8x w6 

2.8x 1 O-3 

4.6x 1, tJ-5 

3.7x1 O-6 

3.7x1 O-5 

3.Oxf, o-6 

5.4x 1 O-6 

1.6x 1 0.4 

1.8x 1 o-4 

3.3xlo-7 

3.8x 10S7 

7.6x lo-L 

l.9x1O-3 

2.0x lo-3 

1.3x lOA 

1.3x10.* 

2.2x lo-4 

1.7x 1o-5 

I .7x 1o-4 

f.4x1o-5 

2.5x 1o-5 

7.3x 1o-4 

8.2x lo-4 

I .6x 1 o-6 

1.8x 1om6 

PCBS 3.4x10-” 

DDE 4.lxlo-6 

Combined 3.6~10-~ 

Chlordane 

Dicofoi 2.8x wn 

Diefdrin 2.2x10J-5 

a-Hexachloro- 4.4x IO-’ 

cyclohexane 

y-flexachlomcyclohexane 

fIexachlor+ 

benzene 

Hexachlor+ 

butadiene 

1 feptachlor 

ffeptachlor 

@oxide 

Mirex 

Pentachloro 

anisole 

Triflurafin 

3.6x10‘” 

2.5x 1o-7 

7.1x1O-y 

* 

8.4x1o.7 

7.4x 1o-7 

1.9x10-” 

1.7x10-” 

1.6x IO-’ 7.3x 10-j 

l.9xlo-5 8.9x 10-5 

1.6~10.~ 7.7xlOP 

1.3x10-’ 

l.oxlO-J 

2.0x 10.” 

1.7x10-’ 

1.2x& 

3.3x1o.s 

* 

3.9xlo-6 

3.4xlo-6 

8.9x10-* 

7.8xlo-y 

6.0x i(S7 

4.Xx IO-j 

9.4x I o-6 

7.8x w6 

5.4x lo-6 

lsxlO-’ 

* 

1.8x1o-5 

1.6~10-~ 

4.2x IO‘” 

3.6x IO-” 

PCBS 6.0x lo-’ 2.8x 10.’ 

DDE 4.6s 

Combined 5.6x 

Chlordane 

Ik4~fol - 

Dieldrin 1.2x I 

a-f iexachloro- - 

cycfobexane 

y-l fcxachlom- - 

cyclohexane 

I fexachlor@ - 

benzene 

I lexachloro- - 

butadiene 

I feplachlor - 

f feptach tor - 

Epoxidc - 

Mircx 

f’entachloro- - 

anisole 

Triflurafin - 

o-’ 2.1N” 

C7 2.6x 1o-6 

tJ-’ 5.5~ 1tS’ 

1.3x10-’ 

9.9xN6 

1.2xlO 5 

Basis: Used upper-hound CPFs CTaMe 6-2) fish consumpion rates of 6.5.30. and I40 g/day. 

Dash indlcater concentration was reporwd as not dewctzd. 

‘Only one value was abws delectwn. so risk nd cornouted. 

(‘ombmed chlordane is the sum of cis- and tram-ddordane ~swners. cis- and trans.nonachltx ~sonwrs. and oxychltrane. 

157 
p,p=DDE 

1o-3 

10' 

10-5 

lo6 

1o-7 

lo6 

O.OOQOO1 o.oooo1 0.0001 0.001 0.01 0.1 1 10 100 1000 

Fish Tissue Concentration 

(mg/kg wet wt) 

Figure 6-l. Graphical tool for estimating upper-bound cancer risk of p,p’-DDE or equivalents 

for different fish consumption rates. 

IS8 
TABLE 6-7 

Noncarcinogenic Hazard Index Values at Targeted and Background Sites 

Based on Fiilet Samples 

TARGETED 

Chemical Maximum Mean Median 

No. of 

Sites with 

Fillet Data 

Biphenyl 

Combined Chlordane 

Chloropyrifos 

DDE 

D ieldrm 

Endrin 

y-Hexachlorocyclohexane 

Hexachlorobenzene 

Heptachlor 

Heptachior Epoxide 

Hexachlorobutadiene 

lsopropalin 

Mercury 

Mirex 

Pentachloroniaobenzene 

Pentach lorobenzene 

Pentachloroanisole 

PCBs 

I ,2,4,5 Tetrachlorobenzene 

1,2,4 Trichlorobenzene 

Trifluralin 

9.8x10-j 

1.2 

2.4x1 O-3 

5.2x10-l 

7.5x10-l 

4.3x1o-3 

2.1x1o-3 

5.9x1o-3 

5.2x1 O-5 

2.9x1 0-l 

4.1x1o-3 

“3 5.1x10- 

10.45 

2.7x1 0-I 

20x1 o-6 

4.6x1 o-2 

6.4x1 o-5 

2.4x1 O-2 

2.8x1 O-’ 

9.6x1 0-’ 

9.3x1 o-5 

1.9x10-” 

5.6x10-’ 

7 1xlo-3 

4.6~10-~ 

N 

s 9.0x10-. 

2.1x10-’ 

2.5x1 0-7 

6.0x1 0-’ 

1.5x10-j 

1.3x10-’ 

4 0x1 o-6 

4.78 

8.8x1 O-3 

4.4x1 0-l 

4.8x10-” 

1.2x10-” 

1 .4x1o-3 

7.2~10-~ 

2.9x1 0-’ 

3.5x10-’ 

7.lx1o-3 

ND 

2.7x1 O-3 

l.5xlo-3 

ND 

ND 

ND 

ND 

ND 

ND 

NS 7.1x10 

ND 

ND 

ii; 

7,8x10-’ 

N9 6.5x1 OND 

106 

106 

106 

106 

106 

106 

106 

106 

106 

106 

106 

106 

182 

106 

106 

106 

106 

106 

106 

106 

106 

BACKGROUND 

Chemical Maximum Mean Median 

No. of 

Sites with 

Fillet Data 

Biphenyl 

Combined Chlordane 

Mercury 

1,2,4 Trichlorobenzene 

3.7x1o-7 

5.0x1 o-3 

2.2x10-’ 

l.oxlo-3 

2.5x10-’ 4 

5.5x10-l 1.5x10-l 

ND 4 

3.3xlCF 

1.2x10-l 1 

4.2x1 0-’ 

1.6~10-~ 

1 .ox1o-2 

1.5x1o-6 4 

PCBs 

8.0x1 O-3 2.0x1 o-3 

N 4 

p,p’-DDE s 1.0x10‘ 4 

(All other chemicals were not detected in background samples) 

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 

Consumption Rate (grams/day) 

1000 100 IO 

0.01 0.1 1 10 

Fish Tissue Concentration 

(mg/kg wet wt) 

100 1000 10000 

Figure 6-2. Graphical tool for estimating upper-bound noncarcinogenic hazard index of 

p,p’-DDE for different fish consumption rates. 

160 
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. Environmental 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. 

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Chemists. 13th ed., pp. 404-406. 

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NTP (National Toxicological Program). 1982a. Bioassay of 2,3,7,8-Tetrachloro-dibenzo-p-dioxin 

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Olson, G.F., D.I. Mount, V.M. Snarski, and T.W. Thorslund. 1975. Mercury Residues in Fathead 

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Palmer, F.H., R.A. Sapudar, J.A. Heath, N.J. Richard, and G.W. Bowes. 1988. Chlorinated 

Dibenzo-p-Dioxin and Dibenzofuran Contamination in California from Chlorophenol Wood 

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18(3):78A-90A. 

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Scott, W.B., and E.J. Crossman. 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 

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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. 

Takamiya, K. 1987. Residual Levels of Plasma Oxychlordane and Trans-nonachlor in Pest Control 

Operators and Some Characteristics of These Accumulations. Bull. Environ. Contam. Toxicol. 

39: 750-755. 

Tobin, P.M. 1984. Memo to S. Schatzow of U.S. Environmental Protection Agency, Office of 

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162 
Trautman, M.B. 1957. The Fishes of Ohio. Ohio State University Press, Columbus, OH. 

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R3-73-033. 

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Protection Agency, Office of Water Regulations and Standards. EPA 440/5-80 Series. 

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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, Office of Water Regulations and Standards, Washington, DC. EPA440/5-85 

Series. 

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Protection of Aquatic Organisms and Their Uses. U.S. Environmental Protection Agency, 

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Environmental Protection Agency, Office of Water Regulations and Standards, Monitoring and 

Data Support Division, Washington, DC. July 1986. 

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Agency, Office of Emergency and Remedial Response, Washington, DC. EPA 540/l-86/060. 

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87 Series. 

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163 
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PCDDKDF in Fish. U.S. Environmental Protection Agency, Washington, DC. EPA/600/3- 

90/022. 

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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 factorsused to estimate risks 

(e.g., CPF, RfD, BCF). 

164 
Glossary 

Bioaccumulation 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, 

BCF The bioconcentration factor (BCF) is the partition coefficient for the distribution 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 

chemical 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. 

CPF 

Combined Combined chlordane is the sum of cis- and trans-chlordane isomers, cis- and 

Chlordane trans-nonchlor isomers, and oxychlordane. 

Congeners 

Cancer potency factor expressed in units of (mg/kg/day)-1 based on experiments 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. 

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. 

GC/MS Gas chromatography/mass spectrometry, a laboratory analytical method 

used in this study for PCDDs, PCDFs, and other xenobiotic compounds. 

Hazard Index 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 

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 Super-fund 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 advocated by EPA was used for this study (Barnes et al., 1989). 

TEF Toxicity equivalency factors for dioxins and furans. These factors express 

the relative toxicity of the 2,3,78-substituted congeners. The values used in 

this study were from the 1989 interim method (Barnes et al., 1989). 

TEQ Toxicity equivalents for dioxins and furans (Barnes et al., 1989). This term 

has the same meaning as TEC. 

Total Chlordane Total chlordane refers to the sum of the measured concentration of cis- and 

trans-isomers of chlordane measured in the same sample. 

TTR Total toxic residue equals the combined concentration of cis- and trans-chlordane, cis- and trans-nonachlor, oxychlordane, and the four chlordene isomers. This combined concentration is used by EPA’s Office of Pesticide 

Programs. 

Xenobiotic Compounds that do not naturally occur in living organisms. 

166 
APPENDIX A 

Laboratory QA/QC Procedures and Results 
APPENDIX A-1 

Analysis of Laboratory QA/QC Data 
Appendix A-1 - 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 analyte 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 pentadioxin/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 analyte recovery 

and total analyte recovery. The bias for specific analytes must be between +50 percent and +130 

percent, except for the following compounds: 

A-1-1 
TABLE A-1 

Laboratory Quality Assurance Procedures 

1. All instrument maintenance schedules maintained according to the manufacturer’s 

recommendations 

2. Gas Chromatography (GC) performance 

a) Xenobiotics 

2. 

1. 

<0.995 

3. 

1. Column resolution (number of theoretical plates of resolution must not 

decrease by more than 20%) 

Relative retention times (3%) of internal standards 

b) PCDD/PCDF 

2. 

Resolution of 1,2,3,4 TCDD from 2,3,7,8 TCDD must be 0.75 

The R2 value of the regression of the relative retention time of all 

biosignificant PCDD/PCDF to the library relative retention should not be 

3. Elution of all PCDD/PCDF during analysis from a GC window defining 

solutions of select PCDD/PCDF congener groups (first eluted/last eluted) 

Mass Spectrometry (MS) performance 

a) Xenobiotics 

1. Sensitivity (signal-to-noise ratio, 3.0 for m/z 198 from injection of 10.0 ng 

decafluorotripenylphosphine [DFTPP]) 

2. Spectral quality (intensity of ions in the spectrum of DFTPP must meet 

specified criteria) 

b) PCDD/PCDF 

2. 

4. 

1. Sensitivity and linearity 

tridecane) which varied 

were evaluated using calibration standards (in pg/μl 

in concentration 

3. 

Mass resolution was a minimum of 5,000 (10% valley definition) 

Percent relative standard deviations for the mean response factors were <20% 

Gel Permeation Chromatography (GPC) performance 

a) Xenobiotics 

1. 

2. 

3. 

Column flow rate (not vary by more than 0.2 ml/min) 

Column resolution (daily injection of performance solution) 

Collection cycle (start and end of the collect cycle must not deviate by more 

5. Silica Gel Chromatography performance 

a) Xenobiotics 

1. Evaluated by its ability to resolve cholesterol from a select model target 

analyte, dieldrin 

A-1-2 
TABLE A-2 

Quality Assurance Parameters for Dioxins and Furans 

TCDD 

Ion Ratio 

0.76&15% 

Methoda Accuracya Precisionb S/N 

Efficiency at 10 pgfg at 10 pg/g Minimum 

>40%,<120% k50% SO% 3.0 

PCDD 0.61f158 >40%*<120% SO% SO% 3.0 

HxCDD 1.23+15% >40%,<120% flOO% flOO% 3.0 

HpCDD 

TCDF 

l.O2fl5% >40%,<120% flOO% flOO% 3.0 

0.76&15% >40%,< 120% k50% SO% 3.0 

PCDF 1.53f15% >40%,<120% SO% SO% 3.0 

HxCDF 1.23f15% >40%.<120% flOO% flOO% 3.0 

HpCDF l.O2Ik15% >40%,< 120% 200% 200% 3.0 

’ Variance of measured value from actual. 

b Variance of difference of duplicates from mean. 

A-l-3 
TABLE A-3 

Bias Analysis for PCDDdPCDFs 

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 

I ,2.3,4.7,8 HxCDF 

1,2.3,6,7,8 HxCDF 

2.3.4h7.8 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. % Bias 

16 9 

13 2 

14 4 

12 4 

13 0 

10 -5 

17 4 

11 -4 

12 -6 

24 -1 

13 8 

11 -4 

11 -1 

14 4 

12 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-l; 

. Pentachlorohenzene: 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-41. 

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 

crhia. 

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 0.00 13 

t.tg/g tissue. Analysis and EPA reference fish (mean value 2.52 pg/g, standard deviation (s) = 0.64) 

throughout the study gave a mean mercury value of 2.87 pg/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, 

1986a) 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 
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 

Mean 

Recoverv Stan. Dev. % Bias 

Tetrachlorobiphenyl 63 16.5 -37 

Pentachlorobiphenyl 90 12 -10 

Hexachlorobiphenyl 108 11 8 

Heptachlorobiphenyi 99 23 -1 

A-l-6 
TABLE A-6 

Bias Analysis for Xenobiotics 

Chemical 

Mean 

Recovery Stan. Dev. 7% Bias 

1.3.5 Trichlorobenzene 25 7 -75 

1,2,4 Trichlorobenzene 25 11 75 

1,2,3 Trichlorobenzene 21 11 -79 

1,2,4.5 Tetrachlorobenzene 32 16 -68 

1,2,3,5 Tetrachlorobenzene 39 12 -61 

Biphenyi 27 10 -73 

1,2,3,4 Tetrachlorobenzene 33 15 -67 

Pentachlorobenzene 43 16 -57 

Trifluralin 86 25 -14 

alpha-BHC 67 18 -33 

Hexachlorobenzene 58 16 -42 

Pentachloroanisole 67 18 -33 

gamma-BHC (Lindane) 64 16 -36 

Pentachloronitrobenzene 71 19 -29 

Diphenyl disulfide 82 26 -18 

Heptachlor 68 18 -22 

Chlorpyrifos 106 16 6 

Isopropalin 84 49 -16 

Octachlorostyrene 96 24 -3 

Heptachlor epoxide 88 11 -12 

Oxychlordane 76 14 -24 

Chlordane, trans 92 15 -8 

Chlordane, cis 97 24 -3 

Nonachlor. uans 96 22 -4 

p,p’-DDE 95 23 -5 

Dieldrin 100 14 0 

Nitrofen 114 20 14 

Endrin 102 14 2 

Perthane 78 32 -22 

Nonachlor, cis 99 22 -1 

Methoxychlor 55 27 -35 

Dicofol 96 27 -4 

Mirex 90 20 - 10 

A-1-7 
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. 

3 d. The detection limit for a batch analysis is not to exceed 50% above the detection limit of 

0.050 @g tissue, or samples are reanalyzed. 

_ 3 . Complete reagent blanks are to produce a mercury signal equivalent to less than 0.15 

pg/g tissue. 

3. 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-1-8 
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 

# of 

Observations 

51 

13 

41 

14 

29 

Precisiod (pg/g) 

s=O.O7X 

s=o.osx 

s=O.O8X 

s=o.2 1 

s=o.o9x 

Concentration 

Range (pg/g) 

1 to 100 

1 to 30 

1 to 120 

1 to 10 

1 to 50 

1,2,3,7,8 PeCDD 25 SO.9 1 

1,2,3,4.7,8 HxCDF 18 s=1.37 

1.2,3,6.7,8 HxCDF 9 s=O.llX 

2,3,4,6,7,8 HxCDF 11 s=o. 17x 

to 30 

to 50 

to 30 

to 5 

1,2,3,4,7,8 HxCDD 11 s=o. 13x 1 to 10 

1,2,3,6,7,8 HxCDD 29 s=O.llX 1 to 35 

1,2,3,7,8,9 HxCDD 8 s=o. 11x 1 to 10 

1,2,3,4,6,7,8 HpCDF 11 s=o.77 1 to 15 

1,2,3,4,6,7,8 HpCDD 33 s=O.O8X 2 to 150 

“X = concentration 

s = standard deviation 

A-I-9 
TABLE A-9 

Intralaboratory Precision Measurements for Replicate Pairs for Xenobiotic Analysis 

Chemical 

Number of Concentration 

Observations Precisiona (ng/g) Range (q/g) 

1.35 Trichlorobenzene 5 

1,2,4 Trichlorobenzene 5 

1.2,3 Trichlorobenzene 5 

Hexachlorobutadene 6 

Biphenyl 5 

1.2,3,4 Tetrachlorobenzene 6 

Pentachlorobenzene 5 

Trifluralin 6 

alpha-BHC 7 

Pentachloroanisole 10 

gamma-BHC (Lindane) 8 

Pentachloronitrobenzene 5 

Heptachlor 6 

Chlorpyrifos 8 

Isopropalin 7 

Heptachlor epoxide 6 

Oxychlordane 11 

Chlordane, uans 14 

Chlordane, cis 13 

Nonachlor, trans 21 

p.p’-DDE 29 

Dieldrin 17 

Endrin 5 

Nonachlor, cis 13 

Dicofol 5 

Mirex 5 

Tetrachlorobiphenyl 14 

Pentachlorobiphenyl 26 

Hexachlorobiphenyl 28 

Heptachlorobiphenyl 21 

Octachlorobiphenyl 6 

Hexachlorobenzene 4 

s=13.05 

s=O.28X 

s=5.39 

s=o.39x 

s=o. 19x 

s=o.35x 

s=o.o4x+5.04 

s=o. 19x 

s=0.05x+1.70 

s=o.25x 

so. 12x 

s=38.8 1 

s=7.44 

s=O.O5X+8.09 

s=38.43 

SO. 13x 

s=o. 12x 

s=o. 10x 

s=o. 10x 

s=O. 16X 

s=o. 17x 

s=o. 10x 

s=o. 10x 

so. 13x 

s=O.O3X+5.66 

s=o.o7x 

So. 17x 

so. 16X 

so. 14x 

s=S. 33 

s=o.15x+1.41 

N/A 

40 to 100 

8 to 120 

I5 to 120 

30 to 150 

4 to 110 

30 to 150 

50 to 200 

2.5 to I50 

2.5 to 250 

2.5 to 240 

3 to 240 

70 to 280 

50 to 250 

4 to 300 

10to500 

15 to260 

4 to 300 

3 to 300 

3 to 200 

4 to 400 

10 to400 

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 

‘X= concenuation 

s = standard deviation 

A-I-10 
standard deviation, s. and coefticient 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 octachlorostyrene, 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 pg/g in the concentration 

range of 0.08 ug/g to 1.79 pg/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 QAIQC 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-i-11 
APPENDIX A-2 

Analytical Procedures and Quality Assurance Plan for 

the Determination of PCDD/PCDF in Fish 
United States 

Environmental Protection 

Agency 

Environmental Research 

Laboratory 

Duluth MN 55804 

EPA/600/3-90/022 

March 1990 

EPA 

Research and Development 

Analytical 

Procedures and Quality 

Assurance Plan for the 

Determination of 

PCDD/PCDF in Fish 
EPA/600/3-90/022 

March 1990 

U.S. Environmental Protection Agency 

national Dioxin Study - Phase II 

Analytical Procedures and Quality Assurance Plan 

for the Determination of PCDD/PCDF in Fish 

Environmental Research Laboratory 

Office of Research and Development 

U.S. Environmental Protection Agency 

Duluth, MN 55804 
NOTICE 

The information in this document has been funded wholly or in part by the U.S. 

Environmental Protection Agency. It has been reviewed technically and 

administratively. Mention of trade names or commercial products does not 

constitute endorsement or recommendation fur use. 

12/89 QA/QC PCDD/PCDF ii 
ACKNOWLEDGEMENTS 

Technical contributions to this research were made by: 

U.S. Environmental Protection Agency 

Brian C. Butterworth 

Douglas W. Kuehl 

ASCI Corporation 

Phillip J. Marquis 

Marie L. Larsen 

Larry G. Holland 

Christine E. Soderberg 

Jennifer A. Johnson 

Kevin L. Hogfeldt 

University of Wisconsin-Superior 

Elizabeth A. Lundmark 

Daniel M. Fremgen 

Sandra Naumann 

Murray Hackett 

Kent Johnson 

Harvey D. Corbin, Jr. 

Dr. Ray L. Hanson 

Wright State University 

Dr. Thomas Tiernan 

Dr. Michael Taylor 

12/89 QA/QC PCDD/PCDF iii 
FOREWORD 

Directed by Congressional mandate, the U.S. Environmental Protection Agency 

during 1983 initiated the National Dioxin Study, a survey of environmental 

contamination by 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) 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 

Research Laboratory - Duluth, was responsible for one part of the Study, the 

analysis of fish samples. The most significant findings of these analyses was 

the observation that fish contamination was more widespread than previously 

thought, and that a primary source of TCDD 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 Dioxin Study. This document describes the 

analytical methods used for the determination of the level of contamination of 

fifteen biosignificant polychlorinated dibenzo-p-dioxins and dibenzofurans in 

fish. A companion document (EPA/600/3-90/023) describes the analytical methods 

used for the determination of levels of contamination of polychlorinated 

biphenyls, pesticides, and industrial compounds in those same fish. 

12/89 QA/QC PCDD/PCDF iv 
TABLE OF CONTENTS 

DISCLAIMER . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ii 

ACKNOWLEDGEMENTS. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ii i 

FOREWORD. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iv 

I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . 1 

II. Sample Preparation 

A. Grinding 

. . . . . . . . . . . . . . . . . . . . . . . . 3 

B. Extraction . . . . . . . . . . . . . . . . . . . . . . . . 3 

C. Percent Lipid Determination . . . . . . . . . . . . . . . . . . . . . . . . 3 

D. Anthropogenic Chemical Isolation . . . . . . . . . . . . . . . . . . . . . . . . 5 

E. Florisil Chromatography . . . . . . . . . . . . . . . . . . . . . . . . 5 

F. PCDD/PCDF Isolation . . . . . . . . . . . . . . . . . . . . . . . . 5 

III. Reagents and Standards . . . . . . . . . . . . . . . . . . . . . . . . 6 

A. Reagents . . . . . . . . . . . . . . . . . . . . . . . . 6 

B. Standards . . . . . . . . . . . . . . . . . . . . . . . . 7 

IV. Instrumental Parameters. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 

V. quality Assurance/Quality Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 

A. General Procedures of Operation. . . . . . . . . . . . . . . . . . . . . . . . 13 

B. Instrumental Quality Control. . . . . . . . . . . . . . . . . . . . . . . . 20 

C. Evaluation of Data. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21 

1. Accuracy . . . . . . . . . . . . . . . . . . . . . . . . 21 

2. Precision. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23 

3. Signal Quality Assurance Requirements. . . . . . . . . . . . . . . . . . . . . . . . 23 

4. Polar Gas Chromatographic Confirmation Analysis. . . . . . . . . . . . . . . . . . . . . . . . 23 

D. Quality Assurance Problems and Corrective Actions. . . . . . . . . . . . . . . . . . . . . . . . 24 

12/89 QA/QC PCDD/PCDF v 
VI. Quantificatlon Procedures. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25 

A. Initial and Daily Calibration of the HRMS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25 

B. Signal Quality . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27 

C. Quantification of PCDD/PCDF. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29 

D. Method Efficiency. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30 

E. Integration of Automated Data Processing and Quality 

Assurance. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31 

TABLES 

Table 1 -- Biosignificant PCDDs/PCDfs . . . . . . . . . . . . . . . . . . . . . . . . 1 

Table 2 -- Minimum Level of Detection Limit . . . . . . . . . . . . . . . . . . . . . . . . 2 

Table 3 -- Internal Standard Solutions . . . . . . . . . . . . . . . . . . . . . . . . 4 

Table 4 -- Calibration Standards . . . . . . . . . . . . . . . . . . . . . . . . 9 

Table 5 -- Relative Recantron lines 4-8 PCDD Isomers. . . . . . . . . . . . . . . . . . . . . . . . 10 

table 6 -- Relative Retention Times 4-8 PCDF Isomers. . . . . . . . . . . . . . . . . . . . . . . . 11 

Table 7 -- HRGC/HRMS Operating Parameters. . . . . . . . . . . . . . . . . . . . . . . . 12 

Table 8 -- Native PCDD/PCDf Spiking Solution. . . . . . . . . . . . . . . . . . . . . . . . 14 

Table 9 -- Codes for the SEC Number and Matrix Type. . . . . . . . . . . . . . . . . . . . . . . . 19 

table 10 -- GC Column Performance Quality Control. . . . . . . . . . . . . . . . . . . . . . . . 20 

Table 11 -- GC Elution Window Defining Solutions for 

D8-5 Column . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21 

Table 12 -- Quality Assurance Parameters. . . . . . . . . . . . . . . . . . . . . . . . 22 

Figures 

Figure 1 -- Database Format for Sample Information . . . . . . . . . . . . . . . . . . . . . . . . 17 

Figure 2 -- 2,3,7,8-TCDD Weighted Calibration Curve. . . . . . . . . . . . . . . . . . . . . 26 

Figure 3 -- Data Reduction for PCDD/PCDF National Dioxin Study . . . 32 

12/89 QA/QC PCDD/PCDf vi 
I. Introduction 

This document, "Analytical Procedures and Quality Assurance Plan for the 

Determination of PCDD/PCDF in Fish” has been drafted in response to the need 

for the Environmental Research Laboratory of Duluth (ERL-D) to perform analysis 

for tetrachloro- to octachloro- congeners/isomers of polychlorinated dibenzop-dioxins and dibenzofurans (PCDD/PCDF), Table 1. 

