Document pexpd2ON0dwqOpVbypZ03xn37

Li** , .. . ,.x.- >;-> -r"`-T':'"*' "** *". ,...m Uiv-^i^'^faiT.'iJuiL. .-'ruiKiiM i..l.v.^rt!iii ^'--:r<y-r" IgC zCdi--7ti. a- .pA^> ; ' X Baseline Concentrations of Polychlorinated Biphenyls and DDT in Lake Michigan Fish, 1971 1 Gilman D. Veith - ABSTRACT Responding lo the recommendations of the Lake Michigan Interstate Pesticide Committee, the author aimed lo estab lish baseline data on polychlorinated biphenyls (PCB's) and DDT in Lake Michigan fish in 1971. Because the past 2 years had witnessed unprecedented legislative action to pro tect food resources and other aquatic species near the top of the food chain from persistent hazardous chemicals, the author also attempted to gauge the impact of cooperative legislative action on the quality of large takes. Thirteen species of fish taken from 14 regions of Lake Michigan in the fall of 197! were analyzed for PCB's and DDT analogs. Mean wet-weight concentrations of PCB's similar to Aroclor 1254 ranged from 2.7 ppm in rainbow smell to 15 ppm in lake trout. Most trout and salmon longer than 12 inches contained PCB's at concentrations greater than the tolerance level of 5 ppm established by the Food and Drug Administration. U.S. Department of Health, Edu cation, and Welfare. Mean concentrations of total DDT ranged from less than 1 ppm in suckers to approximately 16 ppm in large lake trout. The presence of the major chlorin ated hydrocarbons was confirmed by gas-liquid chromatog raphy/mass spectrometry; additional PCB confirmations were obtained through perchlorinatlon. The most abundant PCB's were terra-, penta-, hexa-, and heptachlorohiphenyls which are similar to commercially prepared Aroclor 1254; lesser chlorinated PCB's were present In fish from nearshore waters. > Supported by U.S. Environmental Protection Atcncy Project 16020 nnn. University Engineering Experiment Station, and Univer*Uy of Wincomln Department of Civil and Environmental Engineering, Madison, Wls. 'National Water Quality laboratory, U.S. Environmental Protection Apency, 6201 Concdon Boulesard, Duluth, Minn. 53*04. Vot.. 9, No. 1, June 1975 Introduction This paper identifies and quantifies the most abundant organochlorinc compounds, particularly polychlorinated biphenyls (PCB's) and DDT, in Lake Michigan fish in 1971, By establishing data on PCB's and DDT in Lake Michigan fish as recommended by the Lake Michigan Interstate Pesticide Committee, the author of the pres ent study aimed to develop a 1971 baseline to predict trends of these chemicals in the lake. Lake Michigan contains much higher concentrations of potentially hazardous and persistent organic chemicals than (he other Great Lakes, in part because of their widespread usage in the watershed and their disp-oportionally brief flushing period and low biomass density. Previous stud ies have shown that fish from Lake Michigan approach the action levels for dieldrin set by the Food and Drug Administration (FDA), U.S. Department of Health. Education, and Welfare (7); a major percentage of Lake Michigan fish exceeded the 5 ppm action level for DDT in 1969 (2). Similarly. Veith (J) has shown that PCB concentrations similar lo Aroclor 1254 were greater than 15 ppm or th ee times the FDA action level in large fish captured from Lake Michigan in 1969. Despite the comparatively high levels of DDT. dieldrin, and PCB's in Lake Michigan, there is no unequivocal evidence that they arc endangering aquatic life. Concen trations of these chemicals appear to be below 10 parts per trillion (ppt) in the pelagic water and less than 100 ppt in nearshore waters. However, considerable in direct evidence suggests that the buildup of organochlorine compounds may threaten biological resources of the lake. Other reports have reviewed the chronic 1 ox icily of pesticides and PCB's (4-7). DSh 026071 '. L-O.'.: 2 i ' F-C * V l STLCOPCB4010033 ill Mi ii'jitif'Ufafrrf, r v. v: -/--.r **.*':77C^'7T r~ '^~T '* S . k* **. >> - . A^Vri, fej WmMs:4i *A$T'>.V;'.rCv'-.^+t" '<; St '<i <rv- ' \J *.