Organic Priority Pollutants in Nearshore Fish from 14 Lake Michigan Tributaries and Embayments, 1983

J. Great Lakes Res. 13(3):296-309 Internat. Assoc. Great Lakes Res., 1987

ORGANIC PRIORITY POLLUTANTS IN NEARSHORE FISH FROM 14 LAKE MICHIGAN TRIBUTARIES AND EMBAYMENTS, 1983

Joseph Camanzo Clifford P. Rice David J. Jude Ronald Rossmann

Great Lakes Research Division Great Lakes and Marine Waters Center The University of Michigan Ann Arbor, Michigan 48109 ABSTRACT. Composite, nearshore, whole fish samples of selected species, collected in fall 1983 from 13 Lake Michigan tributaries and Grand Traverse Bay, were analyzed for a wide range of pesticides and priority pollutants using gas chromatography-mass spectrometry. This study was carried out to identify existing source areas for known and previously unrecognized toxic substances. Our strategy was to analyze those resident fish with the highest likely levels ofcontaminants. All fish analyzed (eight species from southern Michigan to the upper peninsula) exceeded the 2 mg/kg FDA action levels for PCBs, while 50% of the samples exceeded the DDTr IJC objective of 1 mg/kg. St. Joseph River common carp (Cyprinus carpio) carried the heaviest contaminant burden of all fish examinedfor PCBs (27.6 mg/kg), DDTr (10.2 kg/mg), and toxaphene (3.3 mg/kg); chlordane levels (0.85 mg/kg) were second highest to those in Kalamazoo River common carp (0.87 mg/kg). Concentrations of PCBs, toxaphene, DDT, DDE, and other pesticides were higher in bottom-feeding fish, such as common carp, than in top predators, e.g., northern pike (Esox lucius). Bottom feeders are relatively fatty fish, and live and feed near contaminated sediments, which increases their potential to bioaccumulate fat-soluble contaminants. Pesticides were also present in elevated concentrations in fish from sites with higher industrial and agricultural development. ADDITIONAL INDEX WORDS: Toxic substances, polychlorinated biphenyls, pesticides, water pollution effects.

INTRODUCTION

ted organics, such as polychlorinated biphenyls (PCBs) and chlorinated pesticides, polycyclic aromatic hydrocarbons, phenols, esters, carboxylic acids, and aliphatic hydrocarbons. Hesselberg and others have concluded that a large number of compounds, not necessary for fish survival and growth, appeared to be accumulating in Great Lakes fish tissue. The main sources of Great Lakes contaminants are industrial discharge, agricultural runoff, hazardous waste dump sites, automobile emissions, municipal effluents, and illegal dumping of toxic substances. Point source releases of PCBs and agricultural use of pesticides in the Great Lakes area have historically been the means of introduction of these contaminants into the Great Lakes

Various studies have documented a wide variety of anthropogenic, xenobiotic contaminants in fish from the Great Lakes and their tributaries. Such studies include work by Clark et al. (1984), DeVault (1984a), DeVault (1984b), DeVault and Weishaar (1983), Hesse (1975), Holden (1970), Jaffe et al. (1985), Kuehl et al. (1976), Kuehl (1981), Kuehl et al. (1983), Miller and Jude (1984), Oliver and Nicol (1982), Rohrer et al. (1982), Schmitt et al. (1981), Veith (1975), and Veith et al. 1981). In a report by Hesselberg and Seelye (1982), 476 compounds were tentatively identified in Great Lakes fish although only eight compounds were detected in hatchery-reared fish of similar species and size. Compounds detected included halogena296

ORGANIC PRIORITY POLLUTANTS IN NEARSHORE FISH

basin. However, because the use of compounds such as PCBs, DDT, dieldrin, and chlordane have been banned or restricted, atmospheric deposition has become a significant source of PCBs and certain chlorinated pesticides in the Great Lakes (Eisenreich et al. 1981). Studies have shown that high molecular weight chlorinated hydrocarbons are carried to sea by the earth's wind system; aerial input, via a combination of rain, dry fallout, and vapor deposition may well represent the major source of PCBs and DDT in the oceans (Bidleman et al. 1977). Once these contaminants enter water systems, they bind to particulate matter in suspension or in bottom sediments, which can in turn provide a continuing source of contamination to the water column. Accumulation of various contaminants in Great Lakes fish at levels in excess of U.S. Food and Drug Administration (USFDA) guidelines has resulted in restrictions of the consumption of certain species. The presence of toxic substances in the Great Lakes, many of which bioaccumulate in fat tissue of fish, is a human health and environmental concern. There is a positive association between the consumption of contaminated fish and the elevation of human body burdens of certain fat-soluble contaminants, such as PCBs or DDT (Humphrey 1985). These burdens are cumulative as a result of the long half-life of these compounds. Consumption of PCB-contaminated fish by Michigan residents caused serum PCB levels and PCB levels in human milk to be significantly higher than control populations (Humphrey 1975). Because some organic contaminants can be transmitted to the fetus across the placenta and to infants through breast milk, the consumption of contaminated fish is of particular concern to women who are pregnant or nursing. The longterm consumption of contaminated fish may also have chronic toxicological effects in humans which are not evident at this time. Polychlorinated biphenyls and some organochlorine pesticides have characteristics of high stability, persistence in the environment, high potential to bioaccumulate, and high toxicity (USEPA 1979a). Presence of these compounds in Great Lakes fish has had a deleterious effect on the development and economy of Great Lakes fisheries. There has been a reduction in the utilization of Great Lakes fish both for commercial and recreational purposes due to contamination. Recent studies have also shown that past elevated levels of PCBs and DDE (a major DDT metabolite), which

297

came about before their use was restricted, may have inhibited reproduction in lake trout (Salvelinus namaycush) in Lake Michigan (Willford et al. 1981). Studies by the U.S. Fish and Wildlife Service have long recorded the usefulness of fish as effective monitors of aquatic pollution. This biomonitoring can be employed to assess the hazard of localized industrialization and agricultural development on bodies of water. Resident fish, particularly bottom feeders and long-lived species such as common carp (Cyprinus carpio), bullheads (Ictalurus spp.), or suckers (Catostomus spp.), are good indicators of these kinds of contamination. The older, larger, fatter fish have a greater chance to accumulate fat-soluble pesticides, PCBs, and other toxic chemicals. The purpose of this study was to analyze nearshore fish collected from the mouths of rivers and embayments around Lake Michigan, in order to detect contaminant problems in resident fish populations. Nearshore areas are the usual recipients of point source discharges and may contain high concentrations of toxic substances, which could be transferred to fish. METHODS

Fish were collected from 13 tributaries and Grand Traverse Bay in State of Michigan waters during 1983 (Table 1). Collection sites were distributed throughout Michigan, including 10 sites from the lower peninsula and 4 from the upper peninsula (Fig. 1). Fish were collected during fall, before resident fish populations were influenced by migratory or overwintering movements. Techniques used to collect the fish varied, depending on the species and water conditions. The primary collection method was electrofishing, but we also used baited trot lines, hook and line fishing, gill nets, fyke nets, seines, and a backpack shocker. At each site, approximately 15 samples of two fish species were collected. We attempted to collect sport fish, or fish that were abundant, and good contaminant indicator species, such as bottom feeders. Two of the following species were collected from each site: common carp, bowfin (Amia calva), channel catfish (Ictalurus punctatus) , pumpkinseed (Lepomis gibbosus) , rock bass (Ambloplites rupestris) , smallmouth bass (Micropterus dolomieui) , largemouth bass (Micropterus salmoides) , lake trout (Salvelinus namaycush), and northern pike (Esox lucius). Fish from each site were separated by species

298

CAMANZO et a/.