Table 1. Biosignificant PCDDs/PCDFs 

Analyte CASRN 

2378-TCDF 

2367-TCDF 

3467-TCDF 

2378-TCDD 

12378-PeCDF 

23478-PeCDF 

2346T-PeCDF 

12378-PeCDD 

123467-HxCDF 

123478-HxCDF 

123678-HxCDF 

234678-HxCDF 

125789-HxCDF 

123478-HxCDD 

123678-HxCDD 

123769-HxCDD 

1234678-HxCDF 

1234789-HpCDF 

1234678-HpCDD 

51207-31-9 

1746-01-6 

57117-41-6 

57117-31-6 

70648-29-9 

40321-76-4 

70648-26-9 

57117-44-9 

60851-34-5 

72918-21-9 

32598-13-3 

57753-85-7 

19408-74-3 

67562-39-4 

55673-89-7 

37871-00-4 

12/89 QA/QC PCDD/PCDf 
These analyses are limited by lack of analytical standards; however isomer 

specificity may be determined using specially developed standards. Analytical 

results will, therefore, be reported as concentration (pg/g) for each gas 

chromatography (GC) peak in a congener class by making the assumption that 

the response for the molecular ion of all isomers in that class is equal to 

the response observed for the isomer for which ERL-D does have a standard. 

The target minimum level of direction (MLD) for specific PCDD/PCDF isomers is 

given in Table 2 below. This document is meant to be only a guideline for 

analyses and may be modified as needed to satifactorily analyze any sample. 

Table 2. Minimum Level of Detection Values 

Target Minimum 

PCDD/PCDF Level of Detection 

TCDD, TCDF 1 pg/g 

PeCDD, PeCDF 2 pg/g 

HxCDD, HxCDF 4 pg/g 

HpCDD, HpCDF 10 pg/g 

12/89 QA/QC PCDD/PCDf 2 
II. Sample Preparation 

A. Grinding: Frozen fish wrapped in aluminum foil are sent to 

the ERL-Duluth laboratory. Now the fish is ground, (whole body 

or fillet), is dependent on the species. Bottom feeders are ground 

whole and predators are filleted with the skin off. Fish tissue is 

ground frozen in a stainless steel power meet grinder. Each 

sample is processed through the grinder three times which 

homogenizes it thoroughly. The ground tissue is stored at 

-20° C in solvent rinsed glass jars with aluminum lined 

plastic lids. 

B. Extraction: Tissue (20 g) is blended with enough anhydrous 

sodium sulfate to dry the tissue (100 g). Two-thirds of the sample 

is placed in a glass Soxhlet thimble, spiked with 100 ul of each Standard 

Solution A and B (Table 3) and then the remainder of the sample 

is added to the thimble. The sample is extracted at least twelve 

hours with a 1:1 mixture of hexane and methylene chloride in a 

Soxhlet extractor. The sample is quantitatively transferred to 

a 500 ml Kuderne-Danish apparatus and prewashed boiling chips 

are added. 

C. Percent Lipid Determination" The sample extracted in 

section 1.8. of sample preparation is used to determine percent 

lipid. After sample concentration, the KD lower tube is placed in a 

60° C water bath under a gentle stream of dry carbon filtered 

air. After any remaining solvent has been evaporated, the lower 

12/89 QA/QC PCDD/PCDF 3 
tube and contents are weighed. The lipid is then quantitatively 

transferred to the macro column as directed in Section 1.D. of 

sample preparation. After transfer, the empty lower tube and 

boiling chips are weighed. The percent lipid is calculated from 

the weight differences. 

Table 3. Internal Standard Solutions 

Concentration Concentration 

Compound in solution (pg/uL) in tissue (pg/g*) 

Internal Standard Solution B. 

12/89 QA/QC PCDD/PCDF 4 
0. 4nthroooaenlC Chemicel Isolotlon: Ihe srnPle extract 11 

qu~nt~trtlvely rrrnrferrrd to I 30 Cm K 2.5 Cm Qt6SS ChrOmaK09raphy 

column (MACRO-columns) fitted with e 300 mi reservoir on top. 

The Column has been packed ulCh 8 PlUQ of 9lass uoot (botron to 

toe), 2 g silica gel, 2 g patesslum Siliceto, 2 0 sodium sulfate 

10 0 cellte/sulfuric acid and 2 g sodium sultete, and previously 

ueehed uitk 100 mL herrne. The column is elutrd with 100 mu 

benzeno/hexrne (5X) and the l luent is coilecred in e xudernr-Denish 

(I(D) rpparrtus (Caution: benzene is e knoun cercinogen). Isooctene 

(1.0 mL) is added, the volume is reduced end then transferred co the 

florisil column. 

E. C[orisil Chrommtoaraohv: A 1.0 cm a 20.0 cm gl8ss chromrtogrrphy 

column fitted uith e 100 mL reservoir is pecked uith B plus of gLe#r 

uool (bottom to too), 5.0 cm (1.5 g) ectivrtrd floriril rnd 1.0 cm 

rodiur sulfate. The fLorisi1 is activeted JC 120' C for 2C hours. 

The column is ueshed utth 20 ml methylene chloridr fotloued by 10 ml 

hrrrnr. Senple rnd tuo 1 ml herrne rinses ere quentitrtively 

epplied in small “pt~gs”. The column is l luted with 20 mL 2X 

mothylene chlorido/hrxane end the l lulto dlscardod. This uash is 

follourd by SO a~ nothylenr chloridr uhith flour directly onto the 

micro cerbon/rilca gel column for PCOO/PCOt isolation. 

f. PCDD/PCOI Jsol8tion: Effluent from the florisil column is 

parsed onto I 4 mm I 200 mm column (micro-column) contrining 

300 l g silicr gol/crrbon (soa sec. 111.A.6) uhich YIS previously 

rlnrrd uitk 10 aI tolurnr foliourd by 10 ml nethylrnr chloridr. 

Iha coluen ir fittrd uith a rolvont rrarrvoir. After the sample 

krr rteort corplrtoly l lutod from the micro-column, the rrrrrvoir 

fr warhod tuicr with 2 q L 25% brntrnr/rethylenr chloride rnd the 
column is finally eluted with en additional 11 mL 25% benzene/ 

methylene chloride. The column is inverted on the reservoir end 

the PCDD/PCDF are eluted with toluene (25 mL). The toluene 

fraction is collected in a pear shaped flask (25 mL) end reduced 

in volume to 0.1 mL in a 60° C water bath under a gentle 

stream of dry carbon filtered air. The sample is transferred to 

a microvial using toluene to 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). 

III. Reagents and Standards : 

A. Reagents: 

1. Solvents: Only pesticide grade distilled in glass solvents 

are used. They are: hexane, isooctane, methylene chloride, benzene, 

toluene, acetone, and methanol (Burdick and Jackson, Fischer 

Scientific). 

2. Sodium Sulfate: Sodium sulfate (Baker 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. 

3. Silica Gel: Silica-Gel-60 (Merck-Darmstadt), is Soxhlet 

extracted eight hours with methanol, placed on solvent rinsed foil, 

air dried for 72 hours, and vacuum oven dried (125°C) for 24 

hours. It is stored in en empty hexane solvent bottle. Prior to 

use it is activated at 105° C for 24 hours. 

4. Sulfuric Acid/Celite : Sulfuric acid (Baker Chemical Company, 

Ultrex) (5 mL) is blended in a 250 mL beaker with Celite 545 

(Baker) (10 g). 

12119 QAlQC PCOD/PCDI 6 
5. Potassium Silicate: High purity potassium hydroxide (Aldridge 

Chemical Company) (56 g) is dissolved in methanol (300 mL). 

Silica-gel (100 g) is added to the mixture and stirred (1 hour, 

60° C). The mixture is cooled and the Solvent is removed using 

a Buchner funnel. The potassium silicate is rinsed twice with 

100 ml of methanol and once with 100 ml of methylene chloride. 

The solids are placed on aluminum foil in a fume hood and allowed 

to dry for approximately 2 hours. The solids are placed in a vacuum 

oven and dried overnight at 105°C. The reagent is placed in a 

rinsed beaker and stored (activated) at 120°C until use. 

6. Silica Gel/Carbon: Silica Gel-60 (100 g) (Herck-Darmstadt) is 

Soxhlet extracted with methanol (200 mL) for 24 hours, air dried 

in a hood, and further dried in vacuum oven for 24 hours. AMOCO 

PX-21 Carbon (5 g) is added and then blended until uniform in 

color. The Silica Gel/Carbon is stored in a closed jar at room 

temperature until use. 

7. Florisil: Florisil 60-100 mesh (Baker Analyzed) is soxhlet 

extracted with methanol for 24 hours, placed on solvent rinsed 

foil, air dried and stored in an empty hexane bottle. Prior to 

use it is activated at 120°C for 24 hours. 

8. Standards: 

1. Analytical Standard Spiking Solution 

Table 3 provides details of the spiking solutions. The surrogate 

analytes are used by the data reviewer to insure that calculated 

MLD values are reasonable. 

2. Quantification Standards : Quantification standards were prepared 

by Wright State University. The concentration of 2,3,7,8-TCDD was 

12/89 QA/WC PCDD/PCDF 7 
5. urlttrttva Strndrrdl: IRL-0 has dovolopad tuo qur\ltrtivo 

rnrlytlcrl StrndBrdr, ono conta(nln( rl\ 75 PCOO’r and all 1Ja 

PCOl’r YII dovotopod from In axtraction of l unlcipat incinerator 

fly ash (Trblor 5 rnd 6) and tho othrr contrlnlng only tho biorignlflcrnt iromors YII dovotopad by rlporuro of flrh to an extract 

of aunicipol incinrrrtor fly rrh and procorrln( tho r8poa.d firh 

for rcoO/PCOr. Thoao atrndrrda mill bo urrd to rrrl9n 

atruccuro8 for iaomor spacltle rn6Lyao8. 

ftandrrd rolutionr are ronicrtod for 5 to 10 l inutor before UIO. 

korosrno (Pfl() ia urod for the inltlal rn9S9 crlibration of tho 

188s rp9ctromatrr. rorfluorodrcrtln (rf0) ir urrd daily for 

drtorminin) maaa rosolutlon on m/1 592.9741. 

12189 QA/OC )CDO/PCDI 4 
Table 4: Calibration Standards 

Concentrations in Calibration Solutions in pg/ul Tridecane 

Calibration Standard W1 W2 W2 W4 W5 W6 W7 W8 

2,3,7,8-TCDD 

2,3,7,8-TCDF 

1,2,3,7,8-PeCDD 

1,2,3,7,8-PeCDD 

2,3,4,7,8-PeCDD 

5 

5 

5 

5 

5 

1 

1 

1 

1 

1 

1,2,3,4,7,8-MxCDD 

1,2,3,6,7,8-MxCDD 

1,2,5,7,8,9-MxCDD 

1,2,3,4,7,8-MxCDF 

1,2,3,6,7,8-MxCDF 

1,2,3,7,8,9-MxCDF 

2,3,4,6,7,8-MxCDD 

1,2,5,4,6,7,8-HpCDD 

1,2,3,4,6,7,8-HpCDF 

1,2,3,4,7,8,9-HpCDF 

OCDD 

OCDF 

13C12 2,3,7,8-TCDD 

13C12 2,3,7,8-TCDD 

13C12 1,2,3,7,8-TCDD 

13C12 1,2,3,7,8-PeCDF 

13C12 1,2,5,6,7,8-MxCDD 

13C12 1,2,3,4,7,8-HxCDF 

13C12 1,2,3,4,6,7,8-HpCDD 

13C12 1,2,3,4,6,7,8-HpCDF 

13C12 OCDO 

13C12 2,3,7,6-TCDD 

13C12 2,3,7,8-TCDF 

13C12 1,2,3,4-TCDD 

200 

200 

200 

200 

200 

500 

500 

500 

500 

500 

500 

500 

500 

500 

500 

1000 

1000 

50 

50 

50 

50 

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 

50 

50 

50 

50 

125 

125 

125 

125 

250 

20 

20 

50 

50 

50 

50 

50 

50 

125 

125 

125 

125 

125 

125 

125 

125 

125 

125 

250 

250 

50 

50 

50 

50 

125 

125 

125 

125 

250 

20 

20 

50 

25 

25 

25 

25 

25 

62.5 

62.5 

62.5 

62.5 

62.5 

62.5 

62.5 

62.5 

62.5 

62.5 

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 

50 

50 

50 

125 

125 

125 

125 

250 

20 

20 

50 

2.5 

2.5 

2.5 

2.5 

2.5 

12.5 6.25 2.5 

12.5 6.25 2.5 

12.5 6.25 2.5 

12.5 6.25 2.5 

12.5 6.25 2.5 

12.5 

12.5 

12.5 

12.5 

12.5 

25 

25 

50 

50 

50 

50 

125 

125 

125 

125 

250 

20 

20 

20 

6.25 2.5 

6.25 2.5 

6.25 2.5 

6.25 2.5 

6.25 2.5 

12.5 

12.5 

50 

50 

50 

50 

125 

125 

125 

125 

250 

20 

20 

50 

5 

5 

50 

50 

50 

50 

125 

125 

125 

125 

250 

20 

20 

50 

12/89 QA/QC PCDD/PCDF 9 
,,11111 -B----- 5: ~~ll~i~r-~lt*“~io” m--------w- r’all,tsr,i_P,PEeP,I2l~lr¶ ---------m--___ 

RRT RR? 

Compound OBS SP2SS4 

.,...,.......,**....*.,...*.. 

1368 

lJ79 

lSb9 

ts7a 

lCb9 

1247 

1246 

1246 

1249 

1266 

7478 

1279 

1254 

1216 

1269 

1237 

1236 

2s7a 

7239 

1278 

1267 

1219 

0.814 

o.a3a 

0.661 

0.912 

O.Q12 

0.912 

0.912 

0.921 

0.921 

0.93C 

O.VLO 

0.960 

0.915 

0.915 

0.915 

0.991 

0.991 

1.000 

1.009 

1.028 

1. oca 

1.079 

0.826 

0.871 

0.94a 

0.916 

1.072 

0.9ca 

0. VbI 

1.014 

1.014 

0.972 

0.990 

1.027 

1.014 

1.027 

1.105 

1.014 

1.014 

1.000 

1.088 

1.072 

1.130 

1.216 

12379 

12369 

124b7 

i 2ca9 

12347 

12346 

12378 

12367 

t 2sa9 

1.320 1.209 

I .3ca 1.307 

1.348 l.S21 

1 .JLI 1.321 

1 .Sb1 1 .2bb 

1 .JbI l.SS2 

1 .coo 1.218 

1.415 1. JbS 

1.4cs 1.465 

124679 1 .620 l.C7S 

12Lba9 1 .btO 1.b73 

12Sbb8 1 .673 l.C?S 

123679 1.700 1 .34b 

125689 1.700 1 .5Cb 

123469 1.700 1 .b81 

12S478 1.764 1 .bOC 

12Sb78 1.775 1.616 

12Sb67 1.802 1.789 

123719 1.802 1.721 

1234679 1.976 2.135 

1234676 2.02s 2.297 

12466 1.224 

12479 1.224 

12469 1.26s 

12368 1.29s 

12478 l.SOI 

1.111 

1.111 

1.2b6 

i .ica 

1.186 

12SL6719 2.2SC 3.225 

12/89 OA/QC tCOD/PCDP 10 
1568 0.7so 

146& 0.752 

2Cbb 0.765 

1247 0.782 

lSL7 0.7at 

1378 0.7at 

1Sbb 0.782 

2568 0.782 

1367 0.801 

1348 0.801 

1379 0.801 

1268 O.bSS 

1248 0.835 

lb67 0.853 

lb78 0.855 

lS69 0.863 

12S7 0.86s 

2b67 o.abs 

12S4 0.810 

2J49 0.810 

1256 0.110 

lb69 0.180 

1258 0.880 

1278 0.902 

1349 0.920 

1267 0.920 

2578 0.939 

2Sib 0.939 

2347 0.959 

2546 0.9s9 

1246 0.959 

1249 0.959 

1279 0.959 

2367 0.97S 

1259 0.9ab 

1269 0.9ab 

S467 0.988 

1209 1.071 

0.777 

0.875 

0.919 

O.bbf 

0.865 

0.85s 

0.919 

1.071 

0.881 

0.900 

0.853 

0.943 

0.919 

0.989 

0.943 

0.943 

0.94s 

1.109 

0.977 

0.977 

0.989 

1.011 

0.989 

1.017 

t.ots 

1.049 

1.169 

1.175 

1.140 

1.193 

0.940 

1.07t 

1.049 

1.206 

1.140 

1.162 

1.264 

l.Sil 

lsc7a 

lSb79 

2SLb9 

12479 

1 SLb9 

23468 

12469 

12547 

12SLb 

i 2s4a 

12S78 

12567 

23489 

12S79 

23478 

12489 

lSLb9 

12369 

2SLbt 

12549 

12589 

1.202 t ,015 

1.217 1.105 

1.217 1.17s 

1.255 1.142 

1.25s 1.2oc 

1.25s 1.278 

1.25s i .27a 

1.25s 1.17s 

1.253 1.231 

1.240 1.216 

1.210 1.216 

1.295 1.252 

1.509 1. SII 

1.309 l.tS7 

1.339 1.557 

1 .SSV 1 .bLb 

t.s59 1.350 

'.SSP 1.571 

1.371 t.612 

l.S92 1.420 

1.446 1.590 

12SCbb 1.556 l.SSb 

134678 t.570 1.370 

12b678 1.570 1 .SC8 

134679 1.570 1.348 

124679 1.602 l.42b 

124689 1 .btl 1.521 

t2S467 1 .bbS l.SSS 

12547b t .66S 1.469 

12Sb78 1.676 1.502 

12S479 1.676 1.4b9 

123469 1.712 1.668 

125679 1.7SD 1.562 

123689 f.744 1 .bbb 

2S4678 l.fb4 2.012 

ltS789 1.827 1.871 

123489 1.827 1.940 

'f&68 1.120 1 .OOb t2S4678 1.9s4 

12461 1.120 1.028 12S4679 1.979 

2S479 1.190 1.065 12Sb689 2.02b 

12361 1.202 1.105 12S4789 2.04s 

12478 1.202 1.121 

13467 1.202 l.lL2 ltS46789 2.240 

12467 1.202 1.160 

t.9S6 

2.00' 

2.161 

2.463 

S.165 

t2/b9 QA/QC Ptoo/PCOI 11 
IV. Instrumental Parameters: 

All gas chromatography/mass spectrometry analytes (GC/MS) will be done 

on a Finnigen-MAT 8230 high resolution GC/high resolution MS (HRGC/ 

HRMS) System. Instrumental parameters are given in Table 7. 

Table 7: HRGC/HRMS Operating Parameters 

Data Acquisition: Multiple Ion Selection Electric Sector Scan. 

Compound Mess Window m/z value 

Quant. Confir.* 

TCDF 

37Cl4-TCDF 

13C12-TCDF 

TCDD 

37Cl4-TCDF 

13C12-TCDD 

PeCDF 

13C12-PeCDF 

PeCDD 

13C12-PeCDD 

HxCDF 

13C12-HxCDF 

1 

1 

1 

1 

1 

1 

2 

2 

2 

2 

3 

3 

HxCDD 3 

13C12-HxCDD 3 

HpCDF 4 

13C12-HpCDF 4 

HpCDD 4 

13C12-HpCDD 4 

OCDF 5 

13C12-0CDF 5 

OCDD 5 

13C12-OCDD 

305.8986 

311.8898 

317.9389 

321.8936 

327.8847 

333.9338 

339.8597 

351.9000 

355.8546 

367.8949 

373.8207 

385.8610 

389.8156 

401.8559 

407.7817 

419.8220 

423.7766 

435.8169 

443.7498 

455.7801 

459.7348 

5 471.7750 

305.9016 

315.9419 

319.8963 

331.9368 

341.8567 

349.9029 

353.8576 

369.8919 

375.8178 

387.8580 

391.8127 

403.8530 

409.7788 

421.8191 

425.7737 

437.8140 

445.7369 

453.7831 

457.7377 

473.7721 

Sample Introduction: Capillary Column, Splitless Injection. 

Ionization: 

Sourer Pressure: 

Electron Impact, 70eV, 1mA Emission Current. 

1 x 10 torr. 

Monitor Temperature: 250° c. 

Mass Resolution: 5000, 10% valley. 

Scan Rate: 1 MIS cycle per second. 

GC Column: 30 m 08-5, 60 m SP2330 

Linear Velocity: 35 cm/sec Helium. 

Temperature Program: 180° C (hold 1 min): 13°/min to 200°; 

3°/min to 270°: 270° hold 4 min. 

Mass windows are monitored sequentially during the temperature 

programs with the windows definded by the elution of standards. 

* Quant. - Quantification ion; Confir. = Confirmation ion. 

12/89 QA/QC PCDD/PCDF 12 
V. Quality Assurance/Quality Control (QA/QC) 

A. General Procedures of Operation 

1. Analysis of Samples: Samples are analyzed inn sets of 

twelve consisting of: 

a. Blank: Method Blank (extraction apparatus) is prepared in 

the laboratory and subjected to the same sample preparation 

procedures as environmental samples. The Method Blank is 

used in every sample set. 

b. Fortified Matrix: Native analytes (100 uL) (Table 8) 

are added to a blank sample matrix. The levels of fortification of native analytes in the matrix spike will be above 

the target detection limit to provide an estimate of the 

method’s sensitivity, and for determination of percent 

accuracy of quantification. This sample may be substituted 

with a reference sample that has been analyzed at least 

three times and a mean value of contamination has been 

established. 

c. Detection Limit Verification Sample: An environmental 

sample with nondetectable amounts of native analyte (determined 

from a previous analysis) will be spiked with native analytes 

(Table 8) and analyzed with the next sample set. The addition 

of the QA/QC sample will be done for only the first three 

sample sets of any matrix type to establish that the 

calculated MLD is achievable. If analytical results show 

difficulty in obtaining the MLD, then this QA/QC sample must 

be in each set. It no problem is experienced, then this 

QA/QC sample may be dropped. 

12/89 QA/QC PCDD/PCDF 15 
Table 8: Native PCDD/PCDF spiking solution (100 uL) 

Compound Concentration 

(pg/uL Tridecane) 

Solution A Solution B Solution C 

2,3,7,8-TCDD 0.50 1.00 1.50 

2,3,7,8-TCDF 0.50 1.00 1.50 

1,2,3,7,8-PeCDD 0.50 1.00 1.50 

1,2,3,7,8-PeCDF 0.50 1.00 1.50 

2,3,4,7,8-PeCDF 0.50 1.00 1.50 

1,2,3,4,7,8-HxCDD 1.25 250 3.75 

1,2,3,6,7,8-HxCDD 1.25 250 3.75 

1,2,3,7,8,9-HxCDD 1.25 250 3.75 

1,2,3,4,7,8-HxCDD 1.25 250 3.75 

1,2,3,6,7,8-HxCDD 1.25 250 3.75 

2,3,4,6,7,8-HxCDF 1.25 250 3.75 

1,2,3,7,8,9-HxCDF 1.25 250 3.75 

1,2,3,4,6,7,8-HxCDD 1.25 250 3.75 

1,2,3,4,6,7,8-HxCDF 1.25 250 3.75 

OCDD 2.50 5.00 7.50 

OCDF 2.50 5.00 7.50 

d. Duplicate Sample: Two separate portions of the same 

environmental sample are processed and analyzed. 

e. Environmental Sample: The total number of environmental 

samples analyzed is eight if the Detection limit Verification 

sample is used; otherwise nine samples are analyzed. 

2. Sample Tracking and Labeling of Samples: 

a. Logging Incoming Samples: ERL-D completes the chain of 

custody forms and informs the Sample Control Center (SCC) 

that samples arrived safely or informs SCC of any problems 

with the samples. Each sample received by ERL-D had 

previously been assigned two numbers by the Sample Control 

Center, the Sample Control Center number (SCC#) and an Episode 

number. The SCC# number is unique for each sample and provides 

12/89 QA/QC PCDD/PCDF 14 
l means for trrckine l given semOle throughout it9 enrlvcla 

end ita Oermenrnt rtorrO0 8t the locker plent. Iho aemotes 

are placed into freetor A upon rrriveL at LRC*OU~~~R, 

homogenized, (see II-A.), and an rliouot (100-500 g) is p,aCea 

into frrexer B. After the srnoler Are extracted t'lev are ~~~ 

into freexer C. If 811 the datr neett 91, requirements after 

aces spectrrl 8n8tysis end qurntificrtion, the sampler are 

trrnsferred co 8 lockrr plrnt for permrnent stor8go t-20’ .:I. 

b. Lepoinq u L8belinc S8mples purinl Pr8p8r8tion: A lrboretory 

identific8tion code (Irb ID) is rlndomly lssignea to each 

Samplr in 8 set of tuelve at tht st8rt of sanplr preoararlgq. 

The code consists of I letter, A through L, drte of 

extr8ction, rnd tuo initirls of the srmple preprr8tion 

chemist, (e.g. Ao9lrlrn1,. ?hlr code is ured to identrfy CYC 

srnplr throughout the rnelysir period. The SCCI, Lab 17, 

srmple description, ueight of srmplr, and amount of anrlyrlcat 

rtrndrrds added to each s8mplr 4re recorded in the srmple 

preperetion Lo9 book at the ttert of l rtrection. The Lao 

10 is uritten on Iebeling t8pa uhich is trenrferred from 

beeker to flrsk during sraple preprrrtion. The leb ID is 

uritten into the MS log book along uith the mess spectrr 

enelvsis number. 

3. psll $vrtrm )enott Treekin%: El&-O bra developed the P8tionsl 

OloriA Study (IDS) Ph8re II, Ilorceuputrtive Po(lut8nts in Fish: 

Sr~ple Treeking Datrbrrr to frcilitrtr record keeping end 

8uapery report genorrtion for arch 8rmpla on the OLC-VAX 11/785 

(Dtgltel Equipment Corporrtion). For l ech seaple, includin9 OA 

sample,, inforprtion pertinent to l ech semple ir entered into tkt 

12/89 Ol/OC PCDO~PCD? 1S 
drtabrar. Ourntificrtion data (finat concantrrtion, ion ratIoI, 

parcrnt r~cov.rY I *Los, 4nd signal to noise) arm aUtOm4tlCJlly 

uploaded to the drtrbasr once all OA criteria hrvr brrn met. 

tigur, 1 is an rxrnplr of the xDS database. 