*c,,W''; -W ; . feu ffi. w ffe` ] 'i ^ w :***'V/I /^Vv- i v.. > j ;|^.f}y /Ur; s:,^ IP $f3j 'J,:) .;* s4 ft:! Stales surrounding Lake Michigan have made a major effort to restock the lake with brown, lake, and rain bow trout and coho and chinook salmon, Between 196.1 and 1970. over 600.U00 rainbow trout were released by Wisconsin alone (8,9). However, Rcinert (2) previous ly noted that DDT and dieldrin levels in eggs of these fish tire similar to concentrations which inhibited repro duction in the studies of Burdick et al. (10) and Mncek (II). Johansson et al. (13) have shown that 15 ppm PCB's (lipid basis) in salmon eggs produced mortality in 50 percent of the samples tested. Death can be ex pected in all eggs when the PC8 lipid content reaches 25 ppm. Although continued stocking of fish may maintain a food resource, many fish contain residue body burdens which make them unfit for consumption. The effect of these fish on mink production in the North Central States has been studied in detail: before DDT and dieldrin concentrations in these fish had been well docu mented, Harlsough (13) indicated that the fish were suspected to inhibit mink reproduction; Atilerich et al. (14) clearly demonstrated that the fish had been the cause of the minks' reproductive failure; and Aulerich and Ringer (IS) reported that DDT and DDD did not have significant adverse effects on mink. Furthermore, dieldrin was lethal to mink at 2.5 ppm in the food when fed for extended periods, but did not appear to affect reproduction at twice this concentration during the ges tation period. Aulerich et al. concluded that feeding coho salmon to mink did not cause reproduction prob lems, but that the disorder is associated with other species of fish and . . appears to be dependent upon the species of fish and its environment" (16). Finally, after the earlier reports that PCB's were present in Lake Michigan fish, Ringer et al. (17) demonstrated that 10 ppm Aroclor 1254 in coho salmon produced 71 per cent mortality in mink and that a mixture of 10 ppm PCB's and 0.5 ppm dieldrin in coho feed produced 100 percent mortality. No kits were born alive when the diet contained 5 ppm or more Aroclor 1254 alone. This clearly indicates that biological resources of Lake Michigan may seriously endanger other species even though concentrations of toxicants are not severe enough to produce readily discernible effects within the aquatic communities. Equally important is the coincidence of high chlori nated hydrocarbon levels in herring gull and other bird populatons coupled with reproductive failures and sub sequent population decline (18). Anderson (19) found that the eggs of the Great Lakes herring gull contained the highest chlorinated hydrocarbon levels ever re ported for that species. He also found that the degree of eggshell thinning in the Lake Michigan gull, whose population declined dramatically in the eariy 1960's, varied from 9 percent in 1957-56 to 18 percent in 1965. In comparison, eggs of gulls on Lake Huron and Lake Superior have exhibited shell thinning of 7 percent and 8 percent, respectively, and those from gulls on the East Coast have remained essentially unchanged. Double- crested cormorants from Wisconsin had eggshells 20 percent thinner than those of gulls, and their eggs had the highest DDE concentrations of any cormorant eggs sampled from interior North America. Golden eagles, which feed primarily on mammals, do not show eggshell thinning as dramatic as that of bald eagles, which feed on fish (19). . Lake Michigan is the only Great Lakes watershed where major persistent chemicals have been curtailed. Al though use of chlorinated pesticides in agriculture was probably diminishing in the late I960`s, the Lake Michi gan Enforcement Conference recommended regulator) actions on many uses in 1968. This recommendation led to restrictions on DDT including its sale in Illinois. Michigan, and Wisconsin. A more detailed summary is presented by Lueschow (20). Monsanto Company, the sole producer of PCB's in the United States, restricted PCB sales in 1970; by April 1971 they were sold only to close-system users. To measure the impact of the unprecedented coopera tive legislative action regarding these chemicals, and to establish baseline data, the Lake Michigan Interstate Pesticide Committee recommended that this study be funded. Sampling Procedures Fish were collected in September and October 1971 with gill nets and pond nets from the four regions of Lake Michigan outlined in Figure 1. Whole fish were stored frozen ( -- 20' C) in aluminum foil or polyethy lene bags for 60 days or less and homogenized while frozen by repeatedly passing them through a meat grinder. All metal surfaces were rinsed with acetone, polyethylene bags were examined for interferences, and the grinder hearing and seal were checked periodically to assure that the sample was not contaminated during storage or preparation. Analytical Procedures REAGENTS Sodium sulfate (Fisher Scientific Co.) was washed with three volumes of 1:1 hexane-acetone and dried at 130 C. To prevent further contamination from cap liners or containers, the Na^S04 was stored tn large glass bottles with aluminum foil liners in the cap. The florisil (Kensington Chemical, Fisher Scientific Co.) was extracted in an all-glass Suxhlet extractor for 24 hours with the azeotrope of hexane and acetone