TABLE 1. Listing of nearshore tributaries and embayments sampled (see Fig. 1), fish species at each site, length, and age ranges.

Fish Species Analyzed

Number of Fish Per Composite Sample

Length Range (mm)

St. Joseph River (SJ)

common carp smallmouth bass

5 7

641-698 230-273

8-11 2-3

Kalamazoo River (KR)

common carp largemouth bass

4 4

581-698 167-249

6-11 2-4

Grand River (GR)

common carp channel catfish

3 6

651-651 322-370

8-9 4-12

Muskegon River (MR)

common carp pumpkinseed

4 3

611-698 133-145

6-11 4-5

White Lake (WL)

common carp bowfin

4 5

644-693 701-744

8-11 7+

Pere Marquette River (PM)

common carp bowfin

6 8

580-683 704-735

6-10 7+

Manistee River (MR)

common carp bowfin

4 4

725-790 705-749

12-17 7+

Platte River (PR)

common carp northern pike

3 6

714-743 571-717

11-13 2-5

Boardman River (BR)

smallmouth bass rock bass

6 3

288-400 205-263

3-6 3-7+

Grand Traverse Bay (GT)

common carp lake trout

3 4

720-790 630-870

11-17

Manistique River (TR)

smallmouth bass northern pike

5 3

232-276 401-473

2-3 1-2

Whitefish River (WR)

common carp rock bass

11 7

568-695 163-192

6-11 5-7

Escanaba River (ER)

common carp northern pike

5 6

581-660 536-725

6-9 2-5

Ford River (FR)

northern pike rock bass

6 5

526-704 173-196

2-5 5-7

Site Location

and immediately stored in contaminant-free plastic bags. Fish were then placed on ice and returned to shore for processing. They were then ranked by size, weighed, measured (total length), age estimated using published age-length keys, individually wrapped in aluminum foil, and labelled. Fish were then grouped into sets of approximately five fish based on similar size. Only the group contain-

Approximate Age Range (yr)

ing the largest fish was analyzed, because it was assumed that size is directly proportional to age, and the older fish have a greater potential to bioaccumulate contaminants. Fish samples were transported on dry ice to the laboratory for storage and chemical analyses. Fish were stored frozen until analyzed. Whole fish, composite samples were homog-

ORGANIC PRIORITY POLLUTANTS IN NEARSHORE FISH MICHIGAN

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I I I KILOMETERS

FIG. 1. Lake Michigan tributary and embayment sampling locations for contaminated fish survery, 1983. Abbreviations for each river are defined in Table 1. Bar graphs show mean concentrations (mg/kg wet weight on the x-axis) for PCBs (P), DDTr (D), toxaphene (T), and chlordane (C). Data are for common carp at all locations, except the Boardman River (BR) where the fish was smallmouth bass and the Manistique River (TR) and Ford River (FR) where the fish was northern pike.

enized using a Hobart® stainless steel vertical chopper which was pre-cleaned with pesticide-free acetone and hexane. In between each sample, the chopper was washed with a Liquinox®-water solution, then rinsed with deionized distilled water and methanol. A second 50-ml methanol rinse was saved for an organic method blank to ensure cross contamination did not occur. Ground fish were placed in glass jars with foil-lined covers and maintained frozen until analyzed. The ground fish samples (20 g) were extracted by Soxhlet methods according to the USEPA Central Regional Laboratories' Standard Operating Proce-

299

dure (Para. 8.4.3.1) which was revised from Method #625 Federal Register 44.223, 3 December 1979 (USEPA 1979b). The results, which are reported in mg/kg wet weight of fish, are not corrected for method recovery. The recoveries of PCBs and p,p'-DDT, for example, based on a spiked sample, were 670/0 and 76%, respectively. The approximate limits of detection were 0.1 mg/ kg for PCBs, 0.2 mg/kg for toxaphene, 0.005 mg/ kg for pesticides, and 0.02 mg/kg for the priority pollutants. The extracts from the fish were split into two aliquots: 1/5 for total lipid determination, and 4/5 for chlorinated hydrocarbon and priority pollutant analyses. Each ground fish sample (20 g) was mixed with 50 g anhydrous Na2S04 , blended, transferred to a pre-extracted Soxhlet assembly, and extracted with 300 mL of 1: 1 acetone/hexane for 16 h. The extract was then concentrated to 10 mL using a Kuderna-Danish concentrator. Two mL of concentrate was transferred to a labelled pre-tared aluminum pan for lipid determination. After evaporation under a fume hood, the weight of this residue was measured as the lipid weight and converted to percent lipid. The remaining 8 mL of the fish sample extract was initially cleaned using gel permeation chromatography (GPC). The GPC had a 25 X 280 mm column with 60 g of Bio-rad SX-3 beads. Flow rate was adjusted to 5 mL/min and all loops and the injection port were purged with 100% ethyl acetate for 10 min. Performance of the GPC was monitored by periodic injection of chlorinated hydrocarbon spiked fish samples, which determined the efficiency of the Bio-rad column and the elution characteristics. Of the 8 mL of fish concentrate injected, 5 mL stayed in the sample loop and 3 mL was used as a wash. The elution procedure was such that the first 150 mL ethyl acetate was discarded and the next 150 mL was saved. Solvent blanks were injected periodically to detect carryover. The 150 mL of extract, which represented half of the original 20-g fish sample, was concentrated and the solvent replaced with nhexane. The extract was again split; 1/5 was used for the analysis of PCBs and pesticides by gas chromatography-electron capture (GC/EC) and 4/5 for the analysis of priority pollutants by gas chromatography-mass spectrometry (GC/MS). The analysis of PCBs and pesticides was qualitatively confirmed by GC/MS. Prior to PCBs and pesticide analysis, fish extracts were subjected to a Florisil (MgSi0 3) column cleanup, which removed residual lipids

300

CAMANZO et al.