The first tno (otters of tha SCC number lndicrtr rhethtr 

the sample ir rn EnvironmrntaL, Nrthod or Matrix Itant, 

Duplicrto Slmplr or 4 mass soectrrt confirmation rnrlysis of 

rn rnvironarntrl ramplo. ALL rnvironmrntrl srmplrr brgin 

with the letter 0, or 5 if it is a maas sprctrrl confirnrtlon 

analysis of l previously rnrLy:od rnvironrentol Sample. 

Ihe Stank and Ouplicrtr srrplrs beein uith the Lottor 0 

foilowed by a D or rn R for duplicrtr or rrfrrencr fish 

rrapir, rrrp*ctivoly. T1bl0 9 lists tka porriblr COdOS 

for the SCC nuobrr, and matrix type. Epirodo numbers for 

@tank8 and Cortifiod Matrix saaplra are entered as 0000. 

12/a9 OIIOC PCDO/PCD~ lb 
___ Ftgyrr _----------------------------- 1: e)staeaso Format for Srmele ln’ormst*on. 

-__-------------------------------------- 

YDS 3hase 1.1: BioJc:Umu~atlve PO~~utanCS in Fish: 

Sampkr rr8cklng Systrn ERL-D loc:25 

EPISODE I: 3000 SCC 1): aRO?lcab 

SrmgLir.9 1ntormrt:or: 

SrmpL~ng Office: 

State L Ciry: 

Sampling Contrcr: 

O~rc samptrd: a/ 01 0 

Sit* Locxtion: 

Lxtitudr: 1( 0 3' 3 " Lonpitudr: Y 0 5' a* 

Anrlysls Lab: 3 3rte Roerived: Q/ 01 0 

Matrix Type: P Rrrun: 0 

AnxlyticxI: P:DD/PC3F Pesticide & Industrtal Chrmicr\r 

Extrrction Date: 7jtcjab o/ o/ 0 

CC/MS ID: MAra 

LAO ID: ~071486Ll4 

Yetght: 20.00 0.00 

% LipId: 5.2 0.0 

Mass LIpid on CPC: 0.00 

Comments: Reference fish 86 

12/19 QA/QC PCOO/PCO~ 17 
rot Phrso II: Iio~ccuau~4t~vr pottutrntr in Fish 

EPISDOC 8: 0000 SEC 8: 01071486 ERL-0 LOC: 25 

DATA FOR IIOSItYlffCAYt POLICMLORIRA~CD DIBERZ00l0xIRS AR0 CURAIYS: 

Anolyt. CAS WO. I/R S/Y ZRCC OL Aaount(og/e~ 

2,3,7,8-TCDf 

2,J,6,7-TCOf 

3,4,6,7-TCDf 

51207-51-9 O.fL 55.75 62 0.0000 5 .tb 

1 .oo 8.21 62 0.9726 MO 

1.71 16.5b 62 O.L1163 ND 

2,3,7,8-TCOO l7CI-01.& 0.71 40.75 

1,2,3,7,8-P~CO~ 57117-41-4 l.fS 14.72 

2,J,c,7,a-Prcof 5?117-31.6 1.10 11.15 

2,J,L,6,7*P~CO~ TObLU-2V.9 0.00 0.36 

1,2,3,7,8-PrCOO 40321.7b-4 0.25 4.24 

1,2,s,L,4,7-Wxcof l 

l,2,3,4,7,8-xxc01 

l,Z,S,b,7,8-nxCOf 

2,S,L,b,t,l-IIxCOf 

1,2,3,7,8,9-nxCof 

70448-26-9 0.00 57.03 

57117.44.9 0.67 28.52 

6D851-34.5 1.25 57.03 

729ia-21-9 0.00 57.01 

(,2,3,4,7,8-RxCDO 5259a-13-5 0.00 29.08 

1,2,3,b,7,1*naCDD 57753.a!-7 1.31 4.67 

1,2,3,7,8,9-UxCDD ?9408-74-s 0.00 29.08 

1,2,3,4,6,7,8-noCDf 67542-39-L 0.62 

r,Z,S,4,7,1,9*wpCDf 55675-89-7 0.00 

1.15 

Il.97 

37.94 

10.50 

71 

54 

54 

54 

57 

c7 

47 

4r 

47 

cv 

LP 

LO 

39 

s9 

s9 

0.0000 

1.0492 

I.6357 

2. i7a4 

4.0729 

0.7327 

1.4654 

O.fS27 

0.7S27 

1.3863 

0.0000 

l.Jl(f 

0.0000 

0.0000 

0.0000 

15.63 

II0 

II0 

MD 

WO 

WD 

uo 

MO 

YD 

WD 

f.25 

YD 

ND 

WO 

5.93 

l Corlutos vith 1,2,3,4,4,7-RxCOf on l 005. 

I/R l Ion Ratio; S/It * Slgnrl to Woirr; 01 m Oetrctton liaft 

12189 OA/QC PCOD/PCOf 10 
tspto 0: ---a CO~J~ ------MS- for the SCC Ny4~~c-4"~ Matrix TIpI --------s--e-w --------- ---s*--- 

SCC numbor first letter OptiOna: 

0 -- Environnentri Srrpl*S 

a -* OA srn~l~s 

5 -- MS confirmation analysis 

soconu l*rrrr 0Otionr for Environmrnrrl Srmplrs 

A - Rr9ion 1 c - Rr9ion 7 

I - RrRion 2 It - lesion 6 

c - Rrgion 3 Y - logion 9 

0 - Region L J - Roeion 10 

f - Region 5 1 - At1 rrgionri data 

f - Region b 

Second lottrr options for DA sarplrs: 

I - Method or matrix blank 

0 - trbrotory duplicrto 

R - Rofrrenco fish or fortified nrtrix 

Matrix type: 

Pf - Prrdrtor fillrt 

UB - UhOlO aottor 

UP - whole Predator 

@f - lotton fillet 

R - Rofrrrncr 

Y - Dlant 

L - Caborrtory Duplicate 

----__--------------________________)___-------------------- 

12/89 QA/eC CCOD/PCDf 19 
g. natrumanta ur\ i tt Fontrot 

1. UehlorlroP raoh 

a. ~rrrtion u Mointrnlnc~: Oprrrt~on and l rintrn8nc~ of 

th. gar chromatograph vi11 be don* according to nanufrcturrr*r 

r*commrndationr. 

b. $orumn Oqrformancr: CC colurn performance uill br 

rvrlurtrd by: 

I . Rg(Olution of 1,2,3,L-TCDO from 2,3,7,8-ICOO 

(Table 10). 

i 1 * Tn. I 2 vait~r of the rrgrrrrion of the sraplo 

rr\rtivr rrtrntion timr of aI\ bloaigniflcrnt PCDD/PCDT, 

to the Library rrlrtivo rrtrntion should not be lrrr 

than 0.995. 

iii. glution of all PCDO/PCOI during l naLy8id frOn a GC uindou 

drfininv solution of srkrct PCDD/PCDP (table 11). 

Rraolutton of l,2,3,C~TCDD from Z,S,t,l-TCDO uilL 

bo used to rva\urt8 g8nrrrl column prrforrrncr. 

Iosolutlon (I) muat br 0.75 or grrrtrr. 

20 
Tsble 11: :c E[Jtt-n ulndou 3e“ninp Solutions far )8-g Co\Jnn _--_----------____----------------- --------------------------*--- 

Conprner Groue E ; . -se-- ---______ ,------lf,=----- CLutl"g ---a-------- -e-e- ----_ Last ilutina 

TCDD '.3,5,8 1.2.8,9 

TCOC ',3,6.8 1,2,8,9 

PICOO !,2,&,7,9 /1,2,L,6,6 1,2,3,6.9 

PeCOF !,S,b,6.d 1,2,7,8,9 

4rc30 j82,k,b,7,9 / 1,2,4.b.ae9 ~,2,3,4,6,7 

MlC3F 1,2,3,66,a 1.2.3.u,9 

I(pcoo 1 ,: 3,L,6,7,9 1,2,3,+5,7,a 

HOCOF r,2,3,c,6,7,4 1,2,J,C,7,8,9 

------------------------------------------------------------------ 

2. Mm Socct-al Dtr+srmance: The prrformrncr of the mass 

sprctromrtrr 1s evelusted for resolution, Sensitivity and 

Linerrity. The mess resolution used for those rnelyser is set at 

s minimum of 5000 (10% vslley aefinltion). The msss spectrometer 

is tuned l ech aey to the required resolutron recording to t-e 

procedures established by the instrument mrnufrcturrr. Senstt’gi:t 

Jnd Linerrity is rvrturtrd by the use of calibration stsnasras 

verying in concentration (Tsble 6). A crlibrstion curve is 

rrtrblishrd for tech stsndsrd. The curve must br linear over tne 

rrnga of concontrrtions used in the crlibrrtion strndrrds. The 

percrnt rrlrtive strnorrd drvirtions for the mean response tact:?) 

must br Ierr than 20 porcant. 

C. Fvrlurtion e u: 

1. bccuracu, : Accur8cy, rho degree to uhich the rnrlyticrl 

nrraurenent reflrctt the true lrvrl present, uill br evaluated In 

two uay8 for each srnple set. Theso are: tha differonce of 

mea8urtront of e PCDD/PCDF isonrr added to l blank mrtrir, or 

dlffrrrnco of measurement of a PCDO/PCDI from the Level in an 

l rtrbtirhrd rrtrrrnco mrtrrfrl; end tho l fflcirncy for rrcovery 

!2/IO PA/QC PCDO/?CDF 21 
of the Internet standard added for oath congenrr grouo. "rc 01 

rrqulrrmrnts for accuracy and method efficiency ere provloea II 

Table 12. Percent Accurlcy and Percent Method Effrcjency 

are defined as follouS: 

measurrd value 

2 accuracy a I 100 ----------------------- 

rnoun t native isomer 

added to blank matrix 

measured vrlur 

z Method l ffici*ncy 1 .-.-*.-------..---......- x 100 

amount internrl standrrd 

added to each saaplr 

Table 12: 9urlity Assurance ParSmeterS __------------------------------ ---------------_-------------------------- 

TCDO 

PC00 

HXCDO 

Hpcoo 

0c00 

TCDF 

PCOC 

HxCDF 

MPCDF 

OCDf 

. . 

Method Accuracy 

Ion Uatio Efficiency at 10 PO/O 

0.76: 15x >cox, (120% :50x 

0.612 15% DCOX. <120x 250t 

1.252 15% ,40x, <120x :100X 

1.022 15% PLOX, cl2Ol :lOO% 

0.86: 152 #40X, 4120% :200x 

0.76, 15% *box, <120x 250% 

1.53+_ 15% l COX, (1201 250% 

7.2s: 15% SLOI, ~120% ~laox 

1.022 15X .&Of, <120x *200x 

1.5s: 151 >sox, <120X ,200x 

. . 

Precision S/Y 

at 10 PO/O Minimum 

:50x 3.3 

250% J.0 

~100% 3 .o 

:100x 5.0 

:100x 3.0 

:50x 3.0 

:50x 3.3 

:100x J.0 

:200x 3.0 

:200x 3.0 

---_---------------_--------~------- --------------------------------------- 

. Varirnce of nersured value fron actual. 

. . vrrirnco of differonce of duplicatea from mean. 

12/89 QA/QC PCDO/PCOI 22 
2. Prrciaion: Procirion, a IOa*UrO of mutual rgrromrnt anon* 

Indlvidua( aeasurrmonts of the sea@ pollutant in rrpl~crtr 

l ~~Dl.1) ig l vaturted for each sampie 8.t by the ratio of 

thr diffrrrnco of duplicrtr vmturs to their morn value. 

Trblo 12 provider OA requirements for precision. Precision 1s 

determined only uhen both v~luor are above the drtrctlon tlmlt. 

Precision is drfinrd as fOIlOur: 

difforoncr betMOOn duplicate srrplrs 

precision . . . ..-------- . . ..-.......-.-........... x 100 

morn vrlur for the duplicator 

3. jiqnal Ou4\ity: The quality of the aoa# #poctroL signals used 

for qurlitrtivo rnd qurntitotive analysis is l vrlurtrd 

using two prrrmetrrs: tha ion intenrity ratio for the tuo ions 

l onitored in each ConOInrr group, and the rignrl to noisr (S/W) 

rltio. lrblr 12 provider PA rrquiraaents for signaL quality. 

In addition, qurlitrttva idrntificrtion uill bo based on 

coolutfon uith the strblr fnotopr labrlrd compound, or rrtrtive 

rrtrntion tire corrrlrtion (foblao 5 Jnd 6). 

4. Polar u oroltatparaphic Confirn~tion Anrlvsi~: Ten 

percent of tha soap10 oftrocts rnelytrd ore rrlrcrtod for 

GC/MS conftrartlon rnrlyris on the more polar SPt350 column, 

(Sup*Lco, Dolafontr, PA). Srmploa uhich uere positive for 

2,3,7,8-TCDO uere saloctrd for rnrlymir. 

I t/a0 QA/OC PcDD/cco~ 23 
0. gualitv Allurrnc~ Problank rnd rorrrctlvq. Jctionc: 

‘rPhIlm ----------- --m--w----- -------w---s--- ~nr~lrslrl,~rslnn -----------MB-- 

MS performance oucrld* aA Adjust MS par4motrrn for rasolutbon, 

rerun initial Curve And rrrnrlyzr 

trmplr(r~. 

SC colunn prrformrncr 

oulridr QA. 

Method l fficirncy outsidr 

of QA. 

AccuraCy oursidr of OA for 

(pitrd matrix. 

Precision of duplicates 

outride QA. 

o*toction of l nalyto in 

blank for 2,3,7,8-TtoO, 

2,3,7,8-TCOC and 

1,2,3,7,6-PC00 

for other rnrlytrr in 

bl ant 

Anrlytr exceed8 crlibration 

standard rrngr. 

Mothod officirncv for blank 

outride of 01 or blank lost 

Roan@Lyxa standard1 and srrplrr on 

modifird or l ltrrnatr column. 

If 2$78-TCOO l athod rfficirncy *La%, 

reanalvle naaDk0 8Ot. If nothod 

rfftcioncy *LOX for rnalvtr8 other 

than 2378.TCOO, flag and report dAtA. 

If more than 20X of tho rnrtvtrr l x@ 

outside of QA for accuracy and prrcirion, rrrnrlvtr the rrm~lr sot. 

Rrrrtrrct and rrrnalvxa all ~rmplrs 

for uhich the lrvol of contamination, 

or MLO, is l 2.S I blank Level. 

Record blank concontratlon in comment 

f4oLd of 8rapl.r. 

YoIsure method afficirncv. Dilute 

aorplr 1OO:l rrapiko with each 

standard rotution (A and I), rdjurt 

voLum0 and rernrivto. 

Rorxtract and rrrnrlytr rll positives 

in sat. 

lrcrure of the comptrrity of theso rnrlyrrr typos, ft fr not rrprctrd tkat 

l II anrlytos uill soot all 91 critrrir. lhrrrforr, a comptrtr review of 

the data by l chemist is orrrntial. Rrrponribllitv for the rvr\urtion of 

data is that of the trrplr proparrtion chrmirt and the l a#8 DDectrometer 

oprrator. Rrviou of the data, inctudl ng 04, and rrrolution of data quality 

probLema in the rrsponribllity of the Prlnciprl Invratfgrtor/Progrri rrrnrgrr 

Resolution of data qurrtionr mry rrqul rm reanrlyrir of ramphas to includr 

the addition of confirmatory ionr or anrlyaia on dffferrnt typea of 

CC columns. 

1 t/10 OA/OC PCDD/PCDf 2b 
VI. Quantification Procedures 

Quantification of analytes is accomplished by assigning isomer 

identification, integrating the area of mass specific GC peaks, and 

calculating an analyte concentration based upon on ion relative 

response factor between the analytes and standard. 

A. Initial and Daily Calibration of the HRMS: An initial calibration 

of the instrument will be performed as needed. This will include 

making three replicate injections of each calibration standard 

(Table 4). Weighted least-squares linear regression is used to 

generate a calibration curve for each analyte. The weighting factor 

is inversely proportional to the variance among the replicate 

injections of each calibration standard. The slope of the regression 

line is the response factor used to quantify the analyte. At Least 

two calibration standards are injected daily to insure that any 

response factors used for quantification and recovery calculations 

do not deviate from the initial calibration by more than 20 percent. 

If the drily calibration generates values outride this margin, and 

less drastic corrective action does not solve the problem, a new set 

of initial calibration curves is generated and the old response 

factor libraries discarded. An example of a typical calibration 

curve, using 2,3,7,8-TCDD as an example, is shown in Figure 2. 

12/89 QA/QC PCDD/PCDF 25 
Figure 2 

2,3,7,8-TCDD 

WEIGHTED CALIBRATION CURVE 

CONCENTRATION 

/ CONCENTRATION 

SLOPE = RESPONSE FACTOR 

12/89 QA/QC PCDD/PCDF 26 
cJlibrJcion curve for the JnJlytJ of inrrrest. 

JnitiJl CJl;brJtion #JSed Methog gt u: ML0 I¶ l stlmJtrQ 

from the rJti0 of the norse JrJJ t0 the iSOtOplCJl~v LIbeLJO 

intrrnrl strndrrd JreJ, piUS three time1 the StJndJrd error of : 7 c 

estimate (SE) for the l re8 ratio, or Y-1x0, of the inltirl 

cJlibrJt!on curve. Thr Y-intercept ([NT) is subtractrd from ~7:s 

quant i ty, in keeplng with the normal formalism for @‘inverse 

prediction” of a point on the X, or Concentration ratlo rris, from 

a point on the Y, or signrl ratio rxis. The SL term is derived 

from rn analysis of variance (AMOVA) performed during the reighreu 

leJSt squeres fit of the initiel calibration curve. This term 

represents the rendon error in the rrpiicrte injections used to 

gonerate the crlibretion curve, the error not JCCOunCed for by the 

linerr model. The ueighting is necessary because of tne relation 

often observed in instrumentel rnrlyris, of increrring vrrirnce 

with incrrraing concentration. n10, recording to this scheme, 

is drfined belou: 

12/89 Qh/QC PCDD/PCOF 27 
whore: NA 

I ssr 

1YT 

C3fb 

c 

SE 

noire JreJ in the uindou for the moJor ion 

of the native analyte, 

Irbrled internrl strndard peak eroa in the 

serple, 

the Y-Jris intercept on the initial ~81 

curve, 

labeled int8rnel stendrrd concentration 

brrcion 

constrnt to adjust for srnple six8 Jnd finat 

VOlUIIO, 

r*rpons* frctor for mejar nrtive ion to 

1s c,* 1,2,5,L-TCDO ion, the slop8 of the 

initial crlibrrtion curve, 

stendrrd error of the l rtiaate of the initlrl 

calibration curve. 

In addi lion, firh tirrue is rp 

tree Internet StJndJrd Solution 6, 

iked ui th surrogate rnriytes 

TJble 3) prior to l xcrrction. 

Thr rurrogete enrlytes serve 41 rn added chock to insure th8t 

ML0 vrhurs crlculeted from the initial celibretfon curve, 

8s dircurred above, are rrrroneble. 

2. StanaL u loisa (f/Nk: The method of determining the signet 

to noirr recio is shorn brlou. 

- Anatyts signal 

b- Nob Signal 

S/N - 

Analyte Signal Pmk Area -I-III-I -mm-- 

Noise Signal Peak Ama 

12189 OIIOC Pcoo/PCOP 28 
The no is0 l reJ ia CJiCUtJt8d by inte9r4tin9 over 4 PeJk ulatk 

l quiva Iant to the rnOlyt* si9nJ1, typicJt\y rbout 10 seconds. 

AnJlyt8 SignJl JeJk Area 

S/Y * . ..*......*..........*...* 

Noise Si9nJl Peak Area 

C. gufintificrtion 01 PCOO/*COf: The concentrrtion of l natura\ 

PCDO/PCOI is determined bY cJltulJtin9 J rerponle factor becuqrn 

PCOD/PCOf end IhO StJble iJOtOpe LlbIIed PCDD/PCOF for the congenrr 

group. crlculrtionr Jro prrfornrd aa follour: 

ttJnd8rd: 

vY . 

A,, a S L ..*.......... 

Al I RI(Y/l) 

uhrrr: R?(N/L) 

Alt 

Al 

CY 

cl 

*L 

vY 

rJrponrr frctor native to Labeled, 

pJJ& Jr8J nJtiVJ, 

perk JreJ Irbrled, 

concrntrrtfon of nrtive rtrndrrd, 

concrntrrtio Of IJbJ1.d BtJndJrd, 

LJb.i@d spiki ng levrl in rrrple 

Irvol of nrti VO JnJtrtJ tn JJmp le. 

1 t/89 OA/QC PCOO/PCOI 29 
0. **the* gfficl*nu: The l othod .ffici.ncy for the rrcovery of stable 

isotogq lrbalod co~eound~ is drtrrmined by crlculrtin( the eaounc of 

stable irotoor 14b*l*d compound in the final ontract and diviainq DI 

Ihe amount spiked into the some10 at the start of the cleanup 

procedure. This IS done by drtrraininq the rrlrtivr rrrponsr factor 

betueon tha Internal Standard Solution C, 13 C,2 1,2,5,4-TCDD 

and the stable iSOtOp0 LabeLed intrrnrl standard (Solution A). 

D*t*rminr Rosponso rector: 

I1 K EIS 

RF l .....-.e-. 

“1s x cl 

whore: Rf n rrrponrr factor, 

*L = sreo of stable iaotopo 1aboLad 

internal ttrndard. (ro(ution A), 

lrts n area of 13C12 l,Z,S,C-TCDO, 

CL a concrntration of strblr isotopr Labeled 

internal atrndard, (SOLutiOn A), 

Cts * concrntration of lSC12 1,2,3,4-ICOD. 

The rrrponrr factor is then used in crtculrtinq the concentration 

of the intrrnrl standard in the finaL solution, 

*L x Ctt 

5 = -*-------- At* x RF 

uherr: CL l concentration of rtrblr iaotopo LabeLad 

intrrnrl standard, (rolutlon A). 
~kr concentration in the finrl solution tinrs the t’nrl VOIU~~ 

l qurla the total amount prosrnt. Iho method efficiency !I then 

crlculrtod by: 

Cl found 

t R.cov@ry , 1.----.-... x 100 

CL xpited 

t. Jntraration d AutomrtrQ u Processing. u Ourlity IIssur)nce: 

QA prrrnrtrrs for mrthod rfficirncy, ion ratios, rrtrntion timr 

corrrlrtionr, signal/noise ratio, accuracy and prrcision are 

nonitorrd with the aid of softuarr either drvrloprd in-house, or 

nodifird from existing programa included with the HRNS data systrn. 

Rru data is sorted and rditrd uring the masr sprctrom~trr’s drdicrtrd 

data system, transfrrrrd to the OEC-VAX systoa and procrrsrd using 

roftuarr progrrar RCACTDR and OCOUAYT (Figure 3.1. Oata is rrvirvrd 

by the Project Ofrrctor boforr l ntOrin9 into the YOS data brsr. 

l2IlV OA/OC Pcoo/PcoI 51 
Figure 3 

DATA REDUCTION FOR PCDD/PCDF 

NATIONAL DIOXIN STUDY 

DAI LY 

CALlSRATION 

STANDARDS, 

, 

INITIAL 

-, CALIBRATION I 

’ LBRARIES 1 I 

SAMPLES 

DEW/AX 1 msRT I I OR 

I ml-PC 

L 

MASS 

SPECTROMEI’ER t 

-r r piEq 

YES NO / DATA\ 

* CORRECThIp 

ACTION 

REVIEW 

DATABASE GENERATE 

FINAL REPORT I 

12/W QNQC PCDWCDF 32 
APPENDIX A-3 

Analytical Procedures and Quality Assurance Plan 

for the Determination of Xenobiotic Chemical 

Contaminants in Fish 
United States Environmental Research EPA 600 3-90-023 

Environmental Protection Laboratory March 1990 

Agency Duluth MN 55804 

Research and Development 

EPA Analytical Procedures and 

Quality Assurance 

Plan for the 

Determination of 

Xenobiotic Chemical 

Contaminants in Fish 
EPA/600/3-90/023 

March 1990 

U.S. ENVIRONMENTAL PROTECTION AGENCY 

NATIONAL DIOXIN STUDY 

PHASE II 

Analytical Procedures and Quality Assurance Plan for 

the Determination of Xenobiotic Chemical Contaminants in Fish. 

December 1989 

Environmental Research Laboratory-Duluth 

6201 Congdon Blvd. 

Duluth, MY 55804 
NOTICE 

The information in this document has been funded wholly or in part by the 

U.S. Environmental Protection Agency. It has been reviewed technically and 

administratively. Mention of trade names of commercial products does not 

constitute endorsement or recommendation for use. 

12/89 QA/QC Xenobiotics ii 
ACKNOWLEDGEMENTS 

Technical contributions to this research were made by: 

U.S. Environmental Protection Agency 

Brian C. Butterworth 

Douglas W. Kuehl 

AScI Corporation 

Phillip J. Marquis 

Marie L. Larsen 

Larry C. Holland 

Christine E. Soderberg 

Jennifer A. Johnson 

Kevin L. Hogfeldt 

Alan E. Mozol 

Wright State University 

Dr. Thomas Tiernan 

Dr. Michael Taylor 

University of Wisconsin Superior 

Elizabeth A. Lundmark 

Daniel M. Fremgen 

Sandra Naumann 

Murray Hackett 

Kent Johnson 

Harvey D. Corbin, Jr. 

Dr. Raymond L. Hanson 

John Dargan 

12/89 QA/QC Xenobiotics iii 
FOREWARD 

Directed by Congressional mandate, the U.S. Environmental Protection Agency 

during 1983 initiated the National Dioxin Study, a survey of Environmental 

contamination by 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) 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 

Research Laboratory - Duluth, was responsible for one part of the Study, the 

analysis of fish samples. The most significant findings of these analyses was 

the observation that fish contamination was more widespread than previously 

thought, and that a primary source of TCDD was discharge from pulp end paper 

production using chlorine. 

A second mote detailed characterization of anthropogenic organic chemical 

contaminants in fish was conducted in subsequent analyses during what is now 

called Phase II of the National Dioxin Study. This document describes the 

analytical methods used for the determination of the level of contamination of 

polychlorinated biphenyls, pesticides, and industrial compounds in fish. A 

companion document (EPA /600/3-90/022) describes the analytical methods used 

for the determination of levels of contamination of fifteen biosignificant 

polychlorinated dibenzo-p-dioxins and dibenzofurans in those same fish. 

12/89 QA/QC Xenobiotics iv 
I. 

II. 

III. 

IV. 

V. 

TABLE OF CONTENTS 

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 

Preparation of Sample Extract. . . . . . . . . . . . . . . . . . . 4 

A. 

B. 

C. 

Sample Handling Methodology . . . . . . . . . . . . . . . . . . . . . . . 4 

1. Shipment of Samples to ERL-Duluth . . . . . . . . . . . . . . . . . . 4 

2. Sample Logging and Coding Procedures. . . . . . . . . . . . . . . 4 

3. Tissue Preparation and Storage Procedures. . . . . . . . . . . . . . . . 4 

Extraction of Tissue Samples. . . . . . . . . . . . . . . . . . . . . . . 7 

1. Soxhlet Extraction. . . . . . . . . . . . . . . . . 7 

2. Fortification with Surrogate Standards. . . . . . . . . . . . . . . . 9 

3. Fortification with Target Analytes. . . . . . . . . . . . . . . . 9 

Isolation of Xenobiotic Chemical Contaminants. . . . . . . . . . . . . . . . . . . 11 

1. Gel Permeation Chromatography . . . . . . . . . . . . . . . . . . . 11 

2. Silica Gel Chromatography. . . . . . . . . . . . . . . . . 11 

3. Fortification with Internal Standards. . . . . . . . . . . . . . . . . . 11 

Standards and Reagents. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 

Analysis of Extracts. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 

A. Gas Chromatographic Operating Parameters. . . . . . . . . . . . . . . . . . . . . . . 13 

B. Mass Spectrometric Operating Parameters. . . . . . . . . . . . . . . . . . . . 13 

Quality Assurance/Quality Control Procedures. . . . . . . . . . . . . . . . . . . . . 14 

A. General Procedures of Operation. . . . . . . . . . . . . . . . . . . . . . . 14 

1. Sample Analysis Set. . . . . . . . . . . . . . . . . . . . . . . 14 

2. Sample Tracking . . . . . . . . . . . . . . . . . . . . . . . 16 

3. Data Storage. . . . . . . . . . . . . . . . . . . . . . . 16 

4. Data Review. . . . . . . . . . . . . . . . . . . . . . . 16 

12/89 QA/QC Xenobiotics v 
B. Procedures for Analytical Quality Assurance . . . . . 16 

1. Gas Chromatography-Mass Spectrometry 

a. Instrument Maintenance . . . . . . . . . . . . . . . . 16 

b. Gas Chromatography . . . . . . . . . . . . . . . . . . . 16 

1. Column Resolution. . . . . . . . . . . . . . . . . . . . . . . 17 

2. Relative Retention Time. . . . . . . . . . . . . . . . . . . . . . . 17 

c. Mass Spectrometry . . . . . . . . . . . . . . . . . . . . . . . 17 

1. Sensitivity. . . . . . . . . . . . . . . . . . . . . . . . 17 

2. Spectral Quality. . . . . . . . . . . . . . . . . . . . . . . . 17 

2. Gel Permeation Chromatography . . . . . . . . . . . . . . . . . . 18 

a. GPC Column Flow Rate . . . . . . . . . . . . . . . . . . 18 

b. GPC Column Resolution. . . . . . . . . . . . . . . . . . . . . . 18 

c. Collection Cycle. . . . . . . . . . . . . . . . . . . . . . . 18 

3. Silica Gel Chromatography. . . . . . . . . . . . . . . . . . . . . . . 18 

C. Criteria for Quantitative Analysis. . . . . . . . . . . . . . . . . . . . . . . 18 

1 . Gas Chromartographic Relative Retention Time . . . . . . . 18 

2. Analyte Identification Criteria. . . . . . . . . . . . . . . . . . 19 

3. Signal to Noise. . . . . . . . . . . . . . . . . . . . . . . 19 

4. Relative Response Factor. . . . . . . . . . . . . . . . . . . . . . . 19 

5. Surrogate Standard Recovery . . . . . . . . . . . . . . . . . . . . . . . 19 

6. Total Analyte Recovery. . . . . . . . . . . . . . . . . . . . . . . 19 

D. Quality Control. . . . . . . . . . . . . . . . . . . . . . . . 20 

1 . Continual Bias Assessment. . . . . . . . . . . . . . . . . . . . . . . 21 

2. Continual Precision Assessment. . . . . . . . . . . . . . . . . . . . . . . . 21 

3. Quality Control Chart . . . . . . . . . . . . . . . . . . . . . . . 21 

VI. Quantification of Target Analytes. . . . . . . . . . . . . . . . . . . . . . . . 22 

A. Quantification Procedures. . . . . . . . . . . . . . . . . . . . . . . . 22 

B. Determination of Minimum Level of 

Quantification. . . . . . . . . . . . . . . . . . . . . . . . 23 

12/89 QA/QC Xenobiotics vi 
Tables 

Table 1 -- List of Target Analytes, Internal 

Standards, and Surrogate Compounds and 

Their Quantitation Ions. . . . . . . . . . . . . . . . . . 2 

Table 2 -- Codes for the SCC Number and 

Matrix Type. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 

Table 3 -- Surrogate Standard and 

Internal Standard Solutions. . . . . . . . . . . . . . . . . . . . . . . 6 

Table 4 -- Target Analyte Fortification 

Solutions. . . . . . . . . . . . . . . . . . . . . . . 10 

Table 5 -- Gas Chromatography / Mass 

Spectrometry Operating Parameters. . . . . . . . . . . . . . . . . . . . 10 

Table 6 -- Composition and Approximate 

Concentrations of Calibration Solutions for 

Full-Range Data Acquisition. . . . . . . . . . . . . . . . . . . . . . . 15 

Table 7 -- Target Analytes with low recoveries 

for this method. . . . . . . . . . . . . . . . . . . . . . . . 20 

Figures 

Figure 1 -- Bioaccumulative Pollutant Study 

Database Output. . . . . . . . . . . . . . . . . . . . . . . 5 

Figure 2 -- Schematic of Analytical Procedures . . . 8 

2/89 QA/QC Xenobiotics vii 
I . INTRODUCTION 

This document, developed for Phase II of the U.S. EPA National Dioxin Study, 

describes the analytical procedures and quality assurance plan for the 

determination of xenobiotic chemical contaminants in fish. The analytical 

approach includes: 

- a simple sample preparation methodology that produces a single 

extract which minimizes analyte losses, 

- a procedure that is cost effective in terms of man power, 

chemical reagents, and instrumentation, 

- a characterization and quantification of a certain set of 

chemical contaminants, 

- an identification of unknown contaminants by screening the data. 

The set of analytes quantified was derived through considerations that included, 

but were not limited to, history (data from previous monitoring efforts), 

toxicology, persistence, bioavailability potential, total yearly production, and 

feasibility of analytes. A list of target analytes is presented in Table 1. 

Limits of quantitation for the Target Analytes are as follows: 

Target Analytes 

(except for PCBs) 

2.5 ppb 

Polychlorinated Biphenyls 

Level of Chlorination: 1-3 1.25 ppb 

4-6 2.50 ppb 

7-8 3.75 ppb 

9-10 6.25 ppb 

Fish were provided by the U.S. EPA Regional labs working with state 

environmental agencies. 

12/89 QA/QC Xenobiotics 1 
Table 1. LIST OF TARGET ANALYTES, INTERNAL STANDARDS, AND 

SURROGATE COMPOUNDS AND THEIR QUANTITATION IONS 

QUANT 

ANALYTE GAS NUMBER ION RRT 

Biphenyl-d10 (Internal Standard) 164 1.000 

Iodobenzene (Surrogate) 204 0.309 

1,3,5-Trichlorobenzene 108703 180 0.461 

1,2,4-Trichlorobenzene 120821 180 0.548 

1,2,3-Trichlorobenzene 87616 180 0.625 

Hexachlorobutadiene 87683 225 0.629 

l,2,4,5-Tetrachlorobenzene 95954 216 0.891 

1,2,3,5-Tetrachlorobenzene 634902 216 0.891 

Biphenyl 92524 154 1.010 . 

1,2,3,4-Tetrachlorobenzene 634662 216 1.015 

Pentachlorobenzene 608935 266 1.378 

Phenathrene-d10 (Internal Standard) 188 1.000 

1-Iodonaphthalene (Surrogate) 127 0.763 

Trifluralin 1582098 306 0.855 

Alpha-BHC 319846 219 0.890 

Hexachlorobenzene 118741 284 0.912 

Pentachloroanisole 1825214 280 0.924 

Gamma-BHC (Lindane) 58899 219 0.979 

Pentachloronitrobenzene 82688 295 0.994 

Diphenyl disulfide 882337 218 1.076 

Heptachlor 76448 272 1.185 

Chlorpyrilos 2921882 197 1.308 

Isopropalin 337820530 280 1.382 

Octachlorostyrene 29082744 380 1.395 

Heptachlor Epoxide 1024573 353 1.406 

Oxychlordane 27304138 185 1.410 

Chlordane, Trans- 5103742 373 1.477 

Chlordane Cis- 5103719 373 1.524 --------- 

Chrysene-d12 (Internal Standard) 240 1.000 

Nonachlor, TransDDE, p,p’- 

Dieldrin 

Nitrogen 

Endrin 

Perthane 

Monachlor, Cis 

4,4' -Diiodobiphenyl (Surrogate) 

Methoxychlor 

Dicofol (Kelthane) 

Mirex 

39765805 

72559 

60571 

1836755 

72208 

72560 

5103731 

72435 

115322 

2385855 

409 0.779 

246 0.805 

277 0.807 

283 0.836 

317 0.840 

223 0.844 

409 0.875 

406 0.876 

227 1.017 

139 1.017 

272 1.079 

12/89 QA/QC Xenobiotics 2 
Ts0tr 1. LIST or TARGET AYALTTES, IYTERYAL STAYOAROS, AYD 

----------------- flJ$llQsATE COMPOUYOS AU0 TrglR OUANTITATIOY IONS ___----------------- -------------------------- 

-------- C’rYllnrld+*-L Interns1 Srrndrrdl 

----------------- -------------------- 34P,,,,1AP20, 

Polychlorlnrtrd Oiphenyls, Cl l-13 

Monochlorabiphenyls 

Oichlorobiphrnyls 

Trichlorobiphrnyl? 

Tetrrcklorobiphrnyis 

Pentrchtorobiphrnyls 

HPrrchlorobipnenyLs 

Meptrchlorobiphrnyls 

octPchlorobipn*nyts 

ronrchlorobiphrnyrs 

Docrchlorobiphenyls 

27323la8 

25312429 

25321666 

26914S30 

25429292 

266016LC 

28655712 

JlC72830 

55742077 

20512L3 

188 0.318 

222 O.b52 

256 0.556 

292 0.57s 

326 0.801 

360 0.818 

394 0.881 

430 1.022 

C6L 1.250 

696 1.218 

12iaP QA/OC Xrnobioticr 3 
II. PREPARATION OF SAMPLE EXTRACT 

A. Sample Handling Methodology 

1. Shipment of Samples to ERL-Duluth: The EPA Regional 

Offices are responsible for the collection of the fish samples. 

Frozen fish wrapped in aluminum foil are sent to the ERL-Duluth 

Laboratory. 

2. Sample Logging and Coding Procedures: The Sample 

Control Center (SCC) or EPA Regional Offices notify ERL-Duluth 

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-Duluth personnel complete the chain of 

custody forms and then notifies SCC that samples arrived safely or 

if there were any problems with the samples (example: a 

mislabeled sampled, no species identification). 

Samples are initially placed in a large walk-in freezer. 

Aliquots (100-500 g) of ground fish tissue samples (sec. I.A.3.) 

are transferred to Laboratory freezer A. Extracted samples are 

stored in laboratory freezer B. Completed samples are taken to a 

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 from which the sample came are entered 

into the data base. Figure 1 is a sample output of the data base. 

The first two letters of the SEC number indicate whether the 

sample is an Environmental, Method or Matrix Blank, or Duplicate 

Sample. All Environmental samples begin with the letter D. The 

Blank and Duplicate samples begin with the letter Q followed by a 

D or an R for duplicate or reference fish sample, respectively. 

Table 2 lists the possible codes for the SCC number, and matrix 

type. Episode numbers for Blanks and fortified Matrix samples are 

entered as 0000. 

3. Tissue preparation and storage procedures: Fish tissue is 

ground frozen at ERL-Duluth 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 jars with aluminum lined 

plastic lids. 

12/89 QA/QC Xenobiotics 4 
Figure 1. Bioaccumulative Pollutants in Fish Database Output 

NDS PHASE II: BIOACCUMULATIVE POLLUTANTS IN FISH 

Sample Tracking System ERL-D Loc.: 1234 

EPISODE #: 4444 SCC #: DP022030 

Sampling Information: 

Sampling Office: ERL-Duluth 

State & City: MN Duluth 

Sampling Contact: Regional Coordinator 

Date Sampled: 8/23/87 

Site Location: MM Lester River @ Lake Superior, Duluth 

Latitude: N 44 24' 34'' Longitude: W 94 24' 53" 

Analysis Lab: D Date Received: 8/31/87 

Matrix Type: F PF Steelhead Species Code: A2 

Sample Composite: 5 

Analytical: PCDD/PCDF Pesticide & Industrial Chemicals 

Extraction Date: 0/ 0/ 0 11/ 3/87 

CC/MS IO: DR871213 

LAB ID: B110387JJ 

Weight: 20.00 

%Lipid: 3.2 

DPE Indication: Mass lipid on GPC: 0.68 

Comments: 

Xenobiotic Definitions: 

QA Flags: 

E - exceeds highest calibration standard 

D - below limit of quantitation 

Limits of Quantitation: 

Pesticides- 2.50 ppb 

PCBs: 1-3 chloro - 1.25 ppb 

4-6 chloro - 2.90 ppb 

7-8 chloro - 3.75 ppb 

9-10 chloro - 6.25 ppb 

12/89 QA/QC Xenobiotics 5 
_______ Fipuro ,,,--A-------,,,,, e--s------ -- w-v--- -- 1 B~orccumut~~ivr PoLlutfnt2 In ftlh Qfir2hfia),Qyleut 

------------ 

EPISODL e: Lb44 SEC I: 0P022050 ERL-0 Lot.: 12sc 

rmrgot Analyto 

t,J,5-Trichlorobentrno 

!,2,&.Trichlorobentrna 

1,2,$~Trichlorobrnttnr 

Wexachlorobutrdirne 

l,Z,C,S-Trtrrchtorobrnlrnr 

l,~,~,5-~cfr~c~~oroa~nrrnr 

B1plltnyt 

1,2,S,L-Tetrrchlorobonz~n~ 

P~nc~chlorobontrn~ 

Tritlurrlin 

Alpha-BHC 

wrrachlorobontonr 

Pentach10roanisoto 

trnmr-BHC (Lindano) 

Pentachloronitrobrnzene 

Oiphrnyl disulfido 

nrptrchlor 

Chlorpyrifor 

lroproprlin 

Oclrchlorostyrene 

Hrptrcnlor Epoxidr 

Oxychlordanr 

Chlordrnr, franaChlordrno, CirYonlchlor, TrrnsDOE. P,P'- 

Ditldrin 

witrofrn 

Endrin 

Perthrnr 

Monrchlor, Cir 

Mrthorychlor 

Dicotol (r;rlthrnr) 

Mirrx 

Total Monochtorobiphrnyl 

Total Oichlorobiphrnyl 

Total Trichlorobipkrnyl 

Totat Trtrrchloroblphrnyl 

Total Prntachlorobiphrnyl 

Total Horrchkorobiphrnyl 

Total noptachLorobiphanyi 

Total Octrchlorobiph~nyl 

Total Xonrchlorobiphonyl 

Total Docachlorobiphrnyl 

Total Pokychlorinrtrd liphrnylr 

CASRM QA Ilrg COYCY (n9f9) 

Mrrcury ( AA anrlyria) 

SURROGATE RLcOVIRr: 

lodobrnzono 

lodonaphthrlrno 

b,b '-Oilodobiphrnyl 

\2/B9 OA/Qt Xrnobioticr 6 

108-70-3 

120-82-l 

87-61-6 

87-68-3 

95-95-b 

63b.90.2 

92-52-b 

63b.66.2 

601-93-5 

1582-09-8 

319.IL-6 

1 Il*TL-1 

1825-21-i 

58-89-Q 

12-68-1 

882-53-7 

76.Lb-8 

2921-68-2 

33820-13-O 

29082.7C-4 

102b-57-S 

26880-bb-8 

5105.71-t 

5103-71-9 

39765-10-5 

72-55-P 

bQ-57-1 

1836-75-S 

72-20-U 

7t.S6-0 

37Sb-CP-C 

72.b3-5 

115-32-2 

2185-85-5 

27s23- 18-O 

25512.b2-9 

25325-68-6 

269lC-33-O 

25b29-29.2 

26601-66.6 

28655-71~2 

3lb72-83.0 

537b2-07-t 

2OSl-2b-J 

7&39-97-b 

YD 

WO 

UO 

MD 

MD 

YO 

0 

WD 

MD 

0 

MD 

0 

NO 

ND 

no 

NO 

WO 

WO 

wo 

YD 

E 

MO 

MO 

MO 

MO 

NO 

E 

NO 

NO 

HO 

110 

MO 

0.34 USlO 

12 

L8 

93 

I.25 

2.34 

IS.2 

2f.b 

1.23 

17.2 

IS.1 

b5.2 

123b 

2t .2 

:a.4 

118 

ll.b 

60.6 

265 

107 

39.8 

56b 
Environmrntrl rrmpl* QA 8Pmplr 

Firrt Letter: 0 Q 

Second Lottor: A -- Region 1 a -- Method blank 

I -- RrRion 2 D -- Laboratory dupllcrtr 

C -- Region 5 R -- Rrfrrrncr firn or 

0 -- Region L fortified mrtria 

E -- RrRion 5 

c -- Rogion 6 

e -- Region 7 

n -- Region 8 

T -- Rrgfon 9 

J -- Rrglon 10 

Matrix Coda Matrix lypr 

t -- fish Y8 -* Yhola bottom 

L -- Lib duOLicrt0 If -- Bottom fillet 

R -- Rofrrancr fish PC -- Predator fillet 

T -- nothod Stank UP -- Yhol l prrdrtor 

1. patraction a Tirrut frnalo8. 

FiRurr 2 is a rchrartic of rho rnrlytlcrl procrduror. 

1. Joahlet Extraction: Ground ffrh tirrur (20 9) is blended 

with Anhyurour sodlua rulfrtr (100 9) in a 2SO nL beaker to 

corplrtrly dry the 6ADptr. Tuo-thirds of the l irturr is 

transferred to A coarao frltted rorhlot l atrrct(on thinblr and 

spiked uith turrogato Standard Solution A (25 ul), Table 3. Also, 

at this tire the Cortffird Matrix Sample and tha tortifird 

Duplicate Sampka, it uaad, ara apikrd milk 25 ul of Target Anrlytr 

Solution (one of rfght Target Analytr fortification Solurfonr, 

frblr 41. thr rrmrinfn( rrmplr ir rddod to the thimble and the 

sample is rxtrrctrd for at lorat 12 hours with hoxrnr/n8thylena 

chloride (l:l, v:v). lhr entract is than quantitatively 

trrnrforred to l Kudorna-Oanirh (r(O) apparatus fittrd uith a 

J-ball Snydrr column and rrducrd in volura to lrsa than 5 aL on l 

steam bath. Tho oxtracts are further rrducrd under carbon 

ftttrrrd air to romovo all aolvrnt. Thr KO rarplr tubor with 

lfpid ara ueighrd. TUO 0.10 g allquota are proprrrd for Gel 

Permeation Chromrto9rrphy (GPC) by.uei9hing into 5 ml tuber. The 

empty r~aplr tubr is dried and reroighod to detrrminr the prrcent 

1 ipid. 

12189 QAIQC Xonobfotlc8 ? 
Figure 2. Schematic of Analytical Procedures 

- I 

TOlMlE3slaw - 

c 

21gsucAGEL 

P 

I3 di- WANE 

b 

: 

12/89 QA/W Xeaobioticr 0 
2. rort!f;crtion ui(h f~rroaatr Standards: 

flch sample 1s fortified uith Surrog~C~ Standard SoLutjon 4 (25 

uL) prior to sornlrt ortraction. tha standards In this (o\~c::~ 

hove been srlrcted to reprosent vartous typos of ckrmic~(~ ‘2.,na 

in the list of target rnrlvtrs, and 4re USed to l VatJIce the 

recovery of trr9et rnrlytrs in clranrd-up l nvironmrntri ~amp:~s. 

Ii,bli-1 Surrogate Standard and Internal Standard Solutions A------- ---------_--_-------------------------------- 

Surrogate Standard Solution A (25 uL) 

SomDounQ Concrotrstion lggL?Il -------------- 

lodobonrrne 125 

1.Iodonrphchrlrnr 125 

6.4 -0iiodobiphenyl 125 

Internal Standard Solution (10 uL) 

$omDounQ Concenrration iyXL?ii -------------- 

9iphrnyl-OtO SO 

Phonanthrena-OIO 7s 

Chrysrnr-0,2 7s 

------------------------------------------------------------ 

3. Fortification uith Target . Anllvtrr. A blank 

matrix sample is fortified with onr of right Target Analyte 

Fortiticrtion Solutions (2) uL), Trblr 4, to rvrlurtr the 

ovorrll accuracy of I subrrt of the target rnrlytrs. Two Dlanr 

matrix sampler will br fortifird uith the Sam* solution 

once in rvrry tivr (20X) rrmpla seta to rvrlurtr prrclrion. 

12119 QA/QC Xonoblotlcr 
solution A: Aroclor 1256 at SO0 u9/mL (A-0 #nd 1000 u9/n\ 

(r-2) in tolurnr. 

Solutions 9.C and 0: Each have Targot Anrlytrs at 125 u9/nl 

o-1, C-l, D-1) and 250 u9/ml (a-2, c-2, 0.2). 

Solyfig”-l --- 

t,2,3-Trichlorobrntrnl 

1,2,C,S-lrtr~chloroD~~z~~* 

liphrnyl 

Atpha-IMC 

Chlordrnr, cis 

Olcofol 

Endrin 

Diphrnyl disuifidr 

wrr~chtorobrntrnr 

Mi rex 

octachtorostyrena 

Prntrchlorobonxone 

Perth@nr 

Soiution s --------- - 

1,2,4-Trichtorobrnxrno 

1,2,3,C-lrtrrchlorobanzene 

Gamma-@llC (Lindano) 

Chlordrnr, trans. 

DOE, P,P’ 

Wi troten 

Hoptachlor 

lsopropalin 

wonachlor, cis 

Oxychlordano 

Pentachloronitrobrnreno 

Triflurriin 

Hrxrchlorobutadirnr 

fotulion e -s-w B-sl,S,S-trichlorobrntrna 

1,2,3,S-Trtrrchlorobanxone 

Mrthonychl or 

Chlorpyritor 

Oirldrin 

Hrprachlor Epoaidr 

Monrchlor, trans. 

P~ntrchloroanisotr 

---------------------------------- --------_-----------_______________ 

12/19 QA/OC Xrnobloticr 10 
C. I$o(rtion d Xenobiotic Chemrcrl Contrminenrs. 

1 . w Permeation Chromrroorrahv; A CPC system is used to 

isolate xenooiotlc chernlcel contemlnents from blotoglcrl motecu,es 

(fish tipid). The GPC cotumn (2.5 X SO cm) (ACE Glass Comprnv) ,s 

packed uith previously swelled Biobeed SX-3. The GPC lnjectlon 

port valve is fitted uith I 0.075 mm stainless stect screen ft(ter 

to remove perticulates. The solvent is pumped ec S mL/nln. Tht 

absorbance of the effluent is montcored with a 254 nm uv derector 

(Varlan Aero9rrph). Each l liquot of extract is diluted rich 2 mu 

of l lution solvent. The supernatrnt is qurncitrciveiy transferred 

into a sample loop of 8 26 port auto-sampler uith three additIonat 

1 mL uashes of the sample vial. The LOOPS of the auto-sampler are 

Loaded sequentially onto rhe CPC column under computer control. A 

CPC performance standard solution (Sec. IV.9.1) is run CO 

determine the collection period. This sample is run prior to each 

srmpte set. Xenobiotic chemical concrninrnts uhich l lutr C 

minutes after the elucion apex of Di-2-•thylhexylphthrlate, 3EHP, 

and 1.7 rimes rhe l lucion volume becueen the apex of OEHP and 

Pyrene are collected in a KD. Each sample (tuo loops) are 

collected in J Single KD. Wexane (10 mL) is added to rhe CD and 

the sample is reduced in volume 0 mL) on a steam bath urlng a Sbell Snyder column. The sample is further reduced in volume to 

0.5 mL uich a scream of dry filtered air at CO0 C prior to silica 

gel chromrto9raphy. 

2. silica tcl Fhramarograohv: A Kontes column packed uirh 

freshly prepared, prrtirlly deactivated silica gel is used to 

remove naturally occurrin9 cholesterol and fatty acids. 

The column (9 mm X 19 cm plus l SO ml reservoir) is packed with 

9lass uool, anhydrous sodium sulfate (0.5 cm), silica 9eL (2.1 g 

about 7 cm), and rnhydrous sodium sulfate (0.5 cm). Ike column is 

pre-•lured uith SO mL of hexane and the serple is quantitatively 

transferred to the column uirh three 0.S mL mechylene 

chloride/hexrne (15%. v:v) urshes. The column is then cluted with 

an additional 58.5 mL of the seme solvent. Toluene (1 ml1 is 

added to the collection vial as a Mkeeperll. The sample is reduced 

in volume (0.5 mL) uith a stream of dry filtered air, LO ' C, and 

qurntitatively transferred with roluene to a capered vial (1 mL). 

3. Fortification rith Internal Standards, The samples are 

reduced to 90 UL and fortified with 10 uL of Internal Standard 

solution (Table 3) and stored in a microviel for GC/NS analysts. 

12189 QA/QC Xrnobioticr 11 
I I I . Standards and Reagents 

A. Reagents 

1 . Solvents: Only pesticide grade distilled in glass 

solvents are used. They are: hexane, methylene chloride, 

toluene, acetone, and cylcopentane (Burdick and Jackson and 

Fischer Scientific). 

2. Sodium Sulfate: Sodium sulfate (Baker Chemical Company 

reagent grade anhydrous) is baked at 650°C in a furnace for 

24 hours, cooled, and stored in an empty hexane solvent bottle. 