and other organic interferences. The Florisil was a PR grade (60-100 mesh), activated at 675°C. Before use, Florisil was activated for 16 h at 130°C in a foil-covered glass container and then stored as a slurry in n-hexane. The elution pattern for parameters of interest was determined before chromatographing the samples. A wad of glass wool and 1 cm of anhydrous sodium sulfate were placed in the chromatographic column (250 mm long x 10 mm ID) with a Teflon stopcock and 250-mL reservoir bulb. A 12-g slurry of Florisil (23 cm above the sodium sulfate) was poured into the column and allowed to settle; then another 1 cm of sodium sulfate was added. The sample was loaded onto the column and the first elution was performed with 60 mL of 6010 diethyl ether in nhexane, followed by the second elution with 200 mL of 50% diethyl ether in hexane at a flow of 4-5 mL/min. The eluates were concentrated to 2 mL using a Kuderna-Danish evaporative concentrator assembly. The second fraction, which contained the pesticides endrin, dieldrin, and endosulfan I, was then ready for GC/EC analysis. Fraction 1 was further fractionated using silica gel chromatography in order to separate PCBs from the bulk of the pesticides. The silica gel Bio-rad-Bio Sil A (1001200 mesh) was first activated at 130°C for 16 h. Following activation, the silica gel was deactivated with deionized distilled water (2% by weight) and stored as a slurry in n-hexane to prevent further deactivation. The same Florisil chromatography column assembly was used, with the exception that 7.5 cm of silica gel was added instead of Florisil. The column was loaded with the eluate (fraction 1) from the Florisil column. The first fraction contained PCBs and p,p'-DDE and was eluted with 90 mL n-hexane at a flow of 1-1.5 mL/min. The second fraction contained the remainder of the pesticides and was eluted with 30 mL of 10% ethyl acetate in hexane. All fractions were concentrated and solvent replaced by nhexane prior to GC/EC analysis. A list of compounds analyzed is included in Table 2. The analyses of fraction 2 from the Florisil column and fraction 1 from the silica gel column were quantified on a packed column GCI EC. These fractions included PCBs, p,p'-DDE, endrin, dieldrin, and endosulfan I. A Varian® 3700 gas chromatograph, equipped with an electron capture detector, 5% SP-2100 on Supelcoport® 2 m x 2 mm (ID) column, nitrogen carrier gas, and computerized data system was used. The GC conditions were: column temperature 190°C, flow rate

(N 2 ) 30 mL/min, injection port temperature 220°C, and detector temperature 320°C. The compounds were quantified by the external standard method using peak area. The PCBs were quantified for Aroclor 1248, 1254, and 1260 using a modificaion of the Sawyer method (Sawyer 1978). The modification included a computer approach to distinguish overlapping peaks based on their homolog composition and then assigning them to their proper Aroclor mixtures. Silica gel fraction 2, which contained most pesticides, was quantified using a Varian® 3700 GCI EC equipped with a Hewlett-Packard® SE-54, 50 m X 0.2 mm ID fused silica capillary column. The conditions were as follows: injection port temperature 220°C, detector temperature 320°C, oven temperature program 100°C-240°C at 1°Imin, carrier gas hydrogen adjusted to a linear velocity of 45 cm/sec, nitrogen make-up gas 30 mL/min. These pesticides were quantified using the external standard method comparing areas of known standard concentration to the identified peaks. Quantification of toxaphene, which consists of a complex mixture of compounds, was performed by comparing specific peaks in a toxaphene standard to peaks in the fish sample. From the standard, 32-38 peaks of the greater than 200 peaks were chosen for comparison, based on base-lined resolution peaks with significant area, and peaks evenly dispersed over the mix. To avoid confusion with technical chlordane, toxaphene standard peaks which overlapped were excluded from the toxaphene match program. The percentage of the peaks matched, versus the number of peaks sought, was calculated. This gave an estimate of the similarity of the material measured to the standard used. Peak matches below 25% were flagged in the reported results as having superfluous subjectivity in making a positive identification for toxaphene in the samples. The remaining 80% of the fraction from the GPC cleanup was directly analyzed for priority pollutants by GC/MS. A Hewlett-Packard® 5993 GC/MS quadrapole system was employed for the analysis. The system was equipped with a 30-m, 0.25-Itm SPB-5 Supelco® fused silica capillary column and a H-P Auto-sampler. The operating conditions were as follows: electron ionization, splitless mode of injection, linear velocity 30 cml sec (carrier gas helium), septum vent 6 mL/min, injection port temperature 250°C, oven temperature program 70°C to 270°C at 2°C/min hold 20 min, scan delay 3 min, mass range 36-450 amu,

ORGANIC PRIORITY POLLUTANTS IN NEARSHORE FISH

301

TABLE 2. Compounds analyzed by gas chromatography/electron capture (GC/EC) and gas chromatographic/mass spectrometry (GC/MS) in fish collected from Lake Michigan and tributary streams, 1983. PCBs & pesticides measured by GC/EC Aroclor 1248 Aroclor 1254 Aroclor 1260 p,p'-DDE p,p'-DOD p,p'-DDT o,p'-DDT Dieldrin Endrin Endosulfan Sulfate I Heptachlor Heptachlor Epoxide a-BHC

{J-BHC )'-BHC Toxaphene Cis-Chlordane Trans-Chlordane Oxy-Chlordane Cis-Nonachlor Trans-Nonachlor Trifluralin Xytron Mirex Methoxychlor Dacthal

Priority pollutants measured by GC/MS Phenol 2,4,6-Trichlorophenol 4-Chloro-3-methylphenol 2-Chlorophenol 2,4-Dichlorophenol 2,4-Dimethylphenol 2-Nitrophenol 4-Nitrophenol 2,4-Dinitrophenol 2-Methyl-4,5-Dinitrophenol Pentachlorophenol Hexachlorobenzene 1,3-Dichlorobenzene 1,2-Dichlorobenzene 1,4-Dichlorobenzene 1,2,4-Trichlorobenzene Dimethylphthalate Diethylphthalate Di-n-butylphthalate Butylbenzylphthalate Bis(2-ethylhexyl)phthalate Di-n-octylphthalate Bis(2-Chloroisopropyl)ether Bis-2-Chloroethylether Bis-2-Chloroehoxymethane 4-Chlorophenylphenylether 4-Bromophenylphenylether

threshold setting 15010, electron voltage 70 eV, electron multiplier voltage 1600 eV. The H-P Batch program automates the GC/MS system by repeatedly acquiring data using the autosampler and processing the raw data. Deuterated phenanthrene (D10) was used as the internal standard for the GC/MS analysis. Compounds are quantified on the basis of a one-mass calibration response, comparing the internal standard response (200 ng) with response of individual compounds. A file was created which incorporated relative retention time and relative response factor, based on selected masses characteristic for each compound of the standard mixture. The H-P Quantid program was then used to search for the internal standard and priority pollutants using the information in the calibrated file to quantify the compounds.