3. GPC Packing: Biobead SX-3 (BIORAD Corporation) are 

swollen in the elution solvent, cyclopentane/methylene chloride 

(1:1, v:v). 

4. Silica Gel: Silica-Gel-60 (Merck-Darmstadt) is activated 

overnight it 225°C. It is then deactivated by adding distilled 

water (1% w:w) and shaken at high speed for four hours to 

disperse the water. The mixture is allowed to equilibrate for 

eight hours. 

B. Standards 

All pesticide standards are made from pure standard materials. 

1 . GPC Performance Check Solution: Prepare a solution of 

5 mg/ml Dacthal, 4 mg/ml DEHP, and 0.2 mg/ml Pyrene. 

2. MS Performance Check Solution: Prepare a 5 ng/ul solution of 

decafluorotriphenylphosphine (DFTPP) in toluene. 

3. Silica-Gel Performance Check Solution: Prepare a solution 

containing 2 mg/ml Dieldrin and 10 mg/ml cholesterol in an 

appropriate solvent. 

4. Internal Standards: Chrysene-d12, phenanthrene-d10, and 

biphenyl-d10 are used as internal standards. Table 1 

indicates which internal standard the target analytes are 

referenced to in quantitation. Table 6 indicator the 

concentration of the internal standards in the calibration 

solutions and in the solution used to add the internal 

standards to the sampler just prior to MS analysis. 

5. Surrogate Compounds: Iodobenzene, 1-Iodonrphthelene, and 

4,4’ -diiodobiphenyl are used as surrogate compounds. Each 

are present at 125 ug/ml (Table 3) in the sample spiking 

solution. Table 6 indicates the concentration present in 

the five calibration solutions. 

128/9 QA/QC Xenobiotics 12 
6. Pesticides and PCB Standards: A stock solution is made 

containing the pesticides listed in Table 1 and the PCB 

congeners Listed in Table 6. Five calibration solutions 

are made at the concentrations listed in Table 6. 

7. Fortification Solutions: The pesticides are divided into 

three fortification solutions at two different concentrations 

(Table 4). Arocler 1254 is used as the PCB fortification 

solution at the concentrations listed in Table 4. 

IV. Analysis of Extracts 

Samples are analyzed on a Finnigan-MAT Model 4500 CC/MS 

with SUPERINCOS software and supplemental public domain software (1,2) 

provided by the U.S. EPA laboratories in Cincinnati, OH. All Target 

Analytes will be quantified individually and the results reported as unique 

values, except for PCBs, which will be reported by total congener at each 

degree of chlorination. An analysis set includes an analysis of a mess 

spectrometer performance check solution tree. III.B.2), an analytical 

standard, an unfortified solvent (instrument blank), and twelve prepared 

sampler. The GC/MS operator reviews the MS performance solution, 

analytical standard, and instrument blank data before starting the analysis 

of samples. 

A. Gas Chromatographic Operating Parameters: A Finnigan-MAT 

Model 9610 GC is fitted with a 60 m X 0.32 mm ID D8-5 fused silica 

capillary column (J & W Scientific) and operated in a temperature 

programmed mode. The capillary column is interfaced directly with the 

ionizer. Injections are made in splitless mode. Specific operating 

parameters are provided in Table 5. 

B. Mass Spectrometric Parameters: A Finnigan-MAT 

Model 4500 mass spectrometer is used in the electron impact mode. 

Specific operating parameters are provided in Table 5. The 

positive identification of target analytes is based upon a reverse 

library search threshold value and relative retention time (RRT). 

Quantification of the target analytes is bared on the response factors 

(RF) relative to one of the three internal standards listed in Table 1. 

Table 1 is formatted so that the target analytes follow the internal 

standard used in quantification. RRTs and RFs are initially 

determined using data from triplicate analysis of each of five 

target analyte quantification solutions (Table 6). 

12/89 QA/QC Xenobiotics 13 
Table 5. Gas Chromatography/Mass Spectrometry Operating Parameters 

GC Parameters: 

Injector Temp.: 250° C 

Initial Temp.: 100° C held for 1 min 

First Ramp: 5° C/min to 175° C 

Second Ramp: 3° C/min to 280° C hold for 20 min 

MS Parameters 

Cycle time: 1.0 second 

Acquisition time: 0.95 second 

Scan Rate: 1.0 second 

Scan Range: 95 - 550 amu 

Electron voltage: 70 eV 

Emission Current: 0.30 mA 

Manifold Temp.: 95° c 

Ionizer Temp.: 150° c 

Transfer Line Temp.: 280° C 

V. Quality Assurance/Quality Control (QA/QC) 

A. General Procedures. of Operation. 

1 . Sample Analysis Set: Analysis of samples is 

done in sets of twelve consisting of: 

a. Blank: A METHOD BLANK (blank extraction 

apparatus) is analyzed with each set. 

b. Fortified Matrix: A blank matrix 

sample is fortified with one of right different 

mixtures of Target Analytes (Table 4) and analyzed 

with each set. 

c. Duplicate: Each analysis set contains 

one duplicate sample. In four of five (80%) of 

the sample sets the duplicate is an environmental sample previously chosen for 

analysis in that set. In one of five (20%) of the 

sample sets the duplicate is a blank matrix 

sample that has been fortified with the same 

target analyte subset as 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 

analytes. 

12/89 QA/QC Xenobiotics 14 
TJbl. 6. Comporirion Jnd ApprorimJtr COnCOntrJtionS of CJlibrJtlon 

solytiq~g for rUlL-aJnp~,eif4,~egyilit’on --a- -- ------------- ---------------_--_-______________ 

CP~94”f’4flp”-,~nOLY4~ 

AnJlytr/lnt. Std./ 

surros4fZ-CEe2!dnd -e-s- CAL 1 -a---w----- -B-s- G&4,2 --s-- CAL ---e-B- 3 CA4,f,,,E!L,Z 

PCI CJL. ConqJners 

Cl, 2. 

Cl2 2,s. 

CL3 2,c,5- 

tkb 2,2',C,bCL5 2,2',I,C,S'- 

CL6 2,2',C,C',5,6'- 

Cl7 2,2', 3*C,5,6,6- 

Cl8 2,2',5,3',C,5,6'- 

t'l0 

ALL TJrqJt AnJiVtJJ 

other thin PC#s listed 

in TrblJ 1 

IntornJl StJndJrdJ 

Chrysrnr-d12 

PhJnJnthrJno-dto 

qiphrnyl-d10 

Surroprtr Compounds 

0.25 

0.25 

0.25 

0.50 

0.50 

0.50 

0.75 

0.75 

1.25 

0.50 

7.50 

7.50 

5.00 

0.50 

0.50 

0.50 

0.50 

0.50 

1 .oo 

1.00 

1 .oa 

1.50 

1.50 

2.50 

1.00 

7.50 

7.50 

5.00 

1.00 

1 .oo 

1.25 

1.25 

1.25 

2.50 

2.50 

2.50 

3.75 

3.7s 

6.25 

2.50 

7.50 

7.50 

5.00 

2.50 

2.50 

2.50 

2.50 

2.50 

5.00 

5.00 

5.00 

7.50 

7.50 

12.50 

5.00 

7.30 

7.50 

5.00 

5.00 

5 .oo 

5.00 

5.00 

5.00 

10.00 

10.00 

10.00 

15.00 

15.00 

25.00 

10.00 

7.50 

7.50 

5 .OO 

10.00 

10.00 

12119 QAIOC xrnobiotftr 1S 
d. g nvirO”mJntJl SJmO(JS: JlnJ Env!ronmontJl 

SJnPlaS Jre SnJtyXea ulth JJCk Sot. 

. . SJmDie r-actinq: 4 JJmplr cractlnq Jnd loqqjnq 

SyStJm is use0 co assure fhlt n0 SJmplJS JrJ 

last tsrr SeeClan I-A). 

5. 3u St?rJJc: Sata folders con,lstinq of a11 

hard Copy 3UtDUt 7s maintained for each sample. 

In addition, rlt rJY CC/MS dJtJ 1s stored on 

mJqnet*C tJDJ. 

c. 3u Pevicu: SC/MS dote is in!tiJi(y rrvieuJd 

Qurlnq sample sot JCQUlsitiOn by the CC/MS oPOrJtOr 

10 JSSUrC t8Jt 1” Instrumental PA prrrmeters are beinq 

met. Finrl revleu Jnd rrlrJs0 of the dJCJ is tn. 

rJJpOnJibiL lty of the Project MJnJgJr. OnCO tkJ pUJ(lty 

JJJUrJ”C, crrrrril hive been mot, the quJntlficJtion 

informJtlOn is l nterrd intO thl dJtJbJS0. aurriry 

rssurrd dJtJ is then transferred to qlOACC/STORET 

for avJilJbi\iry co the EPA Regions. Brforr rJl.JSJ 

to the public, ~11 CrJnsfrrred date iJ verified for 

completeness by the d~tJbJ10 mrnrqer. 

q. GenerJl DrOcJQure~ c AnJLYtlCJ( QUJlitV ASSUrJnCJ: 

1 . w ;~romJtoJrJoky-*~ss oectrometrv System: 

J. ]nstrumJnt MJintJnJnce: The CC/MS system 

is mJintJine6 Jccorainq to the manufacturer’s 

suqqested schedule. The nrintenrnce schedule 

is indiCJted On J cJ\endJr L0CJt.d AeJr JJCh 

instruarnt. ~oq books will be kept for: DJity 

instrument settings; SJmpteS JnJty2.d; 

MJintenJnce; Jnd OJtJ qtOrJq0. Instrumentrt 

proDlens resulting in more then tuo drys of doun 

time Jre to be rrportrd CO the EPA MJSS 

Spectromerry CJcility Supervisor to disculs 

solutions to the problems. 

b. Q& ~hrOmJtoJrJOhY: The PJrfOrmJnCJ Of the 

CC is evaluated by OeterninJtion of the 

number of ChJOretiCJl PlJteS of resolution, and by 

relJtivJ retention Of the SurrOqJte StJndJrdJ. 

12/69 aA/Qc xenobiotics lb 
1 . kb% *C¶oIution: The number of 

th*or@ttCaI pl8t*a of rrsolution, M, is 

determined at the rima the crlibrrtlon Curve 

is genrrrtrd urlng Chry¶rnr-d,,, and monItored 

ulth rrcn sample sot. The vaLue O+ M snrlL not 

decrr~se by more then 20X. The equalian far 9 

is given as tollour: 

I( l !6 (II / Y) 

2 

q here, RT 8 R~t~ntton Tim0 of 

Chryronr-dtO in SOCOndS 

Y s Post width of 

Chryreno-dlD in seconds. 

2. Qetativ* Retention Time; Relativ8 

retrntlon timrs of the intrrnrl standards 

shall not deviate by more than *I- S X from 

the valurs Calculated at the time the 

calibratron curve uas gonrrrtrd. 

C. fjj Soectrometry: The prrformancr of the 

m8ss sprctromrtrr vlll br evaluated for both 

sensitivity and spectral quakity. 

1. Srnsitivitv: The signal to noiso value 

must be at L18st 3.0 or greator for m/x 196 

from an injection of 10.0 ng drcrfluorotriphrnylphospninr (OfTPP). 

2. .Soectral Ourlity; Ike intensity of 

ions in the soectrum of DftPP must meet the 

criteria list*0 brlou: 

_,mLl,_,~~~~~~~~~~rifJrir ------- 

127 30-40x mats 198 

197 * 1x mass 198 

198 bare peak 

199 s-9x mrsr 198 

Lb2 BCDX ma8~ t9a 

-w-s b&Z --w-----s- “mllX-miZlmfC1-- 

12iav OA/OC Xrnoblotfc8 I7 
2. w Permeetton Chromat0QrlDhv: The GPC is 

nrintrined rkon norded 48 drtrrminrd by visual 

inspection (coiuan discoloration, Ialt8, crrctr, l tc) 

l Oa8uronont of ftor r8t8, 8nd rOutin no88uremont of 

contrminrtion of instruaent blrnts. 

4. the flou rate of cne 

CPC 1s mrrrurrd tnree times during 8n l nrtys~~: 

1) before the CPC rrrolution rotution, 2) after itt 

sraplrs are lordrd but before analysis and 3) after 

411 ramp\88 h8vO brrn rnrlyxed. ftou ret* should not 

vary by nor0 th8n l /- a.2 nL/min. 

b. Cj?J Eolumn Rrrolution: h 350 ul injection of ( 

performance solution containing Dacthal (5 mg/mL), 

DEHP (b mg/nlI, and Pyrrn* (0.2 ng/nL) mu8t be run 

drily to l vrlurtr colunn resolution, and to brt*rmjn* 

rnrlyte starting and ending collection volume. 

c. CoLltction CYclc: Proprr operation of the 

GPC wilt also bo rvrlurtrd by rrcoreing the time 

durin9 an analysi8 cycle that the collection/raste 

valve is in tho coktect porition. fhi8 is 

Pccompli8hrd most rr8ity by recording the vrlvr 

position on tho second pm of 8 durl pm recorder. 

Tho start and end of tha coIImct cycle must not 

drvirtr by more th4n l /- 2 aL. 

3. $iLicr m Fhromatoar8ohy: Thr silica get 

column uili be l valurtrd by it8 ability to rr8olvr 

cholesterol from a srlrct model target rnrlyte, 

Oiridrin. A solution (1.0 mL) containing Dirldrin 

(2.5 ag/mL) and choltrtrrol (10 mg/nl) i8 8pitPd onto a 

silica 911 coluan and rluted uith mrrhylrn~ 

chloridr/hrxrnr (?SX, v:v, 60 ml). The rlurnt, 

rn8lyrrd by flrmr ionization detrctor/988 chromatography 

tFID/tC) must not contain aoro than 10X of 

the cho~rrtrrol uhilr at loa8t 90% of the Dirldrin must 

br rrcoverrd. 

C. GriteriC u Ourntftrtivr Analyrir: 1111 of the 

fO\louin# quality a¶8uranCo crltrria murt br met before a 

quantitative value nry bo rrportrd for an rn8lytr. 

1 * u $hromatoar8phic Retativc Retention time: 

Rr\rtivr rotrntion time8 of the trrger rnrlyt8s shall 

not drvirtr by aoro th8n l /- 3 I]( from the val~O8 

rstrblirhrd during the ganrration of the criibrrtion 

curve (8ae trblr 1 for RR1 data). 

l2llP OA/OC Xrnob~otlc8 18 
2. 

3. 

b. 

5. 

6. 

!m Jdentific8tion Criteri8: Reverre 8eerch 

identificerion of an enriyte (SEAR) must have an FIT 

**lU* of 800 or greater. 

3-L u Moire: The qurntification ion must heve 

J *iOnal to noise value of et leest 3.0. 

Rciative Re8Don8e factor: The reletive re8ponse 

factor for eech enelyte qu8ntificrtion ion reLrtivr to 

the appropriate i-ternel StJndJrd qUJnt!fiCJtion i on 

mu8t not devirte by more then 20% frO4I the value 

aeterminrd on tko Previous dry (uithin l 2b hour perloo) 

and uithin 50X Of the meen velue troa the crlibretion 

curve. The terget l nelyte8 Endrin, Dicofol, and Decsc~~orobipn@nyl mu8t not deviete by more than 50% from 

the prrvious day. 

A control thJrt is mJintJinod on the drily response 

fJctor8 for t4cn trrget rnetyte. 

tjurroaate Standard Recoverv: The percent recovery 

(XR) of l Jch SurrogJte rtrndrrd wit1 be detrrnined 

for rll sJmple8, Js 8hOUn below: 

XI8 n 100 tc0/c41 

where ZR8 a surrogete percent recovery 

co = observed concentretion of 

surrogete 

CI = recur1 concentrJtion of 

surrogete added to the ranpie. 

The percrnt recovery must be uithin 25 end lJ0 

percent for iodOnephth4tene and 50 and ISO percent 

for b,b ‘-di iodobiphenyt. The recovery of iodobentene 

quelitrtively indicrter the eatent of l vepor8rive 

losree chef the enelyter listed in Teble 7 ney l rperiencr. 

Tote1 Anelvtt Recoverv;. Ihe overrll eccurecy of 

quentfficetion of l ll terger rnrlyter ir l velueted 

by the enetySi8 Of 8 8Ub8et Of ter#et Jnetyte8 

fortified into J mrrrix blent. Recovery of the 

fortified l nelyter must feLL within the range of SD to 

150% except for thO8e Iistrd in Teble 7. The enrtyte8 

12/89 QA/PC Xenobloticr 19 
Trblr 7. trr*rt Anokytor with LOU rrcovrrior for 

,,,,,,,,,,fhl~,~~l~SPI ---_----------------------- 

l,J,S-trlchiorobentrno 

1,2,C-Trichtorobrntonr 

1,2,5-TrichlorobCnrCnp 

1,2,L,S-Trtrrchlorobrntrnr 

1,2,3,5-TrtrachkorobenzCno 

1,2,3,C-TatrPchloroConxono 

Pmntachlorobontono 

aorrchlorobutrdirnr 

listed in Trblr 7 shou retovoriea that frtt in the range 

of 20 to SOX for tkis method. An rvrragr 4natyt8 

r,covory (XAU) for all trrg8t lnotyt8S mill br calculated 

and must b8 grrrtrr than 35% but lrrr than 150X. 

A control chart for Iota\ anaLye rrcovrry and analyet 

rrcovery is nrintrinra for oath spItin rolution. 

To drtrrmino tOtat OnOiytO rOCOVOry first CltCUtltm 

tk8 prrcont recovery (SR) for l ach fortlficrtion 8nrlytr 

urinq, 

Xl8 l lOO((Ai-lO/Tl) 

rhrr8 XRr 8 l nalytr prrcrnt rtcovary 

Al 8 mrrrurrd rnrtytc concontrltion in 

fortificrtion ranpi rftrr 

rnrtysir. 

li g natural analye concentration in 

sample boforr fortification. 

Ti 8 known true concrntrrtion of 

rnalytr fortificrtion Irvri. 

Than crlculrcr XII by, 

XII I (Sumclrtfon of XUr) /N 

uhrrC N n number of tortlffcatton 

rnrlycrr In spiting solution. 

D. gurlitv Sontrot: Ourlity control chart8 dirptrying 

quantitative birs (XII and prrcillon (XC) are nrlntrinrd 

for 8och rnrtytr urfng tOtUS 121 Bottulro, Lotus Oovrloprrnt 

torporrclon. Parcone bias and percrnt prrcirion will br 

rocordod rnd the control chart will br updrtrd aftor each 

anrtyrl8 88t. Compirtr rtrtlstfcr l ry br done for bias and 

precirion at the complrtlon of the projrct. 

12119 o*/oc x8noblotlcr 20 
Xl 8 (IOO(Ca-Cb)/T) - 100 

uhrrr CA m dotermined concentrrtion after rnrlvsis 

CJ m COnCentration prrsrnt brforr spike rddrd, 

T a knoun vrtur of tko rpikr. 

2. C~pt’-uaL Precision Assessment: 

Precision of quPntificrtion of Pack tArOPt analvtP 

wit\ be PssessPd ,rprrotrly for duplicate rnvironmrntrl 

samples and duplicate fortified matria samplrs. 

tP - 100[(C1-C2)/Ctl 

beher* Cl a concentration of rnrlytr in spika 

ranptr 1. 

c2 ’ concentration of rnolytr in spike 

SrnPle 2. 

CC * Actuat concancration of anrkytr 

for fortified notrir rampto or noun of 

duplicAtr rnvironmontrl srmplrs. 

?A fdstor outZi$b of criteria --mm-- ---w-e- gorr2sylve Actlen -------_-------------~--- -se -------- -ws-- 

OtTPP srnsitivity And/or rrtunr mt 

ion ratios clrrn MS 

Rrlrtivr Rrtrntion limo Adjure GC prrrnetrrs 

flush tt column 

rrplrca tt column 

Rrlrtivr Rrrponsr factors rrtune YS 

r@crlibrPtr 

Rrcovrry of Surrogrcr Standard8 verify MS drtJ 

rrprrt rrmpir rrtrrction 

focal Anrtycr Roeovary (XAR) If XI for 8t Least 80X of 

Carpet rnrtvtos not Listed 

in trblr 1 nrets crltorir 

protrod uith colculrtions, 

12/89 OI/@C Xrnobioticr 21 
VI. Quantification of Target Analytes: 

A. Quantification Procedures 

Response factors are determined for each target analyte and surrogate 

compound relative to one of the three internal standards. The 

response factors are determined by: 

RF = AXCIS/AISCX 

where AX = peak area of quantitation ion for a target analyte 

or a surrogate compound, 

AIS = peak area of quantitation ion for either 

Biphenyl-d10. Phenanthrene-d10, or Chrysene-d12, 

CIS = injected quantity of the internal standard, 

CX = injected quantity of the target analyte 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 target 

analyte concentrations: 

CONC = ((QA * NUM * QRV) * FESV) / (VIA * SIZE) 

where QA = concentration as calculated using the 

response factor from the drily standard, 

NUM = factor to convert to number of ug/ml, 

QRV = 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 recounts for the total lipid present in the 

sample and the amount injected on the GPC. The FESV is 

calculated by: 

FESV = Final Volume (ml) * (Total Lipid (g) / Lipid on GPC (g)) 

12/89 QA/QC Xenobiotics 22 
Calculations for determining surrogate spikes and fortified 

amounts use the following equation: 

CONC = (SA FESV) / (FSRV * SIZE) 

where SA = spike amount, 

FSRV = Final Effective Surrogate Volume, 

FESV, SIZE = same as above. 

The FSRV term is equal to the FESV term. The concentration 

of a target analyte is denoted in the final report if it 

exceeds the calibration range, ('E' flag), or is below the 

quantitation limit, ('D' flag). 

B. Determination of Minimum Level of Quantification 

The calculated method detection limits (MDLs) for the analytes, (determined 

according the Federal Register 1988, Vol. 40, Appendix B, Part 136, 

Definition end Procedure for the Determination of the Method Detection 

Limit, Rev. 1.11), are unrealistically low in comparison to the analysis of 

the xenobiotic calibration solutions over a two month period. Based on the 

analysis of the calibration solutions a minimum level of quantification was 

determined for each analyte, as given in the Introduction, which accurately 

reflects the instrumental detection limits. 

12/89 QA/QC Xenobiotics 23 
APPENDIX B 

ADDITIONAL DATA ANALYSES 
APPENDIX B-1 

Nomographs for Estimating Cancer Risks 
B-1-1 

CHLORDANE 

Fish Tissue Concentration 

(mg/kg wet wt) 
DIELDRIN 

Fish Tissue Concentration 

(mg/kg wet wt) 

B-1-2 
p,p’-DDE 

Consumpllon Rate (grams/day) 

1000 100 10 

B-l-3 

10-3 -) 

10.' y 

1o-5 = 

lo4 -: 

10.’ : 

lo8 2 

1 

II1 1 

1 loo0 loo 10 1 

Fish Tissue Concentration 

(mg/kg wet wt) 
HEPTACHLOR 

Irlrrllr[---r--,-r nl-rl-- r-.lTlrTlq - rr-ITTT”, TemTl T ITllj 

O.ooooOl o.oooo1 O.oool 0.001 0.01 01 1 10 100 1000 

Fish Tissue Concentration 

(mgkg wet wt) 

B-l-4 
HEPTACHLOR EPOXIDE 

lo‘* -3 

1o-3 - 

1o-4 = 

1o-5 : 

1o-6 : 

lo-' 1 

Corn~rnp~~on Rale (grams/day) 

1000 100 10 I 

11 , 

I ’ I- -=q------rl llrrl-IT’1 ~Irrlrr,~---rrr-rlr”[--l- -TITTlq --mrr,rq - I I IT ,117, 

o.oooooO1 o.ooooo1 Oooool 0.0001 0.001 0.01 0.1 1 10 100 

Fish Tissue Concentration 

(mg/kg wet wt) 
HEXACHLOROBENZENE 

102 3 

1om3 = 

10-4 = 

10-5 = 

1o-6 : 

10“ : 

Consumplron Rate (grams/day) 

1000 100 10 1 

1000 100 10 1 

.11 I 

, I I 111111, r I llTTTq I 1 I~rl~n~~-l-r17Tml 1 1 rrllll, 1 77Tl,1,, -~r--,‘r,,r,,, 1 , ,, ,,,,, 

0.000001 o.oooo1 o.ooo1 0001 0.01 01 1 10 100 1000 

Fish Tissue Concentration 

(mglkg wet wt) 

B-1-6 
B-I-7 

alpha-HEXACHLOROCYCLOHEXANE 

Consumphon Hale (grams/day) 

1000 100 10 1 

TI IT--, 

1o-6 : 

1 I,,,,,,, I I1111 1 r-rrmq----r TrrTq-F-TrTrr ,,y--r-r~rr,rrl,-~T-T1nrr~---r7rrrr,l[ 1 I 1 T lrll, 

o.ooooo1 0.00001 0.0001 0001 001 0.1 1 10 100 1000 

Fish Tissue Concentration 

(mg/kg wet wt) 
gamma-HEXACHLOROCYCLOHEXANE 

lo-* 7 

1o-3 ; 

1o-4 3 

low5 x 

lo+ : 

lo-' : 

Consump~~or~ Hate (grams/day) 

1000 100 10 1 

1000 100 10 1 

I I I 

1-v r7’TlTllT-r7lrlq‘-777-TTT~ ,Tl-rlT T , ,-rmT- ,-,-,,r,,r,- 7.1 11 llli, 

O.oooool o.oooo1 0.0001 0.001 0.01 01 1 10 100 1000 

Fish Tissue Concentration 

(mg/kg wet wt) 

B-l-8 
Consumplion Rale (grams/day) 

o.ooooo1 0.00001 0.0001 0.001 0.01 0.1 1 10 100 1000 

Fish Tissue Concentration 

(mglkg wet wt) 

B-1-9 
PCBs 

10.' -j 

lo.* - 

1o'3 z 

10" 3 

1o.5 = 

d : 

Consumption Hare (grams/day) 

1000 100 10 1 

I I 

, I I , I ‘l-q I I 11 In-q-~rr-rrrrn~rrm~ T-r-m,IIT~--T 1,77TT--I ,TTf,ll, -.-:l 1 I nrr, 

O.OOOOOl 0.00001 0.0001 0.001 0.01 01 1 10 100 1000 

Fish Tissue Concentration 

(mg/kg wet wt) 
TRIFLURALIN 

10' -y 

lo-5 I 

lo6 = 

lo.' = 

to.* : 