N-Nitrosodimethylamine N-Nitrosodipropylamine N-Nitrosodiphenylamine Nitrobenzene 2,6-Dinitrotoluene 2,4-Dinitrotoluene 1,2-Diphenylhydrazine Naphthalene 2-Chloronaphthalene Acenaphthylene Acenaphthene Fluorene Phenanthrene Pyrene Chrysene Benzo{a)anthracene Benzo(a)pyrene Indene(l,2,3-C,D)pyrene Dibenzo(a,h)anthracene Benzo(g,h,i)perylene Benzo(b)f1uoranthene Benzo(k)f1uoranthene Anthracene F1uoranthene Isophorone Hexachloroethane Hexachlorobutadiene 3,3'-Dichlorobenzidine Hexachlorocyclopentadiene Benzidine

RESULTS AND DISCUSSION The analyses of the 28 nearshore fish samples, 14 sites, 2 species per site, which included PCBs, pesticides, and priority pollutants, are reported in mg/kg wet weight for whole fish composite samples (Tables 3 and 4). Included also is percent lipid in the fish samples. A positive correlation was observed between fat content in fish and the hydrophobic PCBs and chlorinated hydrocarbon pesticides. This was particularly apparent in St. Joseph River common carp, which had the highest percent lipid of the 28 samples analyzed (23.1 %) as well as the highest contaminant levels. These hydrophobic contaminants preferentially partition into the apolar lipid compartments of the fish. Polychlorinated biphenyls were the most significant contaminant and seemed to occur ubiqui-

CAMANZO et al.

302

TABLE 3. PCBs and pesticide concentrations (mg/kg wet weight) in nearshore fish from Lake Michigan, 1983. Replicate samples are reported as the mean value with the standard deviation in parentheses. Location

Species

Aroclor

Aroclor

Aroclor

1248

1254

1260

Total PCBs

Toxaphene

p,p'-DDT

p,p'-DDD & o,p'-DDT

St. Joseph River

common carp smallmouth bass

9.50 0.06*

16.00 2.20

2.10 0.93

27.60 3.19

3.32(0.57) 0.29**(0.05)

0.070 0.057

1.084 0.061

Kalamazoo River

common carp largemouth bass

6.40 2.60

6.80 1.90

0.40 0.26

13.60 4.56

1.17**(0.26) 0.08*

0.004 0.005

0.097 0.032

Grand River

common carp channel catfish

0.02* 0.14(0.01)

1.00 3.40(0.28)

0.24 0.58(0.04)

1.26 4.10(0.35)

0.23** 0.89(0.18)

0.004* 0.047(0.006)

0.035 0.215(0.018)

Muskegon River

common carp pumpkinseed

0.097(0.06) 0.01*

4.27(0.25) 0.09

0.64(0.12) 0.03*

5.01(0.27) 0.13

2.09(0.58) 0.26**

0.029(0.013) 0.003*

0.28(0.18) 0.004

White Lake

common carp bowfin

0.30 0.88

3.00 8.00

0.12* 1.40

3.42 10.28

1.10 1.55

0.010 0.343

0.185 0.332

Pere Marquette River

common carp bowfin

0.04 0.18

1.60 5.30

0.22 1.00

1.86 6.48

1.07 2.86

0.006 0.257

0.150 0.186

Manistee River

common carp bowfin

0.08 0.10

2.70 3.60

0.33 0.97

3.11 4.67

0.81 2.41

0.009 0.331

0.056 0.222

Platte River

common carp northern pike

0.27 0.06*

5.60 1.80

0.60 0.47

6.47 2.33

0.84 0.52*

0.009 0.039

0.210 0.056

Boardman River

smallmouth bass rock bass

0.05 0.02*

0.34 0.26

0.08 0.13

0.47 0.41

0.33** 0.04*

0.014 0.008

0.011 0.004

Grand Traverse Bay

common carp lake trout

0.64 0.07

5.70 1.00

0.36 0.26

6.70 1.33

1.90 1.38

0.020 0.068

0.208 0.081

Manistique River

smallmouth bass northern pike

1.30 0.72

2.10 1.60

0.02 0.07

3.42 2.39

0.98** 1.31**

0.009 0.031

0.007 0.030

Whitefish River

common carp rock bass

3.50 0.01

6.90 0.08

0.24 0.02

10.64 0.11

1.21 0.73**

0.046 0.003*

0.138 0.002

Escanaba River

common carp northern pike

0.76 0.22

3.10 2.40

0.12* 0.30

3.98 2.92

1.52 3.46

0.006 0.093

0.077 0.076

Ford River

northern pike rock bass

0.29 0.04

2.10 0.35

0.13 0.07

2.52 0.46

0.92** 2.40**

0.024 0.110

0.032 0.005

TransNonachlor

Heptachlor

Location

Species

Cisp,p'-DDE Chlordane

TransChlordane

OxyCisChlordane Nonachlor

St. Joseph River

common carp smallmouth bass

9.015 0.141

0.211 0.003

0.019 0.001

0.061 0.016

0.156 0.017

0.399 0.049

0.004 0.001

Kalamazoo River

common carp largemouth bass

0.342 0.247

0.010 0.003*

0.001 0.000005*

0.005 0.003

0.012 0.005

0.028 0.0001*

0.001 0.001

Grand River

common carp channel catfish

0.159 1.74(0.79)

0.008 0.06(0.005)

0.001 0.008(0.0009)

0.002 0.009 0.025(0.002) 0.061(0.003)

0.024 0.163(0.016)

0.001 0.0015*(0.0007)

Muskegon River

common carp pumpkinseed

2.05(0.20) 0.020

0.142(0.08) 0.0002

0.025(0.009) 0.0001

0.031(0.014) 0.122(0.05) 0.003 0.002

0.406(0.197) 0.004

0.002*(0.0006) 0.004

White Lake

common carp bowfin

1.073 3.442

0.015 0.009

0.002 0.005

0.011 0.144

0.020 0.123

0.055 0.351

0.003 0.001*

Pere Marquette River

common carp bowfin

0.856 2.486

0.009 0.013

0.001 0.005

0.008 0.118

0.014 0.106

0.043 0.240

0.001* 0.002 Continued

ORGANIC PRIORITY POLLUTANTS IN NEARSHORE FISH TABLE 3.