1o.g : 

Consumption Rate (grams/day) 

1000 100 10 1 

11, I 

, I , , , I ,,,I ) I , , q I T I ,-T,-T, ,111, : , , I I ,,I, -r I r-rmry- --r-n-lrrq --l--r, I-rrT- I T I-mrr, 

0.000001 0.00001 0.0001 0.001 0.01 0.1 1 10 100 1000 

Fish Tissue Concentration 

(mglkg wet wt) 
APPENDIX B-2 

Nomographs for Estimating Noncarcinogenic Hazard 

Indices 
BIPHENYL NONCARCINOGENIC EFFECTS 

Consumpl~on Rate (grams/day) 

1000 100 10 

-rrrrl-lq--T--l -rlllT~- ,7-n-- 7‘~--rTm--- 1 ,‘T--TTn T) - TT -7 

.Ooool 0001 001 .Ol 1 

Fish Tissue Concentration 

(mg/kg wet wt) 

B-Z- 1 
CHLORDANE NONCARCINOGENIC EFFECTS 

Consumpllon Rale (grams/day) 

0.001 , , , , ,,,,, 1 I r 11r11, I I I I I ffrf I r-T~r-nm~r-7- r-rr rfnr --rrrrrrrrl 7 T 1 rr,,r, 

O.oooOl 0.0001 0.001 0.01 01 1 10 100 1000 

Fish Tissue Concentration 

(mg/kg wet wt) 

a-2-2 
.ooo1 : 

CHLORPYRIFOS NONCARCINOGENIC EFFECTS 

Consumphon Rate (grams/day) 

1000 100 IO 1 

,Qoool J---- rnr(1~~T ~~ 1 r -7~1.. -- TT1l,i--~~ - 1~~1 rTTlrr v-1 I 1 rrrrr T-- I I 1 r,,,, 

.0000001 .00001 .OOOl .OOl .Ol .1 1 10 100 

Fish Tissue Concentration 

(mglkg wet Hit) 

B-2-3 
loo 1 

10 < 

is 1-I 

'0 

E 

2 

B 

I 0.1 y 

0.01 y 

0.001 -- 

p,p’-DDE NONCARCINOGENIC EFFECTS 

Consumptron Hale (grams/day) 

1000 100 10 

- 

0.0001 0.001 0.01 0.1 1 10 

Fish Tissue Concentration 

(mg/kg wet wt) 

100 1000 10000 

B-24 
Consumphon Hate (grams/day) 

1000 100 10 

o.oooo1 O.oool 0.001 ,001 0.1 1 10 100 1000 

Fish Tissue Concentration 

(mglkg wet wt) 

B-2-5 
1 -J 

.l y 

.Ol - 

a01 < 

.aml 7 

HEPTACHLOR NONCARCINOGENIC EFFECTS 

Consumptron Rate (grams/day) 

1000 100 10 

I 7-r 

1000 100 10 1 

1 

1 

.ooool --t-r I I I Ill”, I T r-r-r~--rl-TTlTrrr TT-Trl rly -l-l-Tl,lnT- 1 -, 111111, 

.OOOOOOl .OOOOl BOO1 .OOl 01 .l 1 10 100 

Fish Tissue Concentration 

(mgkg wet wt) 

B-2-6 
HEPTACHLOR EPOXIDE NONCARCINOGENIC EFFECTS 

Consumption Rate (grams/day) 

1000 100 10 

' ,- I 

1000 100 10 1 

l~liKTT-~-l -1.1 -- I ,,a,, -7 7 ITI~II, I I 

0.001 001 0.1 

Fish Tissue Concentration 

(mg/kg wet wt) 

B-2-7 
HEXACHLOROBENZENE tiONCARCINOGENIC EFFECTS 

Consumpllon Hale (grams/day) 

1000 100 10 

II1 I 

1 

.oool .-f-rnTm1r I I I IlTlIl 1 I 1 I I I rrl7-TrrrrnT-7nTrrr --r--,-r,lTlT(---r--r l-771 10 -1 r 1 1l1111 

.OOOOl BOO1 .OOl .Ol 1 1 10 100 1000 

Fish Tissue Concentration 

(mg/kg wet wt) 

B-2-8 
100 

10 

1 

0.1 

0.01 

gamma-HEXACHLOROCYLOHEXANE 

NONCARCINOGENIC EFFECTS 

Consumption Rate (grams/day) 

0.01 01 1 10 

Fish Tissue Concentration 

(mg/kg wet wt) 

100 1000 10000 

B-2-9 
ISOPROPALIN NONCARCINOGENIC EFFECTS 

Consumpllon Rate (grams/day) 

.oQol 

.OOOOl 

.OOOOl .OOOl .OOl .Ol 1 1 10 100 

Fish Tissue Concentration 

(mg/kg wet wt) 

B-2-10 
Consumphon Rale (grams/day) 

1000 100 10 1 

001 +-i-l-- r----r 11 TT,T\ --7-TTl-rTn7rrlllT 1 1 1 rrrll---T-TT-n-r1il-~ 1 1 r 1 rrn~r-l-Tn,ll, I 1 I1 1111, 

.OOl .Ol 1 1 10 100 1000 10000 100000 

Fish Tissue Concentration 

(mglkg wet wt) 

B-2-11 
MIREX NONCARCINOGENIC EFFECTS 

Consumplron flak (grams/day) 

100 

10 

0.01 

0.001 

0 

1000 100 10 

3 prr1,1 I I 

1 

.000001 0.00001 0.0001 0.001 0.01 01 1 10 

1 I.1 11111 

100 

Fish Tissue Concentration 

(mglkg wet wt) 

B-2-12 
PCB (AROCLOR 1016) NONCARCINOGENIC EFFECTS 

100 

10 

z 1 

0 

+ 

2 

ii 

i 0.1 

0.01 

O.OO! 

Consumplron Rate (grams/day) 

1000 100 10 1 

.oooOl ,001 .Ol .l 1 10 100 1000 

Fish Tissue Concentration 

(mglkg wet wt) 

B-2-13 
Consumption Rate (grams/day) 

loo0 100 10 

r, r1 

.oool 1 I 1111111, I I Ill111, I i ‘.,,I,, I , r,r r,,, , , ,rrTTq---I-l-r,~--T~ T 1 -Try--7 -r-rr,rn, 

0001 .oOl .Ol .1 I 10 loo lOCKI 10000 

Fish Tissue Concentration 

(mgkg wet wt) 

B-2-14 
APPENDIX B-3 

Site Description Matrix 
Key to Table B-3 

Matrix of Episodes and Site Descriptions 

COLUMNHEADING DESCRIPTION 

1. 

7 

-. 

3. 

4. 

5. 

6. 

7. 

8. 

9. 

10. 

11. 

12. 

13. 

14. 

IS. 

16. 

17. 

18. 

EPA REGION The U.S. Environmental Protection Agency Region which includes the 

sample location. 

EPISODE The EPA Episode Number which is specific to each sampling location. 

LATITUDE The latitude of the sample site in degrees, minutes and seconds. 

LONGITUDE The longitude of the sample site in degrees, minutes and seconds. 

STATE The state where the sample was collected. 

WATERBODY Name of the water body where the sample was collected. 

LOCATION The nearest town, road or county to the sample location. 

NSQ Sample site from the USGS NASQAN monitoring network. 

B Background site as selected for study. 

POINT SOURCES: Point sources include the following six categories: 

PPC Site near paper and pulp miII using chiorine for bleaching (includes mills 

using the sulfite process). 

PPNC Site near paper and pulp mill not using chlorine for bleaching. 

REFINERY Site near refinery using the catalytic reforming process. 

NPL SITE Site near an EPA National Priority Lit Site (Superfund site). 

OTHER INDUSTRY Site near industrial facility other than a paper milI, refinery, or wood 

preserver. 

POTW Site near discharge of a Publicly Owned Treatment Works (POTW). 

WP Site near active or former wood preserving activity. 

NONPOINT: Nonpoint sources include the following two categories: 

URBAN Site near urban runoff. 

AGRICULTURE Site near agricultural area. 

B-3-I 
B-3-2 
TAELEB-3 

Matrix UC Episodes and Site Descriplions 

- 

Ii 

I 

I 

I 

I 

I 

I 

I 

I 

I 

I 

1 

I 

I 

I 

I 

I 

I 

I 

I 

II 

II 

II 

II 

II 

II 

II 

II 

II 

II 

II 

II 

II 

Ii 

II 

II 

skk wmlerbdy Lumtkm 

CT QuinipiacRivcr 

2315 41:36:47N 071:5&26W CT Quinncbaug River 

236Y 42:37:25N 07l:u:lOW MA Merrimack River 

3151 4235:22N 072:21:oBW 

3150 4235346N 0720.3:27W 

2356 44:06:1ON 07Oz13358W 

2721 44:15:MN 070:10:MW 

2725 44z3OMN O-Kk15:oOW 

3026 44:lO:aON 07OXk25W 

3028 4504:48N 067:19:25W 

2358 44:XdON 067:55:3OW 

3022 ~323ON OM:O7:15W 

2355 44:49:2ON 068:42:3OW 

2722 43:34:35N 070:33:45W 

3027 43:34:25N 07033355W 

3023 44:543ON 069551XW 

3024 44:54:00N u69:15:15W 

3025 44:41):4ON 06!%24:fNJW 

3152 44:24:42N 071:11:29W 

3426 40:35:45N 074:12:2OW 

342Y 30343ON 07531M)W 

3430 39:1&00N 074:37:3OW 

2651 3!4:36:rnN 074:35:mw 

3427 4039:lSN 074:09316W 

2653 405420N 074:11;00W 

3428 40:43:15N 074:0f:15W 

3433 4028.24N 074:03.40w 

MA Millers River 

MA Otter River 

ME Androscoggin R., 

ME Androsco&nR. 

ME AndroscogginR. 

ME AodrcrsqginR. 

ME BearceLakc 

ME Narraguagus R. 

ME Nurth Pond 

ME Pen-R. 

ME SacoRiver 

ME Saw River 

ME Sandy Pond 

ME Scba&cookE. Br. 

ME Scbarliumk W. Br. 

NH Androsco@n R. 

NJ Arthur Kill 

NJ Dclnwarc Riwr 

NJ Great Egg Harbor 

NJ MuOica River 

NJ Newark Bay 

NJ PassaicRiir 

NJ Passaic River 

NJ Raritan Bay 

3434 4027:fDN 074:03:CXIW 

2654 3~:57:3ON 074123OW 

3304 43:5KiON 076043OW 

32% 42:51:45N 078z52:oOW 

3298 4252.OON 07&52:XlW 

3301 43.202ON 078:43.oOW 

2326 4213:OQN 07&01:00W 

NJ Sandy Hook 

NJ Tams River 

NY Black River Delta 

NY Buffalo Harbor 

NY BuffabRiw 

NY Eiica Mile Creek Olco~t 

NY Gcnusec River BChlKnlC 

330) r42:13:3ON 07lJGaW NY Gcncasu River 

North Haven 

JCWCII City 

7)ng.s ldand 

El-V& 

Bakhvimilk 

Lehistoa 

Turner Falls 

Riky Dam 

Auburn 

Barring 

Chcrryiicld 

ClKSlCdk 

Eddi”gi0” 

uniu” Falls 

u&0 lws 

North Ansun 

NCWpt 

West Palmyra 

Fkrlio 

Carteret 

sakm 

Green Bank 

Elizabeth 

Paterson 

Newark 

Dcxux 

Bufralu 

Buffalo 

Bclmom 

I 

i 

X 

X 

X 

X 

X 

X 

X 

X 

X 

-r 

I 

t 

X 

x x 

X 

x X 

x x 

X 

X 

X 

(bdMbhlbD*~dlbtusrWgtiut) 

lnduslry: chemical & pesticides; clcdronics; plastics; mclalq Superfund 

site (suk”lr) 

Ind.: organic them. & pest., tcxtilrs; Superfund site (Furans) 

lad.: chcm. & pest., industrial WWTP; P&P mill on Nashua R. (drib.); 

Supcrtimd site (solvents) 

Ening Paper Milk; wooded area; Ag.: croplands and grazing folds 

Ervirq Paper Mills; wooded area; Ag.: croplands and grazing fwldr 

Internaliwral Paper, Boise Cascade, James River; Ind.: ~udiks 

lntcrna&mal Paper Co. in Jay 

Boise Cxxade in Rumford; rural;w&d arra 

Ind.: IcaliJes; downstream of paper mills 

Two Mucbqy prowssing planls; blueberry Gelds (pcslicides) 

No industry; woudcd and swampy arca 

James River Corporation on Old Tom 

Same as 3M7, PGTW on upstream [rib. pt is Background site 

Same as mZ, PGIW on upstream [rib. yet is Background sik 

laduslrial WWTP 

IndustriaJ WWTP 

James Riir Corporation 

GAF Corp. (&cm. manufacturing) 

Supcrfuruj si~c (several siws; metals & org. chemicals) 

Background even though has agricultural arca and POTW nearby 

won&d uer 

lAnd6U 

Mucd Paper and P&P mill on (rib.; lnd.: mcV& chcm. & pu&.; 

Supcdund rite (solvcnlm) 

&I Lislcr Ave.: chcm. maaufacluring 

P&P miU cflhrcnt imo bay. Exxon Co.; lnd.: chcm.; Superfund sic (scvcrrl 

sites; melah & org. chcm.) 

Exxu” cu. 

Ind.: &mid, Superfund site (chlorobcnzonc; Hg) 

Five paper mills (PPNC); Air Brake Co ; hydropower; dairy hcldr 

Ind.: chemical. reel, pcuwhemiol; landlills 

Allied Cbcmkd (maauftiwcr uf HCB); Jan&ilk 

id.: Harrisoa Radiator; drew (HCB); Ag.: orchard, and cropIan& 

Same as 3309. Sampled below &Imon~ Dam. Superfund site is 

approximately IO miks upstream (heavy metals, hydrourtnms) 

Same as 2326 

B-3-3 
TABLEM (amt.) 

- 

1 

II 

II 

II 

II 

II 

II 

II 

II 

II 

II 

II 

II 

II 

II 

II 

II 

II 

II 

II 

II 

II 

II 

II 

11 

II 

Ii 

II 

II 

II 

III 

Ill 

Ill 

III 

Ill 

Ill 

Ill 

Ill 

- 

rru 

L 

3306 

3259 

Mm 

3321 

3322 

3260 

2328 

2329 

3323 

3324 

3325 

3326 

3300 

3297 

3299 

3302 

3303 

3412 

3305 

2322 

3308 

Ml1 

I307 

5327 

3432 

u31 

I210 

I147 

Km 

m 

Km 

f149 

I100 

1317 

NY GrasaRiwx Maurma 

4040fHJN 073:W NY Great SadBay 

4040145N 073: 19:OOW NY Great South Bay 

41:16:3ON 07%57zOBW NY HudamRivcr 

43.a.aN 073:36:3oW NY HudaonRiwr Fort Miller 

41:aOzOON 13’7357:MW NY HudacmRiver P&akiB 

403840N 0735&.40W NY JamaicaBay New York 

4&37:45N On:477MW NY JamaicaBay New York 

43:51:3ON 073:2Z03W NY LakeChamplain Tiraga 

43:20:25N 07&43:14W NY LakeOn~uia OLco(l 

43:14MN 077:32.mW NY IakcOnrarin R-U 

4Oz48MN of3:4S.%lOW NY LiukNcckBay Loqlasuud 

4&47MN 073z45.%klW NY LittkNcckBay Lag I& sound 

UI~~S~ON 07MMXJW NY Manhaucl1&y l-t?Ir4Oz5OAON w3:4OA5W NY Manhaaaml Bay Lc4l# la. swod 

43:15:3ON 079S0:45W NY NiaR.D&a P0HC.f 

43fi)3MN tDBz5&55W NY NiiaRiwr Niqua Falls 

43ztLwoN 07&53:45W W N&araRivcr 

43: I&MN 07903: low W NiquaRiir 

U: 12dON 075.-W NY Oa~chkRisw 

1328MN 076:31M)W r(y OnqoHarlmr 

445IUON 071:44zOOW VY Ra4FmttcRii 

u:59am 073:21:00w W RichelkuRiir 

45zO&tKtN 07&21zOfJW ‘IY RichcJicuRkc.r 

13:ll:IsN 077z31:3ow YY Rocbeater Embay. 

(4:4233ON 075:28:XlW W SI. Lamcncc Rinsr 

R- Pt. 

R- Pt. 

RnChUlu 

lO2&20N 074:02:15W W Upper Bay New York 

17:59:4ON 06634625W ‘R Guayanilla Bay 

18:26:Y)N lBi6M:3OW ‘R SM JuanHarbor 

LB:52:20N U77*15W X E.PrnomacRivtr 

l852JoN onaw x PotomicRiiPark 

w35.m u75z12z >E IndianRiwr 

L%48:wN 075:39:uw )E Red CJay Creek 

Iy:35:4oN 075:37:mw IE RcdLioaCrcck 

S!k4):58N 075:45:37W )E White Clay Creek 

&1536N 076:31:3oW 4D BaKimorc Harbor 

l92&OON OROIMW AD Pot- R.N. Br. 

San Juaa 

DC 

N.dWtiBr 

RLlUd&&d 

t$2tCnmer 

Tbpsoll 

Baltimore 

Wrsternporl 

!!!!!LE 

X 

X 

X 

X 

wlMawac~ 

.- --.- -.___ 

NPI. CUber 

m: rrm: m IlhJ Mb Id Rnw 

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 

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 

Sampled below ALCOA’S outfall (PCB concern); GM 1 RcpoJds(2 

same as 3320 

SUIK as 3319 

Same aa m, ht.: chcm.; P&P mill 150 river miles upstream; Supcrfund 

site (PCB) 

FOCI M&r Pulp and Paper (Fin&, Pyruyn & Co.) 

Same as 2m, Ind.: chrm.; P&P mill IW river miles upstream; Superfund 

site (PCB) 

lad.: chcm.; airport; burdtill 

lnd.: &cm.; airport; landtilt 

lntcrnalional Paper Co. 

Ag.: l ppk orchards and croplands 

Ind.: them (Kodak); Site a1 IIIC mouth dGecwr River 

Same as 3324 

sa”u as 3323 

sanuaa3326 

sameu3325 

Ind.: chcm.; Olin. Duponl. Gxidca~al (HCB); Ag.: orchards, huulfdl 

lad.: chcm.; Olin, Dupont, Gaidms~al Chem. (WC’B). (companies 

duwnstream of she) 

Ind.: chcmiwl 

lnd.: chcm.; Olin, DuPont, Otidentrl (H(B); Ag.: orchards 

Newton Falfs Paper Mill (defunct since OJcu.rbcr 1984) 

lnd.: Chemicnf 

Potsdam Paper and Norfolk Paper (PPNC); ALCOA, GM, Rcyndds 

(upabeam of mwth) 

Ind.: chemical 

Pomkrosa Fibers (OUI of business more than 4 years); Dow chcmiul in 

Canada 

Sampkd at 69th Slrcet Pier 

Cuibbuln Gulf Rctining Corp.; landtill 

Ind.: metal plating. mining; iJkgaf dump (Jar&i); Ag.: mushroom IL’hcmical spill (HCB concern); Superfund silt (HCB) 

Westvaw (iadirect); rural 

B-3-4 
- 

2 

III 

III 

111 

III 

II1 

III 

III 

III 

Ill 

Ill 

Ill 

Ill 

111 

Ill 

III 

Ill 

Ill 

111 

Ill 

I11 

III 

Ill 

Ill 

Ill 

Ill 

III 

Ill 

Ill 

Ill 

III 

Ill 

III 

III 

Ill 

Ill 

IV 

IV 

- 

m 

I 

2231 

3103 

3316 

3161 

3420 

3094 

3095 

3096 

3318 

3419 

3310 

3101 

2215 

2212 

3104 

3415 

2211 

3414 

3315 

2216 

3422 

3421 

2225 

2228 

2227 

2220 

3423 

3424 

31Y3 

3258 

2503 

3314 

3311 

3312 

3313 

23l-u 

23oY 

l.albl& l.e&da 

39:3Y:31N @76:1&28W 

393iNlN 076zlOW 

11:25:2ON 07%44zlOW 

3956:3oN 075: 14:3sw 

3953:42N 076:49zO9W 

00:02:24N 07):w:zUW 

3953:MN 075:11:4W 

3951:36N 075:18:4OW 

sYW8IUb+ IatdbJ 

MD SusquelunnaRivtr Ccmohso 

MD Sus~urhnnaRii Cooohao 

PA ClJrL Riir 

PA C&b Creek 

PA codorlw cre& 

PA Dc.lawue River 

PA Dckwirc R&r 

PA Del~wue Rivu 

Torrudak 

Schuyuill JDCI. 

=Jw= 

WZMON 078:24:2oW PA Frankstown Branch KlJddersmiot 

12:09:25N IXKTM7W PA Lake Erie Eric 

M:39:4ON @75:14:3SW PA L&ii River Earn 

(0:03:4ON 075923W PA l&k V&y Creek PMii 

4Oz17:3ON 07952:33W PA Monoqpkk Riva ckirton 

395&UON K’s:ll:ZJW PA Scbuylkill River PtlilUklpbL 

39S&PN 075:11:33W PA Schu)ikill Riwx 

41:23:3DN D75:48%ww PA Susquchsnar. N.Br. 

UMN.fNJN l?76:XMklW PA Surquelumu R&r 

11:18:MN K’5+3:45W PA susquc&nM Riir 

ti21:WN 076:233ooW PA unioncMJl 

ll:33:22N 07?41:28W PA Young woawnl cr. 

16:33:10N 07654:57w VA Blackwater River 

M:47:1SN MlSXkMW VA Jackson River 

B7:35:mN O792HOW VA James River 

K’i40315N 078M:lOW VA J- Rirer 

36%:13N DTIm59W VA No~cwmy Rii 

37346303N on:l!It57W VA Pamtmkcy River 

%7:31:55N lT76:48:4oW VA Pamtmkcy River 

37332:OlN 076%38W VA Pamunkcy River 

37301:45N 07&55MlW VA Roanoke River 

)6:49:48N 076:17:3fJW VA S.Br.Elizhah R. 

)B:27:00N u)l:&iUW WV -Rivu 

Rllucm 

ColumhiJ 

PithlOO 

Hllwmr 

wed Pah 

WUI Pails 

lhoknul 

NOhlk 

Nitro 

)B:31:3ON 081:54~37W 

FMlkOON 080.51:52W 

Kk09:lON 080.42SW 

l9z31:lON 077:52:3OW 

11:32:48N Ofl9dOt45W 

12:24:41N llW243OW 

WV KJMwk Rii 

WV Ohio River 

WV Ohio R&r 

WV Opcqm Creek 

U Al&mu Rivu 

&L AlAm River 

urp 

X 

MwratNJICYI ----.---~ ..- -._ WI. m 

WC rrw wr u&y #lb Id wlw 

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 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

Perneck Papers in Jobsoobw ~rurrl;acidrLt&* 

ow rcr pknl (defuncl fur more rlmn 5 pn); IJdii 

P.H. GUlfelder in Spring Grow 

CUJSISI Eqk Poinl Oil Co. in NJ; lnursynic cbcm. 

Mobil Oil in NJ; Ind.: ckm; muhipk sources; &: crophds (truckiq d 

VP-t-W 

Appktm Paper oa tkc Junh R&r (Hdtcr Creek) 

Hammermill Papu (indirect); railyard; hod procusing phr 

sled ioduury 

P&i Railyard (hic~aic KB pobhu) 

Ind.: imqaliccbun. uld pa. 

Smw as 310+ two rcfiirieq hd.: org. &em. & pal.; P&P mil& 

supcrfund tic (PCP) 

Same u 2212; two refiiriu, lad.: org. c&m. & *.; P&P rill, 

superfuad lik (PCP) 

SupeJflmd rile (kwy mctJk) 

Gldkldc~ (lhchkrl) a0 milu uplream OJ tribuy 

Superhmd site (k.iq mds); Ad nhiw daiqc 

Phcide-~ 

Uniaa Camp Catpodm in Franklin 

weumcocorporJliuo 

Lgll qricukure; rud 

Westvra, (PPC); Vii&h Fhrr aad Nckoaa Edwudr (FPNC) 

UaicaCampka0miksdowutrurdu@iqaitc 

Uprream from tbc Cl~urpeakc Corpoftiia 

Ckaepukc Capur~~ioa (upstram d&e) 

CburcpuLe Corporhon (downstream drirr) 

Rural 

Id: pemicidqlrichkK~udapric~(DowMd 

MoJsJmo); nml 

Id: pe&idcI (M-o); nral 

Quaker State Oil Rdii rlc~l idurtrier; ubu rvdl 

Ap orchurb, rural 

Alabama River Pulp Cnmpaoy 

Id.: urganic cbcm. & pun.; Fence-poet cmpuy, 4: rroplub 

B-3-5 
- 

Ii 

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 

- 

Lu 

A!- 

3360 

3170 

2302 

3372 

3328 

3171 

3169 

3168 

3331 

bulrl L.drlb 

32:U7:SSN oLIs:O3:43W 

31:2!unN 085:22:06w 

31zO4:OlN 087zCEy1W 

31:25:07N 088:26:45W 

33: 17:24N 086:21:42W 

31mO2N a85:13:24w 

33:tiLSN 086:31:46W 

a.52:m Om57:48w 

3oL~ooN 087:20 15w 

3332 30:3&52N 081:29:28W 

2151 3023:WN oB5:33:24W 

3329 mo1m 083:46:oow 

3334 295Oz31N 065l’I:WW 

3174 27:12:16N 480347328w 

21411 272854N 080:2l:lOW 

3333 30:07:38N oL15:392!iW 

2142 29138MN 081:37:32W 

3173 3lOlMBN oBl&OOW 

2152 x%21:3oN lmm4:54w 

3330 3WB:oON 083:lS:oOW 

3337 31:39mN 08l:4!RmW 

3177 34SOlN @3:4030W 

337s 3339i24N 084:4&25W 

3376 33:28:37N tXJ454~04W 

33-n 33: l6:45N 085.96.9oW 

3378 3m8.mN m5zo4mw 

3178 34355:lXlN 083:10%XlW 

3179 34:27XlON tX3:57:MW 

2294 3291:2ON Ut356:MW 

3176 XI52:tXtN 084365XlW 

3336 30343:37N ola3Z~W 

wi!M 33:2225N 061:56:35W 

3175 32lOsN rnl.~rn 

3338 33mmN lw:56%Knv 

3180 31:18MN 084z45amw 

3335 31ztXlSN lB1:31:35W 

Sld9Wdh+ Lmdvm 

AL Chalt- CotlO41~ 

AL LIwc~awhr~chcc R. Henry Co, 

AL GnwukRiver IL Brcwlar 

AL -River NJGA Pue 1 

AL CoosaRk cmuPioes 

AL Cowarts Creek Houutoa Co. 