303

Continued

Location

Species

CisTransOxyp,p'-DDE Chlordane Chlordane Chlordane

CisNonachlor

TransNonachlor

Heptachlor

Manistee River

common carp bowfin

0.547 2.093

0.008 0.007

0.001 0.004

0.006 0.117

0.014 0.097

0.033 0.299

0.002* 0.001

Platte River

common carp northern pike

2.210 0.913

0.019 0.005

0.003 0.002

0.016 0.015

0.027 0.031

0.071 0.095

0.002 0.001

Boardman River

smallmouth bass rock bass

0.027 0.013

0.001 0.0004

0.0001 0.0001

0.004 0.001

0.005 0.002

0.013 0.005

0.003 0.001*

Grand Traverse Bay

common carp lake trout

1.660 0.542

0.037 0.015

0.005 0.003

0.016 0.016

0.035 0.031

0.080 0.001

0.002* 0.002*

Manistique River

smallmouth bass northern pike

0.052 0.472

0.001 0.005

0.001 0.001

0.011 0.015

0.004 0.016

0.027 0.044

0.003 0.002

Whitefish River

common carp rock bass

0.539 0.014

0.016 0.0002

0.001 0.0001

0.010 0.001

0.QJ8 0.001*

0.044 0.003

0.008 0.001*

Escanaba River

common carp northern pike

0.922 1.120

0.005 0.007

0.001 0.002

0.008 0.024

0.012 0.040

0.032 0.125

0.001 0.003

Ford River

northern pike rock bass

0.920 0.068

0.003 0.00

0.001 0.001

0.014 0.016

0.017 0.004

0.048 0.00

0.002 0.001

Dieldrin

a-BHC

Location

Species

Heptachlor Epoxide

iJ-BHC

'Y- BHC

Trifluralin

Xytron

St. Joseph River

common carp smallmouth bass

0.062 0.0002

0.286 0.048

0.050 0.003

0.001* 0.0003*

0.006 0.001

0.126 0.008

0.012 0.004

Kalamazoo River

common carp largemouth bass

0.001 0.0001 *

0.007 0.034

0.048 0.005

0.001* 0.0003*

0.001 0.0004

0.026 0.011

0.009 0.002

Grand River

common carp channel catfish

0.001 0.017(0.001)

0.006 0.151(0.023)

0.0004* 0.006 0.021(0.002) 0.001 *(0.)

0.001 0.005(0.)

0.015 0.05(0.07)

0.004 0.005*(0.)

Muskegon River

common carp pumpkinseed

0.024(0.01) 0.0003*

0.11(0.055) 0.001*

0.034(0.032) 0.001 *(0.) 0.001* 0.007

0.002*(0.001) 0.001*

0.022(0.02) 0.004

0.039(0.025) 0.007*

White Lake

common carp bowfin

0.002 0.020

0.020 0.205

0.020 0.023

0.001* 0.001*

0.002 0.002*

0.012 0.034

0.005* 0.008*

Pere Marquette River

common carp bowfin

0.003 0.025

0.007 0.237

0.021 0.028

0.001* 0.001*

0.001* 0.002*

0.010 0.021

0.007* 0.069

Manistee River

common carp bowfin

0.003 0.016

0.023 0.123

0.018 0.016

0.001* 0.001*

0.001 0.0004*

0.012 0.018

0.008* 0.026

Platte River

common carp northern pike

0.004 0.002

0.020 0.021

0.038 0.015

0.001* 0.001*

0.002 0.002

0.003 0.004

0.007* 0.007*

Boardman River

smallmouth bass rock bass

0.0003* 0.0003

0.014 0.003*

0.009 0.005

0.001* 0.001*

0.001 0.001*

0.011 0.008

0.007* 0.007*

Grand Traverse Bay

common carp lake trout

0.020 0.020

0.194 0.249

0.060 0.097

0.001* 0.001*

0.003 0.004

0.008 0.011

0.009* 0.034

Manistique River

smallmouth bass northern pike

0.005 0.0003*

0.003* 0.017

0.012 0.007

0.001* 0.001*

0.011 0.001*

0.005 0.006

0.006* 0.008*

Whitefish River

common carp rock bass

0.014 0.0003*

0.048 0.003*

0.058 0.006

0.001* 0.001*

0.002 0.001*

0.008 0.003*

0.009 0.008*

Escanaba River

common carp northern pike

0.003 0.003

0.015 0.013

0.029 0.010

0.001* 0.001*

0.002 0.002

0.068 0.100

0.026 0.006* Continued

304 TABLE 3.

CAMANZO et a/. Continued

Location Ford River

Location

Species

Heptachlor Epoxide

northern pike rock bass

0.00 0.006

Species

Dieldrin

a-BHC

0.014 0.007

0.011 0.018

Mirex

{3-BHC

'Y- BHC

0.001* 0.001*

0.001* 0.026

Trifluralin 0.004 0.055

Xytron 0.008* 0.005*

Methoxychlor

Endrin

Dacthal

Endosulfan I

St. Joseph River

common carp smallmouth bass

0.001* 0.0003*

0.118 0.002*

0.027* 0.027*

0.003* 0.003*

0.002* 0.002*

Kalamazoo River

common carp largemouth bass

0.001* 0.0002*

0.006* 0.001*

0.027* 0.027*

0.003* 0.003*

0.002* 0.002*

Grand River

common carp channel catfish

0.0003* 0.0005*(0.)

0.002* 0.022(0.03)

0.027* 0.027*(0.)

0.003* 0.003*(0.)

0.002* 0.002*(0.)

Muskegon River

common carp pumpkinseed

0.001*(0.) 0.001*

0.01(0.007) 0.005*

0.027*(0.) 0.007*

0.003*(0.) 0.001*

0.002*(0.) 0.0005*

White Lake

common carp bowfin

0.0005* 0.001*

0.004* 0.005*

0.027* 0.027*

0.003* 0.003*

0.002* 0.002*

Pere Marquette River

common carp bowfin

0.001* 0.001*

0.004* 0.004*

0.027* 0.027*

0.003* 0.003*

0.002* 0.002*

Manistee River

common carp bowfin

0.001* 0.0005*

0.005* 0.003*

0.027* 0.027*

0.003* 0.003*

0.002* 0.002*

Platte River

common carp northern pike

0.001* 0.001*

0.029 0.005*

0.027* 0.027*

0.003* 0.003*

0.002* 0.002*

Boardman River

smallmouth bass rock bass

0.001* 0.001*

0.005* 0.005*

0.027* 0.027*

0.003* 0.003*

0.002* 0.002*

Grand Traverse Bay

common carp lake trout

0.001* 0.001*

0.054 0.005*

0.027* 0.027*

0.003* 0.003*

0.002* 0.002*

Manistique River

smallmouth bass northern pike

0.001* 0.001*

0.004* 0.005*

0.027* 0.027*

0.003* 0.003*

0.002* 0.002*

Whitefish River

common carp rock bass

0.001* 0.001*

0.005* 0.005*

0.027* 0.027*

0.003* 0.003*

0.002* 0.002*

Escanaba River

common carp northern pike

0.0004* 0.001*

0.003* 0.004*

0.027* 0.027*

0.003* 0.003*

0.002* 0.002*

Ford River

northern pike rock bass

0.001* 0.0005*

0.028 0.003*

0.027* 0.027·

0.003* 0.003*

0.002* 0.002*

* Below limit of detection. The limit of detection value is reported. ** Less than 25010 of peaks matched to specific standard peaks used for toxaphene quantitation.