AL lnlandbke Bbud Co. 

AL M&k River luuwcr. 

FL 1lMikCrcck camFL Amelia River Fernandii & 

FL Econlinn Creek Panama cily 

FL Fcnhulbway River Perry 

FL Gulf co. Canal SI. Joe 

FL LalrcOkee&obcc OkFL Mainculal Vero Bach 

FL Si.AndrcwBay Panama c* 

tl. SI. Johns River P&L 

PL SC. JohnsRiver Gram Cv. Spr 

PL SI. Ma+ River Mreknoy 

FL W~hlacaochc Riw BlucSpriq 

GA Allamak~Rivcr JMP 

GA Clut~abwcbeeR. GliDesbilk 

GA Chall~ R. AurtcU 

GA Cluttabuo&eR. Whitcsbuq 

GA ChattahoochR. Franklin 

GA Chsl~almocb~ R. DomldNnvi8c 

GA Chattoqga River -vm 

GA Chcatrtce R&r ahlwcL.M 

GA Fliit River L Black&u 

GA Lake Scminok 

GA North River (mouth) SC. Mary% 

GA SwannabRivcr -wt-~ 

GA SawumhRiwr Sawnoak 

3A Savannah Riwx A%=- 

3A Spring Creek Early cwn1y 

3A TurtkR.(muuth) S.Bruos&kR 

X 

X 

X 

X 

X 

X X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

NONMIN 

-__- 

rcr 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

Seural them. & pat. plants; Hydru-power 

Clumpion Intwnirliuwl Corp. in Cantonment; rural; swamplam& 4.: 

aoprwb 

IIT Rayoakr. Inc. 

Buckeye Cellulose; rural; swamplam& Ag.: graz& Ii&s 

3. Joe Paper (iodireci) 

Cdkdcd below salinity structure 

Somhwcrl Fora( Ind., Ioc (indircd) (lone Cool* Corp.) 

GUI+ Pacific Cqoratiun 

woodtwumemplNl 

IIT Rayaaicr, Inc.: swamp&n& Ag.: croplands 

Town dLklun&: bcavy ~wIs, wood pmluc& A&: cbkkco farms aad 

orchards 

BaribudaaHwy92 

Grul Soulhera Paciftc Paper Company 

Procter & Grmhk (Buckeye Cellulw) 

Grul Suuthcrn Pa&c Paper C~nnpany 

Gilm~ Paper Cumplny 

Federal Papcrbuard in Pond, Gwqia Pacifq Ind.: pen. 

JbiHowardP+ur(PPC),UniaaCIlpudStae-Carp. 

VW; Nudur pau 

Ponder- Fikn (bdiru%) 

Brunswick Paper k Pulp 00 Ike Turtk R.; mahhmd; wcw.kd UC& MC: 

graziq lads 
TABLE B-3 (amL) 

- 

E.i 

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 38:24:22N 082z35:52W KY 

3339 36:55:41N IXZXO552W KY 

3182 36:55:27N 08652:47W KY 

2056 38:C~I30N CI855613OW KY 

Bii Sandy R. 

Mhsisippi River 

Mud R&r 

Ohio River 

2341 38:44:29N 084:57:52W KY 

3181 38:00:3ON C@5:56:3OW KY 

0hio River 

Ohio Rii 

3446 3832422N 082:35:52W KY BigSandyR. 

3185 3025:OON OLIYtiMW MS Bernard Bapu 

2126 32:20:41N 0%51:48W 

3445 M:lY:32N C8Qb31:oOW 

3341 W:25:2ON CUX3l:lOW 

3340 31:13:28N oL19:02:5OW 

3435 3125:OON 09l:XkMW 

2133 32:29:14N 0903WW 

3184 3228:00N 090:4!&:0W 

3344 3423:WN U78:10%1W 

2139 35:40:02N 093M:23W 

3165 34z43:MN 0793924W 

3345 35:15:06N 082:40345W 

3164 3556:45N ohl:19:2oW 

3342 3436:3ON 078:y):COW 

3167 j35:50:3SN 13785&2oW 

3166 [35:08:OON 0839l5W 

2138 ‘35:15:29N on:35.S)9W 

3395 3s:ll:%N 077306:45W 

3343 35132:OSN 082:54:4OW 

3346 3S:Sl:SSN 076:45:4OW 

MS 

MS 

MS 

MS 

MS 

MS 

MS 

NC 

Bi8 Black River 

Ckenon Effluent 

Escalawpa River 

Leaf River 

Mississippi River 

Y-River 

Yazoo River 

Cape Fear River 

NC 

NC 

NC 

NC 

NC 

NC 

NC 

NC 

NC 

NC 

NC 

Catlklsbur8 

WicLlilk 

Russcllvillc 

WCSI Point 

Markland 

WCSlpOillt 

caktlsburg 

Gulfporl 

Bokna 

Plrclgouh 

Moss Point 

New Au@Wa 

NllClUZ 

RedwoOd 

Redwood 

Ricgehuood 

C~~~doocbcc Creek CattaloocMc 

Deep River R-ur Dam 

Frcnck Broad River Pi Forest 

HJW River saJlapJhaw 

Lumber River Lumbcllon 

Mcdlim Pnnd Morri.wilk 

Nmtbalia R&r Macon Co. 

New R&r KiNlw 

Neuse River New Bern 

Piiwn Riwx Clyde 

Roanokc River Plymouth 

!e!LE 

3349 335lzO8N 08&37:32W SC Wtiu~~RRivcr Enslover 

2X1 35:m45N 1X?7:4958W TN BufhbRivcr FlJtwoodJ 

3189 35:55:37N 084:58:18W TN R. Loudw Rcs. 

2298 35:16:3lN 0?&58%W ‘TN Hakhic River Bdivar 

3350 35:19:08N 084:48313W TN Hiwasee River CJlhONl 

2297 36:0(1:56N B83:4954W TN HulstonRivcr Kmsvilk , 

3385 35:59:25N 081:31:32W NC Yadkin River Patk,morl 

3347 34142:3ON oLa:51:5OW SC CatarvbsRiver c.alJwbJ 

3186 3245:%N 07953:lOW SC CkarksumHarbur C~wles~w 

3348 3321:UN 07!%18:34W SC Sampi River Gcocgcrown 

3187 : 32:29:46N 080331:33W SC SI. Hckna Sound 

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 xx 

x x 

X 

X X 

X 

X 

X 

X 

X 

x x 

X 

X 

X 

X 

X 

X 

X 

x x 

NONNNHl 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

(FrlyLLr~*eulydum~&) 

Ashland Oil Inc.; Ind.: chcm,. iron and steel; cnal min& timber 

Wcstvam Ccrpnra6on; Ag.: uuplands 

lad.: metrl plating; rcndcring plant; Ag.: crnplands 

Same as 3181; lnd.: chcm. d pcsl.. rcfmry, Ag.: crops; Supcrfund silt 

(PCB’s; solvcnts; diuxins % furans) 

W~IC Industries; mukipk suurccs; rural 

Same as 2056; Ind.: chcm. & pest.. rcfincly. Ag.: crops; Supcrfund site 

(PcB’s; solunls; diNiN k furas) 

Ashland Oil refmcry, caal mining 

Ind.: chcm.; wuud lrcrlmcnt; (gas recovery) refinery, rural; Superfund site 

W=nW 

Ag.: SO+N JIXI c&on 

Ckcvrun rcfmry, lnkrnsliunal Paper; skipyard; fertilircr compmry 

Intcrnatinnal Paper Company 

lzaf River Fcucs~ Pruluds 

Inlernatinnal Paper Company 

Smne as 3184; lnd.: paper; ferlilizer planI 

Same N 2133; Ind.: paper; fertilizer plant 

Federal Paper Board; rural; swampland; wuoded area; Ag.: croplands 

CrUmpiw Paper (PPC-indircd soura); woudcd area 

Easta (sulfiie mill using chlorine); rural; wwded area; Ag.: croplands 

Ind.: 1ex18c.q rural; &: croplands 

Alpha Cellulose (sullilc mill using chlcrinc) 

K.oppcrsCompny (wood Irul.); Superfund site - woud Ireat. (PCP) 

Wcycrh8cuser Company 

Wcycrhxuscr Crmpmry 

C3umpion Imcrnstionul in Canton; rural; woudcd area; Ag.: croplands 

Weycrkaeurcr Company on Wckh Creek; rural; wooded area; Ag.: 

crop&n& 

Sakd Air Ccrporrliun (mrkcs vbsbanl paper for meal Irays) 

Buwatcr Carolina; rural; wouded area; Ag.: uopbds 

WNIVJCO Paper and Pulp; A- ckemiul plant 

lnlcrn8ld Papu Ccmpany; rural; wnoded area; Ag.: unplands 

Union Camp CcrpuraIOa, rwJ, wwudcd area; Ag.: un+& 

lnd.: aluminum 

Bowler South Paper Company, rural; wnnded area; Ag.; crupbds 

Industry: melals 

B-3-7 
TABLE B-3 (Cd.) 

- 

2 

N 

N 

N 

N 

N 

N 

N 

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 

m , 

4 

zi3444 

3188 

3404 

3351 

3190 

3401 

2379 

2383 

3113 

2380 

3114 

3115 

31 I7 

2059 

wue lad@& 

3633302N CCC35zC0W 

35:05z15N 090305:3OW 

3%03:54N 085:2Q%JW 

36101:2ON 083:12Mw 

35%24N 083:10:52W 

35:5OclJN 0&(M:l3W 

35:03:54N 086:16:39W 

37:37:3lN oB9:25:42W 

41:3%47N 088mo7w 

4J:52:13N O88zJ8:3lW 

41:1%1BJ 088:45:JOW 

39z43:mN o!al:3law 

38:323ON 09Oz15fBW 

4221:loN 087z4934OW 

4J:37:JON 087:29ASW 

T 

I 8u WdwbdY - 

TN J4oJsmn R.. S. Ibrk 

TN MbalNippiRiver 

-I?4 NkkajackReaavdr 

m FigeonRiver 

TN FigeQnRlrer 

IN Tenncualtiur 

774 TemcssccRlvu 

IL Big Muddy Riva 

IL DaFlallaRlver 

IL FaxRiva 

IL Jllhob River 

IL Mbaiasippi River 

IL MUlUlHDEfIluent 

IL L4keMkhlgM 

IN lndlaMHuluK~. 

3356 41:37:1ON 087m15w IN In&JuHutBxCan. 

2oa 38:07:5ON 087156:XnV IN WlbvhRlVCf 

2057 38:30~45N 087:17:3OW JN WlliKRlver 

3119 42:33:oON 085:WfBW MJ AllcganLake 

3118 45mOoN 087maJW MI BacaNbaRher 

199) 43:03mN 083:4&45w MJ PllntRJva 

3120 42:3!KXH 082:lOSKbW MI KabmuooRJvcr 

3122 4J:47mN On59mW MI MtmolioccRlva 

1998 43: lJzO5N 086:14:55W Ml MuakcgmLakc 

3148 43:l5:05N 086:14:55W MJ Muskegm~ 

2432 43:19z57N 086308342W MI Muskc8onRJva 

2410 42: 16:45N 083307:2OW Ml RougeRiva 

2431 46:29145N 084:22:25W MI SIMuysRJvw 

2430 44343oN 085:15:1OW MI T&q-non R. 

2435 47:55:23N 069dX42W MI WashingtmCnxk 

2387 44:16:08N 093:2lMW MNcmulmLllrc 

2437 44:41:33N 093:38:35W MN h3JmMouRJvcr 

3112 45:58:17N 094:2295W MN MJasis.si~lRlvcr 

3125 44:33:34N 092:25:47W MN MbsissipplRlver 

2385 48:36:29N 093:24:13W MN Rainy Jtiur 

3001 4&3%29N 092:53:34W MN Rainy River 

2416 41:295ON 081:42:IOW OH Cuyahoga River 

23% 39:33:44N 084:18:19W OH GIU~ Miami River 

2439 39 15:53N 084:4O3OW OH Gna Miami River 

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 

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 

w-~tbmtld~d*rdw 

MeadcNpomlkm (chlurinr: Dioxide pcess) 

Mapx, Exam. Union nfherks: cen8xt Inany; suyban paxuiag 

lnd.. them; coke; rendering; milyanb; ballIll 

CJnmpJon Intmu~ in Nunh CamJinv 

Cbunpion lnlcmrlimal in Noah Crrullnv 

Tcnaew River Pulp and Rpr in Cmtw. Rc 

Jnd.; them. & ps~.; Unti oil. Teara Mobil; AmmunWoa pkn~ 

ccbwxc~(dewdng) 

SIX cheolk~uaudcal plaNs (Famdic~l&aon) 

Open lake sumpie; Superfual sir (PCBJ YI Wuukegaa Huba 

SulE” 33% Amoce oil; bid.: prhurlly slrxl; w&#waEf: sqer6Md PY 

(PCB) 

same as 2059; Alnoco oil; Ind.: Jrimalily slcull; w8suwJu; sqclfund Jr 

mm 

Id.: ckm. & pt.; coal mhlng; (riu •~ the mnud~ d hc Wabash R.) 

Hydm-poq cd llwng 

lilmrkdpcB- 6un pqxr dehking; supelfuad ske (PCB) 

MeadCoqxsadm@bwdulPCBcwuaml~bnJ 

Au-k mamfacturing (heavy mrub and uibJ 

INdwkdpcB cc4uadNuonrilclsJDwnsIremrlorChunpkm InomwimaJ CofpoaJm 

!3omlPqler(kdirecl);mwer&ch.plarN; Ag.:NdI.; umem31411; 

Wl*lrlle(pcB) 

Sam Rpa ulldireet); m,wer & CJmn. plain; Ag.: odl.; sum II 19%; 

supedwJ she (Pm 

FUUpUKUnOfbbrfJmfl (scact Fq=r C-y) 

lnd.: heavy ad;ckm.; ataambk (PCS’s in cUkcn~) 

84 M&r Rpr; Algoma siecl; dlulghg 

Candlan Bkach Kill P&P mlll about W miks upwmd in llnakr Bay. 

ont 

Ashland OiVKoch Relining; urban NIW# hiwxical m amlaminaUm 

Boise Cascwle on both sides uf the riwr 

Site b stwe ~hc dan. Boise CaruQp outfall ia hdow dam. 

Id.: ctum.; uil. 

Appkwn f%pen and Mimi hpm (&inking): I&: tmzub anduchur 

Soq P&P mill ldciting); Pnxtu wuJ Gun* Ag. m 8upelrumJ ti 

B-3-8 
- 

El 

Rr -. 

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 

Vf 

VI 

VI 

VI 

VI 

VI 

VI 

VI 

v-l 

VI 

VI 

VI 

VI 

-- - 

w e 

# 

2618 

ldnm& lM&dm 

39:24:4ON 084:33:14W 

3132 Wl7:36N 082:55:4aW 

3135 44:49339N 091:30:38W 

3136 45:2405N 091:33318W 

3137 4S:SS:OON oQQ.26:4lW 

2429 44:27:39N 088933OW 

3138 44: 16: ION 088ZZ18W 

3140 44:13:24N 088z27334W 

3143 44f043N 088:3lMW 

3144 43z32:lM 089:27:36W 

2422 46:36:2lN 09052:3DW 

3134 44fil:Y)N 088M):IsW 

3141 43:03:26N 087:SIWW 

2427 45zO3zl6N w744:sow 

3142 43:4351N 087:4lMW 

3110 4458zoON 092z46.aW 

L397 45L37mN Oa9:25:14w 

2&x3 C4:16:00N as9z53mw 

3106 U:l63oON IB953:oOW 

3107 45:OlmN n8P39:09w 

3108 45:10:31N 089%k@lW 

3109 44w5m im37:45w 

314s 15:26: 17N 089343:%6w 

3146 44:52:5m om8:nw 

2023 35:2056N 094:17354W 

3ofio 34:X41 N 0!?296:38W 

3062 w: IomN 091:43356w 

3061 13: IO:JEN 091:393oOW 

3078 34:50:39N 092:07 2ow 

3443 34:09mN 091:31fmw 

ml5 33333:27N 091:1(:15W 

21118 35S43N 092124SW 

3073 3556:33N 092dJ7rO5U’ 

ml6 33:33m uMm28w 

3452 1334 I5N O’M.06:MW 

3077 33:57:17N 094:21:49w 

2017 33:14:32N 093:WSEW 

.slmtl 3053:MN 093:ZS:MW 

ml3 32:4OzU)N 091:43:lKIW 

SdWdddJ lmmmm 

OH HamiRon Canal Hamilton 

OH SciuloRiwr Cbillicolbe 

WI Chippew River Eau Claire 

WI FlambcauRiver E. Ladysmitb 

WI Flambuu River Park Falls 

WI For Riwr DePae Dam 

WI FoxRiwx APwm 

WI FoxRiver Ur ButteDMort 

WI FoxRiw Osbkosh 

WI Fox River, uppa PMlge 

WI LakeSuperior Asblaad 

WI Ma&-R&r Chillon 

WI MiJwautee Riva Milwaukee 

WI Peshtigo R. Harbor Pcsbtigo 

WI She-R&r Kobkr 

WI SlCroixRiw Hudsoo 

WI Wise. R/Boom J&e RhineJaoder 

WI WiiaRircr U.PenteowdlpI 

WI wii ‘n Rim u. PcnlcaweU fl 

WI WiisinRircr BrOkaw 

WI WiiaRiur Merrill 

WI wiscana ‘n Riwx wausau 

WI WisamsinRiver MobrWSkifl 

WI wismnsl ‘II River RahcJdd 

AR Arkmws River Van Buren 

AR Arkansas River IAtk Rock 

AR ArkansasRiver Pine Bluff 

AR Bayou DcLoutrc El Lhdo 

AR B~ycm Melo Jacksonvilk 

AR Bayou Melo Reydetl 

AR MishuippiRitcr Arkansas Ciq 

AR N. SyJamore Creek fifiy Si 

AR N. Sylamore Creek Pity Six 

AR RedR&x ldex 

AR RedRiver ill&X 

AR Rolling Fork River De Owen 

AR Sulphur Riw Teurkana 

I A Anacoco Bays Deridder 

LA BapuBcmeldce OakRi&e 

-a- 

(bCl~~lhRVklUlQdf&~*) 

X X X Canal ON G. Miami R.; Ap@etoa Paper; Atialioa plans; slecl; 

bydro-powx; Superlund site 

X ic X Mead Corporation on Paint Creek; Ind.: inorg. chcm. b pest.; Superfund 

Jilt 

X Pope and Talbot (deinking) 

X Pope and Tdhot (deiaking) 

X X X Fiambeau Paper; Ag.: croplands and grating fKlL 

X X X Fort Howard, James River, Green Bay Pkg., Nimkt Paper, Champion 

X X Kcrwin Paper Company (dcinking). Gladtfelder, WI Tissue, Kimberly Clark 

X Glad~felder, WI Tissue Mills, Kerwin Paper (historiul PCB contamination) 

X Peoderosa (deinkii) 

X X X HisloriuJ PCB contamination 

X Jmnes River-Dii Northern (d&king); rural 

X X X Incineralor; H2G softena @at; Ag.: aoplands 

X X Ind.: metaJs (historical PCB coatrmination); MO-400 Industrial dischugu 

X X Badger Paper MilJs, (indirect) 

X X Superfund site (b&laiuJ PCB amtrminalioo) 

Anderson Window& wood treatment plant 

Upstream of-r miJJs 

X X X X Nekmu, Fat Edwards, Consolidated Kr~fi; Vulon mat. (rubber & 

p&tic); same ml 3106 

X X X X Net-port Edwards, ConsoJidated Krah; Vulcan mat. (ruhlw B 

pkJlk);-as2608 

X W~usau P8per (sulfite mill) 

X Ward Papa (&inking) 

X Wood Iralmenf ptanl rite is between paper mills. 

X Rbiilaodcr Paper Company 

X X WeFrbxuser. half doren small milts; Ag.: aoplrnds 

X X 

X X X 

X X X Iticrr&onaJ Paper Company. nwded area; Ag.: aoplrnds 

X X lion Oil Company 

X Superfund rile (dins); rural; wvoded area 

X X X hrtrum about 30 miJes of the JaeJuontilk site (3078) 

X X PoIlaleb Corporaliuq Ag.: aopJands 

Smue 8s 3073 

SME~aDlS 

X X X Nekoom F!dwuds Pqr Gmpuy 

X X X Nekoou Paper; Jime and gml ties; Ag.: aq ud gr- lun& 

X Wad treatment phnt no Bern Creek 

X lnternationrl Paper Company in Texas 

X X B&c Southrn Co. (Boise Crude); rurd, Ag.: cropirnd 

X HCB use in l gricuburc 

TABLEIt3(amt.) 

B-3-9 
TABLE B-3 (cd.) 

- 

Er 

P 

-i 

V 

V 

V 

V 

V 

V 

V 

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 

\‘I 

VI 

VI 

VI 

VI 

VI 

VI 

VI 

VI 

ZU 

iu 

# - 

33% 

3442 

3353 

m63 

ma2 

3352 

ml54 

3082 

2532 

3065 

3066 

3418 

3416 

mm 

2544 

MB7 

3425 

w74 

3105 

3093 

307Y 

2021 

w)76 

WI 

lo26 

Km!3 

3084 

KlB5 

Rx6 

ME9 

Klel 

u&l 

HI75 

NW3 

m 

D72 

D7l 

!283 

m3 

D3-J 

m8 

m4 

- 

-lam@du BYW~ lmdhm 

3&12xnN 093:17aow LA BayouD’Ituk Sulfur 

30%?:36N 090.Z2ZlW LA BayouLabarck Norw 

32:3laN fnw54:oow IA Ba)wLaFourck Baurql 

3oom.am 093:aimw LA CalcaskuRiwr Moss lake 

32zokooN m47tlow IA Dqde-River Ho&e 

32:33:aH4 09l:SI~W LA Lakehim SWl 

l3lto2m cPluTo2mw LA Lake Pon~chr~ri~ New Orkur 

32:44:ooN 091:ll~ooW IA LakcPw4ihK.c 

3oz4%3oN a91 :23:45w LA Missi&ftpiRivu, sl. Frucnvillc 

xlmm 091:n.w IA Mississippi River B&on Roqc 

306m 0!31co1mw U MGssippiRivcr Uaim 

3omm4 091:17aW LA Miuiu&i Rirr &chary 

33zaosmi cwmmlw LA OwzhhrRiver 3-a 

32mmN u9737m LA OuacbiiaRivu Mara 

3IHO23N @XI21:42W LA Ta&&oeRiwr Robert 

32:35:abN 091:56.00w LA W-kmBrakc swarlz 

32333m 091:55mw IA WhamBrake SWUC? 

35:46sN 105:392w NM RioMur Temro 

35:13:42N (MI:31:3sW OK Fork Cobb Rcwvoir Fti Chbb 

~&MOON 095:16tKtW OK For~GibsrmRcr. F’yrer Creek 

36:52m 0%:56mw OK KwRuerv& 

34alllN 094:36:45w OK KhmichiRivcr Bii Cedar 

33:57:aw 094:35.mw OK tittk River Goahler 

13.56m 095mmw 

w:l4zO3N @J6%32W 

3ll:41mN 095:I4.tmW 

I69 k42N 097SO6W 

ta5ssN lwzu:4lW 

l9mA4lN 091:58:5ow 

~7:5l:xN4 091:3mow 

Il:25sBN 091:3356w 

38:57z35N 05%:41:13W 

lBiWtlW 096z52ztXIW 

Il.uBm 09):&39w 

295mw lnm54.mw 

wlwllw 1053.~ 

P)lI:I5N 09&21:43W 

0:55:25N 091:02. I2W 

l29354N 091:47:4BW 

ll:409N 093:4oaW 

11:33.mN o!n:3l:29W 

11:34:53N m2.323W 

DK RedRivcr 

DK Waahitr River DlUWOOd 

OK Webkrr Paul M-brx ArropCdor~ Harliqa 

r’x Bru.snRivcr Freeport 

TX HourlooSbipChnl Moryn Pair4 

TX hoer Harbce Ct~pus Ckiii 

TX fak&Rqbura Luf’km 

rX LIVE River Edns 

rx rbk+ikrhy 

rx Nrs4aRiw.x Dad 

rX Nab Rivet (a&f) Porn Artkw 

TX RioGrvdcRiwr El Puo 

TX SuA~~oebRiru @hadorf 

IX So. ForkRo&yCr. &ise 

IA Cedar Rinx PalO 

IA Des Moines R&r fkr Moines 

IA DesMuincsRivcr Des MoirK!s 

IA MisbippiRivcr Lc LhkC 

NllNTS(MlWE8 

.- _-- - ----- 

NFL CMiri - 

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 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

{r-h~uwm@rd~~ti) 

Ciip PetrokrP Corpwalion, In&: cbeo. -- 

SkN d Norw Rcfiiriu, SkU ckniul pfanl 

Inlcrnliurl Paper canpay. rural 

caow. Ir.; lad.: ckn. 

Above Bayou IaFourck. Tbii dammed water kcds Wham Brak. 

Gee+ P8c& CarpoAm, Crown ZAkrbacb; Iw rcliwrkr 

Id.: auflii sour- A&: crw and pziq 

Gwr* Pa&c ud hmu Madiwa Paper; rural; wooded arCa 

Gwr& PIcirr unl lncc~innal Paper; rural; wooded rru 

Gcoc~PacifiiiaArkaau&Ag.: uopMdguioglrsJr 

Same a 342$lucrn&mal Paper Co. (dischrga to 8. LtFourck) 

Smw a 3087, Internahmal Paper Co. (discbargr to 8. LaFottrck) 

Al.: uqhdq @f course au Ik rile 

R&cUTiiMia 

V&am Plant in Wrlh, Kansas (ckniul paxsing flati) 

Heavily wooded uu; 4.: cutk 

Wood kafmcat: Tbmrpsm L~~mbcr, Hullman Prcscrvcr, Nii flrra. 

Prcwvw 

Weyubeuscr Chapany 

Ken McUoz RcfiiCqmrriuq Total Pc(rokum. Iac. 