tously at the nearshore sites sampled (Fig. 1). Total PCB concentrations from these samples ranged from 0.11 mg/kg to 27.6 mg/kg; the highest concentration was observed in common carp from the St. Joseph River. Other high PCB concentrations were observed in Kalamazoo River common carp (13.6 mg/kg), White Lake bowfin (10.3 mg/kg), and Whitefish River common carp (10.6 mg/kg). Although these results are for whole fish, these

values are well above the USFDA action level of 2 mg/kg total PCBs in edible portion skin-on fillets. All 28 composite fish samples exceeded the International Joint Commission's (IJC) objective of 0.1 mg/kg total PCBs for whole fish (IJC 1978). Of the three Aroclors analyzed, Aroclor 1254 was most often found in highest concentrations. Relatively low total PCB levels, less than 0.5 mg/kg, were found in Muskegon River pumpkinseed,

ORGANIC PRIORITY POLLUTANTS IN NEARSHORE FISH

305

TABLE 4. Concentrations (mg/kg wet weight) of priority pollutants and percent lipids in fish from Lake Michigan tributaries and embayments as determined by gas chromatography-electron capture and gas chromatography-mass spectrometry. Replicate samples are reported as the mean value with the standard deviation in parentheses. Location

Species

Isophorone

Bis (2-ethylhexyl) phthalate

Lipid Phenol

(070 )

St. Joseph River

common carp smallmouth bass

0.* 0.74

0.62 0.*

0.* 0.*

23.1 3.7

Kalamazoo River

common carp largemouth bass

0.12 0.72

0.* 0.*

0.* 0.*

5.9 3.1

Grand River

common carp channel catfish

0.* 0.*

0.* 0.*

0.16 0.06(0.09)

4.0 13.5(0.)

Muskegon River

common carp pumpkinseed

0.94(1.25) 0.40

0.* 0.*

0.02(0.05) 0.*

17.9(1.1) 2.4

White Lake

common carp bowfin

0.66(0.69) 0.*

0.* 0.*

0.* 0.*

15.4(0.) 12.1

Pere Marquette River

common carp bowfin

3.13 0.*

0.* 0.*

0.09 0.*

11.0 13.5

Manistee River

common carp bowfin

0.* 0.76

0.* 0.*

0.* 0.*

10.5 11.5

Platte River

common carp northern pike

2.32 0.*

0.* 0.*

0.* 0.*

14.7 3.5

Boardman River

smallmouth bass rock bass

3.61 1.44

0.* 0.*

0.* 0.*

5.4 3.5

Grand Traverse Bay

common carp lake trout

0.47 2.33

0.* 0.*

0.* 0.*

16.2 18.8

Manistique River

smallmouth bass northern pike

1.03 0.*

0.* 0.*

0.* 0.*

4.5 2.1

Whitefish River

common carp rock bass

0.88 0.69

0.* 0.*

0.* 0.*

16.4 3.0

Escanaba River

common carp northern pike

0.41 0.48

0.* 0.94

0.* 0.*

12.9 2.9

Ford River

northern pike rock bass

0.* 0.*

0.* 0.49

0.* 0.*

3.0 3.1

* Not detected.

Boardman River rockbass and smallmouth bass, Whitefish River rockbass, and Ford River rockbass. Total PCBs were highest (27.6 mg/kg) in common carp from the St. Joseph River and second highest (13.6 mg/kg) in common carp from the Kalamazoo River. Rohrer et al. (1982) reported total PCBs for coho salmon (Oncorhynchus

kisutch) and chinook salmon (Oncorhynchus tschawytscha) fillets from the St. Joseph River (8.2 mg/kg and 4.4 mg/kg, respectively) to be the highest of the Great Lakes sites they studied. Horvath and Greminger (1982) reported a mean PCB concentration of 4.5 mg/kg (range: 0.1-47.0 mg/kg) for 69 common carp collected from the Kalamazoo

306

CAMANZO et al.

River in 1981, which is lower than levels (13.6 mg/ kg) we recorded in 1983. Polychlorinated biphenyls are a group of compounds used previously in a diverse number of industrial applications. Some of the major uses have been in fire-resistant hydraulic and heattransfer fluids, insulation in electrical transformers and capacitors, carbonless copy paper, and as plasticizers (Kimbrough 1980). Due to government restricted use of PCBs for closed systems only, and Monsanto Chemical Company's reduced production in the 1970s, the level of PCB contamination in fish has been declining over the past 10 years. This decline has been described as a first-order loss kinetics for Great Lakes lake trout (DeVault et al. 1985). The continued existence of PCB contamination in fish reflects continued availability to the food chain due to slow biodegradation of PCBs, PCB contamination in the sediments, and atmospheric deposition. The pesticide DDT, which was banned in the U.S. in the 1970s, and its metabolic products (e.g., DDE and DDD) were also present in all samples analyzed. The concentration of DDT residue (DDTr), which includes DDE and DDD, ranged from approximately 0.03 mg/kg to 10.2 mg/kg with the highest concentrations again occurring in St. Joseph River common carp. DDTr exceeded the IJC objective of 1.0 mg/kg in 50% of the samples. High levels of DDTr, greater than 2.5 mg/kg, were also found in Grand River channel catfish, Muskegon River common carp, White Lake bowfin, Pere Marquette River bowfin, and Manistee River bowfin. The lowest levels of DDT and metabolites (less than 0.7 mg/kg) were present in Muskegon River pumpkinseed, Boardman River rockbass and smallmouth bass, Manistique River smallmouth bass, and Whitefish River rockbass. Nearly all DDT residue detected was p,p'-DDE, a highly stable metabolite formed by dehydrochlorination of the trichloroethylene moiety (Keil and Priester 1969). Toxaphene, a complex mixture, was also analyzed, and a range of 0.04 mg/kg to 3.72 mg/kg was observed, with the highest concentration occurring in a replicate sample from St. Joseph River common carp. Samples also having high toxaphene concentrations were Escanaba River northern pike (3.46 mg/kg), Pere Marquette River bowfin (2.86 mg/kg), a replicate from Muskegon River common carp (2.51 mg/kg), Manistee River bowfin (2.41 mg/kg), and Ford River rock bass (2.40 mg/kg). Toxaphene has traditionally been used as