Fort Howard PIpcr Camp~y 

HCBMSC 

Al Da Ckmical outrrll 

~~lra*ional and Sii Pap; Iwr refineries; Ag.; cruplrd 

Cbmph Intcrutimal Cwpcua~ion on Ihe AngcliPl River 

Tcrpk-Ewy hr.. ia Dibdl wl Badea OWmiul (reria) 

Tmp&-Erly Iw. im Sikbu, TX; IWO refwurics; hi.: ckr. & pu(. 

Ckwa USA, Iw, El Pm RcGq colpvy 

Ha*clHN 

Backgrand site 

AboW 50 mika downstream d WUcrloo 

Upsham ah11 IO mikr from a KYIW 

&low PWW (prctrcalmcnl plan) 

Upsham of lock and dam ti fhwnf~nt {rhwc dam) 

- 

B-3-10 
- 

El 

VI 

VII 

VII 

VII 

VII 

VII 

VII 

VII 

VII 

VII 

VII 

VII 

VII 

VII 

VII 

VII 

VII 

VII 

VII 

VII 

VII 

VII 

VII 

VII 

VII 

VII 

VII 

VII 

VII 

VII 

VII 

VII 

VII 

VII 

Vll 

Vll 

IX 

IX 

IX 

IX 

II 

- 

AE 

LI 

I 

I 

I 

I 

I 

I : 

I : 

I : 

I : 

I : 

I : 

I : 

I : 

I : 

I ; 

I : 

I ; 

I : 

I ; 

I : 

I : 

I : 

rul 

L 

2191 

2190 

3036 

2194 

3039 

2201 

xl4ll 

3047 

3048 

al49 

3045 

2199 

x344 

3046 

3050 

3042 

3043 

xl4091 

2205 

3197 

31% 

3200 

3236 

3237 

3235 

3234 

1122 

llO5 

114lll 

)lll 

fI(N 

II99 

1110 

11% 

11% 

lo98 

3266 

3282 

3288 

3285 

- 

40307N 09s:yI:UW 

4036ff7N 0953834W 

37:32:34N 097:16:29W 

37:32:35N 097:16:29W 

36:02:MN CHOzO73W 

36:023N cEmo73ow 

39z42:36N 091:2l&iW 

38352333N 09OilU26W 

37:17:46N O893M6W 

39:07:52N MWt758W 

39zll:llN 093:53:45W 

39344:32N 094:51L36w 

19:11:14N 093:53:45W 

37S15N 093:48145W 

l1:15:32N 095:u:2Dw 

t1.98:18N 095:52:4OW 

t1:45342N 103%02w 

lO59MN O%zOl:18W 

18:U:00N 106tOlM)W 

8938:lON 10(:57:3OW 

tilQ3IN 1OMJzOOW 

(6:lOdON 112:46%W 

l7:Ol MN 114:21:20W 

f5z4435N 111tO5cO4W 

l7Sk14N 114dlMW 

Ik47:48N 1@98z12W 

17:U:IUN 103315dMW 

l9:oozm 097: 13:45w 

Pamaw 097: 13:45w 

12sk42N 096zu:45W 

i2Sh45N 096:33:15W 

f4m49t4 am49aw 

ti4s:loN lll:u:l5W 

ll:mxlN m35i45w 

12:W:27N 106341:31W 

3Ml5%lON llML?~W 

33:lLdlON 115:37m 

ti4l:C@N 121:U~W 

33346zOON 1 I8.aziXtW 

IA NishnatmtuaRivcr Hamburg 

IA Nirhorbat~Rii Hamburg 

KS ArkarasRii Derby 

KS Ark-River Derby 

MO little River D&cb 81 Horacnvilk 

MO l.Atk River Dii4 81 Horwrs+ilk 

MO MiduippiRiw Hannibal 

MO MississippiRii west Albo 

MO Mi&si~+Rii cape GirderI 

MO MissouriRiver KMSUCily 

MO MiwouriRii -a 

MO MissouriRiver St Joseph 

MO MisunuiRivu -a 

MO 04cRku RtXC& 

NE MksouriRiir Omaha 

NE MisaouriRivcr &lkvuc 

NE NacbPbmRii Mcqcw 

NE Pl&leRivcr L4luidk 

CU -River Salida 

M SouthPlat~cRiwr kavcr 

CO S1.VrianRivr.J w 

MT C3arkForkRivu WUSDspLo 

MT ClukForkRivcr Husm 

MT ~O&tiiRivu B~ZCNO 

MT GooseBay L&aide 

MT Yc8ovntoueRivcr Billiqs 

NLI LittkMisaouri R. WrfodCky 

ND RcdRii PurbLu 

ND Red River PC&@ 

SD ~SiousRivu Akra 

ED ~!GctusRiwr Akrm 

PD C&kCreek Hill ay 

UT Jord~Rinx SdlL&Cby 

WY-River Lard 

WY NorfLPkfteRivcr Acxm 

AZ GikRii Gii Bad 

CA AlamoRiver cdipurk 

CA BlancoDrti !blimn 

CA cubrrdoLqoa LoqBcacb 

rlrQ 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

TABLE B-J (cont.) 

rollmlioumx6 

--- _-.--- 

NPL o(Lr 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

:: 

X 

X 

X 

X 

x x 

-lnl .uln Dwcripom 

(FrLuuw Ia I& *wly .I Ih -pH.Y *I@ 

Ind.: &cm. and pest.; mc~ak, hydrquwer; - as 3042~oppuaitc aider d 

rim 

same as 3036 

same as 2190 

Same as 3039. Below Wichita 

Same as 2194. Below Wichita 

Same as 3040. Rice @owing region 

Same as 2201. Rice growing region; heavy pedcidc USC 

Fish collected near dowmwn area. 

Ind.: &cm. ; bcavy mrtak; bcavy shipping traffic 

Collrckd al POTW outfall. Proctor & Gamble prpcr producls, Ag 

croplPnds 

Same as 3046 

Same as 2199 

A&: croplands 

Ind.: &cm. and pest.; metah, hydra power; same a~ 2191 - oppdc sides 

of river 

Dcfuncl wood lrcalmcnl plant 

Stone Conlaincr Corporalion 

Sugar bee1 procfuing planI; croplands; Same as 31 I1 

Sugar bee1 processing plant; croplands, Same as 2100 

Same as 3199 

SW IS 21D9 

Id: peslicidu; Supcrfuud rife (chlorobwle0Ca) 

Railroad tic rruhg plain (defunci) 

Cotton growing region (New Phoenix) 

HCB use in agricukurc 

Mukiplc sources 

Mukiplc sources 

B-3-11 
- 

lc 

Rl 

i 

I)1 

I.% 

I> 

IZ 

I> 

I> 

I)1 

IX 

IX 

IX 

IX 

IX 

IX 

IX 

IX 

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 

L- 

: 

'1 

; 

'I 

7 

i 

3 

3 

3 

2 

3 

3 

3 

3 

3 

3 

2 

3 

3 

3 

w 

# 

iiT3 

3286 

3271 

3272 

3275 

3276 

3289 

3451 

3354 

3283 

3355 

> 

31:47 ISN Il1:17:33W CA Harbor Park Lake HarborC%y 

y):34m Iu:lltmJW 

37:55YooN 122:21tIOw 

4054OON 124tUMOW 

4052:OON 124.90MW 

36:48:ooN 121:46mw 

34.01:45N I I8:4u:4SW 

373573ooN 121:IB~W 

33:*T:OON I lEIO.~W 

37:56:00N 121:19:ooW 

3290 )7:57.uDN 12l:M:00W 

3274 I1:55:aJN 124.07tiknv 

3357 ~~.05:m 12 I .u:abw 

uti? 

32m 

1287 

ma 

1281 

1264 

wo 

1269 

I278 

!O37 

1261 

1262 

!776 

12M 

,241 

246 

nm 

24 

245 

252 

250 

249 

158 

47.3 

2s6 

24n 

to3 

1 

1 

; 

I 

1 

6 

6 

5 

6 

5 

5 

4 

4 

4 

4 

4 

4 

4 

>4 

f0:27:OON 122: I 1:OOW CA Sacrmmm~oRkr Andcrum 

lO:D!MMJN l2Ellz1lOW CA Sxmmcn~o River Red Bluff 

33:tiMN 118tizIXlW CA San Gatwicl River Longlk&b 

)4:24:mN 119:3MNlW CA Sanra Clara River smla Paula 

l42OXNlN I19:04:oOW CA Santa Clara Rir Smna Paula 

w4:27N l18:31:2sW CA Santa Monica Bay La Aqclcr 

13:55:00N 118:2EmW CA Slmrl Bank (Pac. 0.) La A&es 

l7:43:0ON l21:09:oDW CA StanislausRiter Ripn 

19:24:M)N l23M:MW CA Upper Eel River potter V&y 

19146 UN IS5zOS:33W HI HomoliiStrum Hib 

!l:l&IXlN 157:59zIYJW HI Purl Harbor Middk Loch 

!2:04:3oN 159L?zaw HI W&a PaekkaaSt. Kmui 

15:4omN 11l:40:00w NV Cobrrdo River Blw H-r DI 

0:~3ON 14927:35W AK Bird Creek Bird 

~1:13:2ON 149:51:21W AK Ship Creek Anchorage 

7:03:00N 133:M:oOW AK Silwx Bay SiIka 

,1:32:42N 151:30:45W AK Susicnr R&r SllSiIo~ 

8~4 I :OON 134:03:ooW AK VaoderbilI Creek Junuu 

S:U:JSN 13l:U:aOW AK wudclwc Ketcbikao 

3:48:29N ll7:oo:I5W ID BoircRiver Puma 

7:3&05N 116:43:15W ID Coeur d’Akoc UC Cocur d’ALac 

7:33:07N I l6:P.~W ID Cocur d’Aknc Rii Cocur d’Akw 

2:37:25N 1 l4:31:WW ID Rock Creek TwinPalls 

3:00:08N 1IS:lZMW ID Snake River Kings Hill 

6:25:15N 117XJ2.01W ID Snake River Lcwislon 

7: l9:08N 116:3X3%’ ID SI. Joe Riwx St Marie 

5:37: 19N 122:45:2oW OR Columbia River PorllMd 

CA Haylark Creek H+Nk 

CA lauituo~d Richmond 

CA MadRiver Al-la 

CA MadRiver%& Atcata 

iCA Moss tradiiDm. Moss Loudly 

ICA Mou1hdMdiiCr.Mdibu 

ICA New Mormon Se Stock1on 

‘CA New Rinr WC.SlRlOdd 

CA OMM- Sbqb Stockron 

CA Pm of S~ocklon SIockloo 

CA RowdyCreek Smith Rivrr 

CA Sacramento fkha Anlioch 

s!!L! 

X 

X 

X 

X 

X 

X 

X 

X 

rrnur RauN!m .-_. -_. _--__ ----__ -- WI, rmm 

rm rrNc wr Rh Inn Iti rww 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

McNamur & Peepe (bisIorM PCT siIc) 

Mukipk lalrccs 

skara Pacifii (lliuaical PCP siIc) 

IJailed H&born: pcs~icidc prcrulia plul in &l’s (PCXI’s, DDT, pb) 

Molkh-Ada 

sknr Pbciiu 

Mukipk sources 

PGTW T+nCrtJ;~aiqlaad(hanu) 

McCormick ud Baa&r (wood prcurvcn); Superfund Ic (wh’cda) 

Mukipk sasrcu (HCB use) 

McCormick & Buoer (wmd pwcmrs); A&: croplands & or&; 

Superfund silt (srhmls) 

MrCamick & Bticr (wuod fw-IX); Superfund tic (soh=olr) 

Arcala Lumhcr Canpmy (hislorid PCP tic) 

Gaybcd -timer Corp.; Iml.: dwnt.; refir): pswx m; Al.: 

orcbdaMderopludr 

sirapaPJpucaapu):=-.-== 

hmmd IalcmaIid (rccydcd ppu); A&: cropbnck and eat& 

SiRlprOr PIpU w, P&K COd PIpcr 

Sulcn3281 

smKrrn48 

El Ziqundo R&q, Hypwba PDTW ou~fJI, makipk sources 

KYIW: Hyfxrion aatfd 

Mukipk loalccs 

. . 

s* yard wirb rtuKdTd PC& Suf#crfund she; landlid 

Alaska Pulp Cunpnay 

w ,kihK carp. (suuile 4); Krlditi Pulp md PrQcr 

Id.: silw minig 

MiRiq 

B-3-12 
TABLE B-3 (Conl.) 

Ptm+TSnlRClcs 

__. ..- - 

NPI. 4Mwr 

NOWWNT~ 

--1 Addltiaml Sltr Dscrtpaon 

I I 

EPAiFp&d. 

3216 /4S:Sl:VN 122.47.3YW (OR CuIumhId Rrvcr 

321x 46:OY:2lN 123 24:OOW ‘OR 

3219 45:3Y: ION I20 S6MW OR 

7201 45:36:06N I22.4?:57W OR 

.Ps 

X ‘i 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

X 

Sr. l~clcos 

Wauna 

Dalles 

I 

Portland 

3208 44:03:WN I lh:S7:00W OR Malheur Rlvcr 

1212 43:46:5YN I I7:03:09W OR Owyhce Rjvcr 

1205 45:26:33N I23,14:07W OR Tualarin Rrvrr 

3215 45:27:4ON 122:45:3OW OR Tualatm River 

7206 4S:34:53N 122.44:3YW OR Wlllamem! River 

3217 44:23:16N I27 14QZW OR Wlllamcuc Rrvcr 

3213 45: 17: I7N I22 SR.03W OR W~llnnnxc River 

3437 45: 17:38N I22 46:ORW OR Wlllamritc Rrvcr 

7226 47,23:3ON 122:37 7XW WA Burley I.agoon 

1431 

1220 

122 I 

3222 

1439 

3440 

3441 

?I63 

3191 

Ontano I 

Owyhcc I Chewy Glove I 

Cook Park 

Pornand 

Hallsey 

Newhureh Pool 

Wllsonvdlc 

Purdy 

I 

46.15.3hN 121 57.S7W 1 WA Columbia R (lower) Esruary 

46:07:SON 122:SY-27W WA (‘olumbla River I.~~flpVlKW 

46fl6:OON I I R:SS:OOW WA Columbia Rtvcr ‘Tri (‘itics 

45:34:08N 122:24:42W WA Columhla RIVU Camac 

46:lS:MN 123.33:32W WA Columbia Rrvcr Wendy IFland 

46f033N 122:51.04W WA Columbia River Kalama 

4558:OSN 122:49.\YW WA Cnlumhla River Deer I\land 

47: 16: l2N I22.25:SOW WA Comn~ncvrrmt Ray Tacoma 

465X:WN 123:53 WW WA Grays Harbor 

46:57:13N 123:Sl.ISW WA Grays Harbor 

Boise Cascade (indIrect) 

James River Corporation in Clalskanic 

Hydm-power (PCR’s gcneraled): fond pnressing plant; Ag.: arch. & 

cmplands 

Five paper mills using Cl bleach. two papr mills nrn using Cl hleach; 

shipyard ! 

x ; 

X 

X 

X 

X 

x 

X 

Minor industries; Ar.: cmplands 

Ind. them.: smelters; shrpyardc; timber 

Hallsey Pulp Company (Pope and Talhrul; Ag.: cn@nds 

Dcinking plant; other pulp mills upslrcam: Ap.: cnjplands 

Below transformer and scrap med salvape yard: below Superfund SIIC 

(FCB) 

Weyefiaeuscr and Longvrcw Fiber Company; AR.: croplands & prazing 

fields 

Boise Cacade: Ap.: cmplanda & grazing fields 

Crown Zellerbach (James River Corporatmn) 

Borse Cascade and Weyerhaueser. hqvrcw Fihcr downstream 

Boise Cascade and Weycrhauescr. Longvicw Fihcr downsrrcam 

Boise Cascade and Weyerhaueser. lnngvicw Flher downstram 

Simpson Tacoma Krdll, IJS Oil and Rcfinmp; hcavrly industriali&: 

Superfund cut tComrnencement Bay) 

IlT Rayruurr. Inc. (sulfire mill. nonchlonne) 

Weyerhaeurrr Company (sulfite mdl. chlonnc) 

Champion Paper Company; heavily mdusmallxd: Superfund sur 

Sunpcnn Pulp Mrll (wood overlay product<) 

ITT’ Raynntrr. Inc. 

X 

X X! 

X 

X 

X 

X 

x xx x 

1162 47: 17:OSN 122:24:28W WA Hylcboz Waterway Tacoma 

3227 47:14:20N 122.02.44)W 1 WA Oakland Bay Shelton 

32YS 48:OR:WN 123:24:4SW ‘WA Pnr~ Angelex Harbor Pan Angelcc 

3294 48:06:3ON 122:4S:3OW (WA Port Townsend Pan Townsend 

2247 47:12:.52N 122:20:2SW ! WA Puyallup River Puyallup 

2246 47:49:52N 122:02:SOW WA Snohomich ?&nrrx 

3223 4R:Ol :S2N 122: I3:oOW ) WA Stcamhoar Slough Everett 

X 

x x 

X 

X 

X 

x ! i X 

x 

X 

X 

x I 

X 

X 

X 

X Slmpzon Paper Company (down~r~am) 

X Liphl a~nculfurc, tlmhcr 

We) .vxuscr Company and SI‘OII Paper Company; Sup&und FII~ 

19olvents) 

x ’ 

(;rorpia Pa~fic Isulfire proce$r) 

X 

I 

X 3224 ‘48:45:01N 122:29:02W ‘WA Whalcom Warerway Relllnpham 

X 7231 46:22:42N I IY:ZS:2YW (WA Yakima Rtvcr Richland 

X I 3230 147:lI:lON 120:02:3OW ‘WA Yakrma River Cle Elum 

B-3-13 
APPENDIX B-4 

Dioxins/Furans: Episode Numbers Used in Statistical Tests 

(By Category) 

TABLE B-4 (Cont.) 

302s 

3037 

3073 

3074 

3075 

3 166 

3169 

317s 

3 179 

3 187 

3200 

3205 

323s 

3248 

3309 

3320 

3430 

Total 

PULP & PAPER 

(Chlorine) (PPC) 

Episode 

20 15 

2016 

2017 

2138 

2142 

2294 

2302 

2304 

2355 

2385 

2422 

2427 

2532 

2721 

2725 

3062 

ME 

IA 

NM 

TX 

NC 

AL 

GA 

GA 

SC 

co 

OR 

AK 

ID 

NY 

NY 

NJ 

33 

State 

AR 

AR 

AR 

NC 

FL 

GA 

AL 

AL 

ME 

MN 

WI 

WI 

LA 

ME 

AR 

3080 

3081 

3088 

3107 

311s 

3122 

3146 

3150 

3151 

3152 

3192 

3217 

3218 

3220 

3221 

3222 

3224 

3237 

3245 

3246 

3256 

3260 

3267 

3303 

3316 

3317 

3318 

3328 

3329 

3331 

3332 

3333 

3335 

3336 

3337 

3339 

3340 

LA 

TX 

IA 

WI 

Ml 

MI 

WI 

AMA 

NH 

WA 

OR 

OR 

WA 

WA 

WA 

WA 

AK 

AK 

ID 

NY 

CA 

NY 

PA 

MD 

PA 

AL 

FL 

FL 

FL 

FL 

GA 

GA 

GA 

KY 

MS 

3341 

3342 

3343 

3344 

3345 

3346 

3347 

334s 

3349 

3350 

335 1 

3353 

3395 

3403 

3404 

3416 

341s 

3420 

3421 

3422 

3423 

3424 

3425 

3435 

3452 

Total 

MS 

NC 

NC 

NC 

NC 

NC 

SC 

SC 

SC 

TN 

TN 

IA 

NC 

TN 

TN 

LA 

LA 

PA 

VA 

VA 

VA 

VA 

LA 

MS 

AR 

78 

INDUSTRY/URBAN 

(INWJW 

Episode State 

1994 MI 

2023 AR 

2057 IN 

2060 IN 

2191 LA 

2210 DC 

2215 PA 

2220 VA 

No data available for dioxim/furans. Number of data values varies by chemical. 

B42 
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 

3 100 

3101 

3103 

3111 

3113 

3115 

3120 

VA 

VA 

VA 

AL 

NY 

NY 

MI 

OH 

NY 

NY 

NY 

NY 

NY 

NY 

NY 

PA 

ME 

IA 

IA 

IA 

KS 

MO 

NE 

NE 

MO 

MO 

MO 

MO 

MO 

MO 

AR 

LA 

LA 

OK 

TX 

PA 

3 134 

3141 

3 144 

3147 

3149 

3164 

3165 

3168 

3 172 

3174 

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 

WI 

WI 

DC 

DE 

NC 

NC 

AL 

AL 

FL 

KY 

TN 

TN 

TN 

co 

SD 

OR 

OR 

OR 

UJA 

WA 

PULP & PAPER 

(No Chlorine) (PPNC) 

Episode State 

3089 OK 

PA 3090 OK 

3091 OK 

3092 IA 

IL 3093 TX 

IL 3108 WI 

MI 3112 MN 

3114 IL 

c No data available for dioxins/furans. Number of data values varies by chemical. 

ID 

ID 

ID 

VA 

CA 

CA 

CA 

CA 

CA 

CA 

CA 

NY 

3297 

3298 

3299 

3300 

3301 

3302 

3306 

3307 

3310 

3311 

3313 

3314 

3315 

3321 

3322 

3324 

3326 

3327 

3411 

3412 

3426 

3428 

3432 

3438 

3443 l 

Total 

PA 

NY 

NY 

NY 

NY 

NY 

NY 

NY 

NJ 

NJ 

PR 

WA 

AR 

106 

TABLE B-4 (Cont.) 

B-43 
3135 WI 

3136 WI 

3137 WI 

3138 WI 

3140 WI 

3143 WI 

3145 WI 

3184 MS 

3191 WA 

3270 CA 

3287 CA 

3294 WA 

3330 FL 

3360 AL 

3375 GA 

3376 GA 

3377 GA 

3378 GA 

3401 TN 

Total 27 

WOOD PRESERVERS 

WV 

Episode State 

3076 OK 

3077 

3110 WI 

3167 NC 

3173 FL 

3196 

3197 co 

3271 CA 

3273 CA 

3274 CA 

3278 CA 

Total 11 

TABLE B-4 (Cont.) 

REFINERY/OTHER 

INDUSTRY (R/I) 

Episode State 

2026 OK 

2380 IL 

2383 IL 

3061 AR 

3063 IA 

3069 TX 

3071 TX 

3072 TX 

3086 LA 

3095 PA 

3096 PA 

3125 MN 

3 183 KY 

3264 CA 

3312 

3431 PR 

3434 NJ 

3442 IA 

3444 TN 

3446 KY 

Total 20 

* No data available for dioxins/furans. Number of data values varies by chemical. 

B-4-4 

TABLE B-5 

Other Xenobiotics: Episode Numbers Used in Statisticai Tests (By Category) 

NASQm (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 NE 

3042 NE 

3050 MO 

3104 PA 

3199 SD 

3281 CA 

3308 NY 

Total 40 

AGRICULTURE (AG) 

3261 HI 

State 3272 CA 

AR 3414 PA 

AR 3415 PA 

AR Total 6 

AR 

OK POTW 

AK Episode State 

2122 

ND 2152 FL 

Episode State 2322 NY 

MS 2280 TX 2432 MI 

FL 2358* ME 2544 LA 

FL 2478 ID 3308 NY 

FL 3050 MO 3450* CA 

IA 3082 LA 3451’ CA 

NE 3083 LA Total 8 

VA 3084 TX 

VA 3099 DE BACKGROUND (B) 

WA 3 105 OK Episode State 

WA 3158 ID 2110 SD 

TX 3170 AL 2139 NC 

TN 3171 AL 2216 PA 

AL 3180 GA 2283 TX 

NY 3193 VA 2397 WI 

ME 3208 OR 2435 MI 

MI 3212 OR 2651 NJ 

MI 3282 CA 3022 ME 

MI 3352 LA 3023 ME 

MN 3437’ OR 3028 ME 

OH Total 19 3037 IA 

ID 3073 AR 

LA SUPERFUND (NPL) 3074 NM 

NV Episode State 3075’ * TX 

IA 3097 DE 3166 NC 

3226 WA 3169 AL 

+ No data available for other xenobiotics. Number of data values varies by chemical. 

++ Data available for mercury only. 

B-5-1 
TABLE B-5 (Cont.) 

3 178 GA 

3200 co 

3205 OR 

3238 AK 

3248 ID 

Total 21 

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 

3334 

State 

AR 

NC 

GA 

AL 

WI 

LA 

ME 

ME 

WI 

MI 

MI 

NH 

WA 

WA 

WA 

AK 

AK 

NY 

CA 

NY 

PA 

PA 

FL 

GA 

GA 

3340 MS 

3341 MS 

3342 NC 

3348 SC 

3395 NC 

3403 TN 

3416* LA 

3418* LA 

3420 PA 

3421 VA 

3422 VA 

3423 VA 

3424 VA 

3425 LA 

3435 MS 

Total 42 

INDUSTRY/URBAN 

(INWURB) 

Episode 

3043 

3044 

3045 

3079 

3085 

3101 

3120 

3149 

3172 

3174 

3189 

3190 

3203 

3234 

3235 

3236 

3244*’ 

State 

NE 

MO 

MO 

OK 

TX 

PA 

MI 

DE 

AL 

FL 

TN 

TN 

OR 

3307 

3315 

3411 

3412 

3426 

3428 

3438* 

Total 

3258 

3269* 

3275** 

3276 

3283 

3285 

3286 

3289 

3296 

3298 

3306 

VA 

CA 

CA 

CA 

CA 

CA 

CA 

CA 

NY 

NY 

NY 

NY 

PA 

NY 

NY 

NJ 

NJ 

WA 

35 

PULP & PAPER 

(No Chlorine ) (PPNC) 

Episode State 

3090 OK 

3091 OK 

3 108 WI 

3112 MN 

3135 WI 

3136 WI 

3140 WI 

3 143 WI 

3145 WI 

3191 WA 

3287 CA 

3294 WA 

3330 FL 

3360 AL 

c No data available for other xenobiotics. Number of data values varies by chemical. 

l * Data available for mercury only. 

B-5-2 
TABLE B-5 (Cont.) 

3360 .4L 

3376 GA 

3377 GA 

3401 TN 

Total 17 

WOOD PRESERVERS 

OW 

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 

* No data available for other xenobiotics. Number of data values varies by chemical. 

f. Data available for mercury only. 

B-5-3 

eEPA 

United States 

Environmental Protection Agency 

(WH-551) 

Washington, DC 20460 

Official Business 

Penalty for Private Use 

$300 

*1992* _--.- 

THE YW OF