an insecticide for cotton plants in the cotton belt region, which includes areas in the southeast, midsouth, and southwest United States. Because comparatively little toxaphene has been used in the Great Lakes watershed, atmostpheric transport from areas in the south and southwest U.S. offer the most cogent explanation for the accumulation of these residues in the upper lakes (Rice et al. 1984), an explanation which has also been postulated for other contaminants (Eisenreich et al. 1981). The technical chlordane components including cis-, trans-, oxy-chlordane, and cis-, transnonachlor were also analyzed; St. Joseph River and Muskegon River common carp had the highest concentrations. Technical chlordane, including its various components, found in common carp from these sites reached levels of 0.85 mg/kg and 0.87 mg/kg, respectively. Technical chlordane contamination ranged from approximately 0.01 mg/kg to 0.87 mg/kg. Elevated technical chlordane concentrations were also observed in White Lake and Manistee River bowfin, which contained approximately 0.52 mg/kg and 0.62 mg/kg, respectively. Heptachlor and heptachlor epoxide were not substantial contributors to the pesticide contamination at the sites studied. Concentrations in fish ranged from below the limit of detection to 0.06 mg/kg, the highest being heptachlor epoxide in St. Joseph River common carp. The concentration of dieldrin residue, which was banned in Michigan in 1974, ranged from 0.001 mg/kg to 0.29 mg/kg, with the highest concentration occurring in St. Joseph River common carp. Elevated levels of dieldrin were also found in Grand Traverse Bay lake trout, Pere Marquette River bowfin, and White Lake bowfin (0.25, 0.24, and 0.21 mg/kg, respectively). The pesticide alphabenzene hexachloride (BHC) ranged from 0.001 to 0.10 mg/kg, with the highest concentration occurring in Grand Traverse Bay lake trout. The {3- and ')'-BHC isomers generally occurred below detection criterion, with the exception of Ford River smallmouth bass which had a {3-BHC concentration of 0.03 mg/kg. Trifluralin concentrations ranged from 0.003 to 0.13 mg/kg, with the highest levels occurring in St. Joseph River common carp. Escanaba River northern pike and common carp also contained relatively high trifluralin concentrations, 0.10 mg/kg and 0.068 mg/kg, respectively. The pesticide xytron occurred in concentrations less than 0.07 mg/kg; the highest was in Pere Marquette River bowfin (0.069 mg/kg). The com-

ORGANIC PRIORITY POLLUTANTS IN NEARSHORE FISH pound methoxychlor, which has a structure similar to DDT, is a popular substitute for DDT. It was present in low concentrations (less than 0.06 mg/ kg), with the exception again being St. Joseph River common carp (0.12 mg/kg). The remaining pesticides analyzed, which included mirex, endrin, dactal, and endosulfan I, occurred at levels below detection criterion. The results of the priority pollutants analyses, quantified by GC/MS using the internal standard method (Table 4) showed that of contaminants on the USEPA priority pollutant list, only three were detected: isophorone, bis(2-ethylhexyl) phthalate, and phenol. Isophorone concentrations ranged from not detected to 3.61 mg/kg in Boardman River smallmouth bass. Other fish samples with elevated isophorone levels were one of the replicate samples from Muskegon River common carp (3.34 mg/kg) and Pere Marquette River common carp (3.13 mg/kg). Bis(2-ethylhexyl) phthalate was present in three samples at levels higher than detection criterion; they included Escanaba River northern pike, St. Joseph River common carp, and Ford River rock bass (0.94, 0.62, and 0.49 mg/kg, respectively). This phthalate ester is produced at the rate of 180 million kg/yr and is used mainly as a plasticizer (Tinsley 1979). Because of the wide distribution of plastics, phthalates are commonly released into the environment and have been detected in a wide variety of environmental samples. Phenol concentrations ranged from below detection criterion to 0.16 mg/kg, with the highest occurring in Grand River common carp. These levels were relatively inconsequential compared with other priority pollutants. CONCLUSION These fish contaminant data illustrate the environmental persistence in the Great Lakes of banned or restricted industrial pollutants and pesticides such as PCBs, DDT, chlordane, and dieldrin. The occurrence of currently used organochlorine pesticides was also documented in fish from the nearshore sites studied. There is a strong correlation between sites of industrial and agricultural development and contaminants found in resident fish. The St. Joseph River flows through a heavily industrialized and well developed farming area and contained fish with the highest contaminant levels among rivers sampled. Elevated concentrations of PCBs, DDT residues, toxaphene, chlordane, dieldrin, and methoxychlor were observed in com-

307

mon carp from this river. Fish from the Kalamazoo River, which passes through an industrialized city, also contained elevated levels of PCBs from past paper mill discharges, while pesticide levels were negligible. Fish from White Lake contained elevated levels of both PCBs and pesticides. The Grand River, Muskegon River, Pere Marquette River, Manistee River, and Platt River contained fish with moderate levels of PCBs and pesticides. The Boardman River, which flows through Traverse City, Michigan, had the least contaminated fish of any examined during the study. Grand Traverse Bay fish showed low pesticide contamination with moderate PCB residues. Fish from Upper Peninsula tributaries, including the Ford River, Escanaba River, Manistique River, and Whitefish River, were substantially less contaminated than lower peninsula fish, which is a reflection of the more pristine environment there. One exception was Whitefish River fish which contained elevated levels of total PCBs. Bottom-feeding species had dramatically higher levels of contamination when compared with benthivores and predators. One of the reasons which can account for these facts is that the bottomfeeding species (common carp, channel catfish) were generally older fish having a longer exposure time to bio-accumulate contaminants. They were also usually fatter fish than the other species examined in this study, with the possible exception of lake trout. In the Whitefish River, common carp contained levels of PCBs two orders of magnitude higher than rock bass. Organochlorine hydrocarbon compounds readily partition in the sediment by adsorbing onto organic or inorganic particulate matter, thereby making the hydrophobic contaminants more accessible to the food chain of bottomfeeding species. Based on available data and FDA action levels (2 mg/kg for PCBs), the Michigan Department of Public Health has issued a health advisory on common carp from the lower reaches of the St. Joseph, Kalamazoo, and Manistique rivers because of excessive levels of PCBs. Our data support this action and suggest consideration be given to adding health advisories on common carp for the lower reaches of the Grand, Muskegon, Pere Marquette, Manistee, Platte, and Whitefish rivers, and White Lake and Grand Traverse Bay. In addition, our data suggest that the Kalamazoo River is an important source of PCBs, that heavy loads may be reaching Lake Michigan, and that consideration

CAMANZO et al.

308

be given to classifying the river as an IJC "area of concern." The Lake Michigan tributary sites with fish containing elevated levels of contamination are potential sources of contamination to the Great Lakes. These data indicate that a potential for human exposure and adverse effects on the overall ecosystems of Lake Michigan exists. Continued monitoring combined with stricter government regulation of industrial and agricultural contaminants are essential to protecting public and environmental health. Fish advisories can be implemented only with adequate fish contaminant data. ACKNOWLEDGMENTS

We would like to extend our thanks to Scott DeBoe, Phil Hirt, Janet Huhn, Pamela Mansfield, Laura Noguchi, and Frank Tesar for their care and perseverance in the collection of fish. Phil Hirt and Janet Huhn ground up all the fish. We gratefully acknowledge the cooperation extended us by Robert Hesselberg, USFWS, National Fisheries Center-Great Lakes, who gave permission and advice on use of their grinding machine. We express our appreciation to George Noguchi for his work in preparing and analyzing the fish samples. John Hartig reviewed the manuscript and provided useful suggestions. Marion Luckhardt is thanked for manuscript processing. This project was funded through a grant from the Great Lakes National Program Office, U.S. Environmental Protection Agency, Grant R005736-01. Contribution No. 461 of the Great Lakes Research Division, The University of Michigan. REFERENCES Bidleman, T. F., Rice, C. P., and Olney, C. E. 1977. High molecular weight hydrocarbons in the air and sea: rates and mechanisms of air/sea transfer. In Marine Pollutant Transfer, ed. H. L. Windom and R. A. Duce, pp. 323-331. Lexington: Lexington Books. Clark, J. R., DeVault, D., Bowden, R. J., and Weishaar, J. A. 1984. Contaminant analysis of fillets from Great Lakes coho salmon, 1980. J. Great Lakes Res. 10:38-47. DeVault, D. S. 1984a. Contaminants in fish from Great Lakes harbors and tributary mouths 1980-81. U.S. Environmental Protection Agency. EPA 905/3-84003. Great Lakes National Program Office, Chicago, Illinois.

DeVault, D. S. 1984b. Polychlorinated dioxins and polychlorinated furans in fish from the Great Lakes and Midwest. U.S. Environmental Protection Agency. EPA/3-84-006. Great Lakes National Program Office, Chicago, Illinois. ____ , and Weishaar, J. A. 1983. Contaminant analysis of 1981 fall run coho salmon (Oncorhynchus kisutch). U.S. Environmental Protection Agency. EPA 905/3-83-001. Great Lakes National Program Office, Chicago, Illinois. ____ , Willford, W. A., and Hesselberg, R. J. 1985. Contaminant trends in lake trout (Salvelinus namaycush) of the Upper Great Lakes. U.S. Environmental Protection Agency. EPA 905/3-85-001. Great Lakes National Program Office, Chicago, Illinois. Eisenreich, S. J., Looney, B. B., and Thornton, J. D. 1981. Airborne organic contaminants in the Great Lakes ecosystem. Environ. Sci. Technol. 15:30-38. Hesse, J. L. 1975. Contaminants in Great Lakes fish. Staff report by Michigan Water Resources Commission, Department of Natural Resources, Environmental Protection Branch, Bureau of Water Management, Lansing, Michigan. Hesselberg, R. J., and Seelye, J. G. 1982. Identification of organic compounds in Great Lakes fishes by GC/ MS; 1977. Administrative Report No. 82-1, Great Lakes Fishery Laboratory, U.S. Fish and Wildlife Service, Ann Arbor, Michigan. Holden, A. V. 1970. International cooperative study of organochlorine pesticide residues in terrestrial and aquatic wildlife, 1967/1968. Pest. Monit. J. 4:117-135. Horvath, F. J., and Greminger, J. E. 1982. Contaminants in Kalamazoo River fish. Michigan Department of Natural Resources, Publication No. 37300042. Lansing, Michigan. Humphrey, H. E. B. 1975. Evaluation of changes of the level of polychlorinated biphenyls (PCB) in human tissue. Final Report on FDA Contract 223-73-2209. Mich. Dept. of Public Health. ____ . 1985. Michigan sport-fish consumption advisories, philosophy and procedures. Report by Michigan Department of Public Health, Lansing, Michigan. International Joint Commission. 1978. Status report on the persistent toxic pollutants in the Lake Ontario basin. Great Lakes Water Quality Board, Windsor, Ontario, Canada. Jaffe, R., Stemmler, E. A., Eitzer, B. D., and Hites, R. A. 1985. Anthropogenic, polyhalogenated, organic compounds in sedentary fish from Lake Huron and Lake Superior tributaries and embayments. J. Great Lakes Res. 11: 156-162. Keil, J. E., and Preister, L. E. 1969. DDT uptake and metabolism by a marine diatom. Bull. Environ. Contam. Toxicol. 3: 169-171.

ORGANIC PRIORITY POLLUTANTS IN NEARSHORE FISH Kimbrough, R. D. 1980. Topics in Environmental Health. IV. Halogenated Biphenyls, Terphenyls,

Napthalenes, Dibenzodioxins and Related Products. New York: Elsevier/North-Holland Biomedical Press. Kuehl, D. W. 1981. Unusual polyhalogenated chemical residues identified in fish tissue from the environment. Chemosphere 10:231-242. _ _ _ _ , Leonard, E. N., Butterworth, B. c., and Johnson, K. L. 1983. Polychlorinated chemical residues in fish from major watersheds near the Great Lakes, 1979. In Environmental International, Vol. 9, pp. 293-299. Kuehl, D. W., Kopperman, H. L., Veith, G. D., and Glass, G. E. 1976. Isolation and identification of polychlorinated styrenes in Great Lakes Fish. Bull. Environ. Con tam. Toxicol. 16: 127-132. Miller, T. J., and Jude, D. 1984. Organochlorine pesticides, PBB, and mercury in round whitefish fillets from Saginaw Bay, Lake Huron, 1977-1978. J. Great Lakes Res. 10:215-220. Oliver, B. G., and Nicol, K. D. 1982. Chlorobenzenes in sediments, water, and selected fish from Lakes Superior, Huron, Erie, and Ontario. Environ. Sci. Technolo 16:532-536. Rice, C. P., Samson, P. J., and Noguchi, G. 1984.

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Sawyer, Leon D. 1978. Quantitation of Polychlorinated Biphenyl residues by electron capture gas liquid chromatography: Reference material characterization and preliminary study. J. Assoc. Chem. 61 :272-281. Schmitt, C. J., Ludke, J. L., and Walsh, D. F. 1981. Organochlorine residues in fish: National Pesticide Monitoring Program, 1970-1974. Pest. Monit. J. 14: 136-208. Tinsley, I. J. 1979. Chemical Concepts in Pollutant Behavior. New York: John Wiley & Sons. p. 114. U.S. Environmental Protection Agency. 1979a. Water related environmental fate of 129 priority pollutants. Volume 1. EPA-440/4-79-029a. _ _ _ _ . 1979b. Standard operating procedure:

Analysis of non-volatile extractable organic compounds: Sample extraction and screening by gas chromatography. Method 625. U.S. Environmental Protection Agency. Federal Register 44:223. Veith, G. D. 1975. Baseline Concentrations of Polychlorinated biphenyls and DDT in Lake Michigan fish, 1971. Pest. Monit. J. 9:21-29 _ _ _ _ , Kuehl, D. W., Leonard, E. N., Welch, K., and Pratt, G. 1981. Polychlorinated biphenyls and other organic chemical residues in fish from major United States watersheds near the Great Lakes, 1978. Pest. Monit. J. 15:1-8. Willford, W. A., Bergstedt, R. A., Berline, W. H., Foster, N. R., Hesselberg, R. A., Mac, M. J., Passino, D. R. M., Reinert, R. E., and Rottiers, D. V. 1981. Introduction and Summary. In Chlorinated Hydro-

carbons as a Factor in the Reproduction and Survival of Lake Trout (Salvelinus namaycush) in Lake Michigan, pp. 1-7. U.S. Fish and Wildlife Service Technical Paper 105.