to re move traces of organic impurities. The solvent was evaporated from the florisil at 100 C, and the solid was heated at 650 C for 2.5 hours for activation. If not used immediately after heating, the florisil was heated to 105' C before use. 22 __ DSW 026072 Pesticides Monitoring Journal STLCOPCB4010034 detectors (Of. 250 me). Columns were 2.0-m-by. 1 .finttu-ID glass coils packed with .2 percent OV-Hj) un 1 20/ 140-mcsh Gas-Chrom Q. The carrier gas. purified NT. was maintained at 20 ml.'min: the injector, column, and detector temperatures were 240'. ISO*, and 220 C. respectively. Chromatograms were recorded on a Varian model A-25 dual pen recorder. Previous work (21) showed that fish from Lake Michi gan contain mixtures of PCB's that closely resemble tbc Aroclor 1254 produced by Monsanto Companv, al though PCB's both lieavicr and lighter than those most abundant in Aroclor 1254 were also present. The fish extracts contain predominantly those PCB's u-hich elute at 70. 84. a doublet of 98 and 104. 125. 146. and 176: peak height of p.p'-DDE is represented here as 100 (Fig. 2). The presence of DDE precluded the use of the 98 and 104, PCB component in the quantita tion. and PCB's based on Aroclor 1254 were deter mined by summing the heights of the 70. 84. 125, 146, and 174 PCB components when peak height of DDE is 100. This method also decreased the effect of minor compositional variations on the analytical result. r", T:\..l 1> . .' f .Ar * . ' ' Mm', C '':. ' FIGURE 1. Sampling regions for collecting fish, Lake Michigan--1971 Other analytical components included: Silicic acid: Hexane: Acetone: Ethyl ether and methylene chloride: Glau wool. Glassware: Mallinckrodl Chemical. Alt grade, Ramsey and Patterson. Used directly from reagent bottle. Sketly D. Redistilled in glass from DriSodlum, Fisher Scientific Co. Fisher Scientific Co.. MCB. Redis tilled In class from Dri-Sodlum, Fisher Scientific Co. MaMInckrodi Chemical. Pesticide-Dual ity solvents. Used directly from re agent bottle after periodic checks showed no interferences. Soaked in acetone, rinsed with 1*1 acetonerheasne mixture. Wished thoroughly with hot detergent; rinsed once with hot water, twice with distilled water, again with 1:1 mixture of redistilled acetone:hexane. preparation oi samples Procedures lo extract and remove the bulk of the lipids have been described previously (21). Because of the high relative concentration of p.p`-DDE in Lake Michigan fish. DDE was quantitated directly by dilut ing 10 percent of the nonpolar florisil eluatc to the appropriate volume for gas-liquid chromatographic (GI.C) analysis. PCB's were separated from TDE and DDT isomers with a modified Armour and Burke pro cedure which omitted Celitc 545 (22). Quantitative gas chromatographic analyses were con ducted on an Aerograph 1745-20 gas chromatograph equipped with dual conccntric-tuhc electron-capture Vol. 9, No. 1, June 1975 - MITCMriOM VOlUtfC L FIGURE 2. Chromatograms of PCB ntixiurts in Aroclor 1254 and fish from Lake Michigan DSW 026073 r,y 11> yyi m wpS5T t >Tr\r ."yr- . . ' r ,* m *" . ' n f' -U - . * .' . ' a % '-U -k>` *T-` ; '-U- *V i'* *' ' -4-1 i. . lx -IN'-.. . .A*.- .tM U; v- i' '.v. r' f jr ,- . STLCOPCB4010035 U I, l.iut* ^1-*- '...-A..*J^tL-U- V-Wl <'.^111 t---i*J^-`l .AInr,11 i "S-S--- '^a` in n nil ! 7i; V.-,y "V1'1 'V ` ; ' f . . 'A-.- ' Recovery of PCB's from fish tissue averaged 85.1 :+ 4.3 percent, whereas recovery of DDE was greater than 90 percent. The precision of the method outlined above is summarized in Table 1, which lists means and stan dard deviations of the analyses of six replicates of sev eral fish species for PCB's, DDT, and lipids. The stan dard deviation for PCB analyses ranged from 5 percent in smaller fish to 14 percent in large coho salmon. The decrease in precision in analyses of large coho resulted from the difficulty of homogenizing larger fish. Pre cision was poorest in DDT analyses, where the standard deviation ranged from 8 to 23 percent with a mean of approximately 14 percent. This reduced precision re sults from losses during silicic acid chromatography which is used to quantitate the TDE and DDT isomers. The precision of DDE analyses was greater than those for DDT analyses, which was anticipated because of the fewer manipulations of the extracts. The standard deviation ranged front 7 to 18 percent, but the average deviation was approximately 10 percent. Because of the relatively simple procedure, lipid analyses were most precise, exhibiting standard deviations from 5 to 7 percent. TABLE I. Precision of chlorinated hydrocarbon determinations for PCB's, DDE, DDT, and lipids In selected fish, Lake Michigan--1971 Specie* No. JU.PLI- Aroclor CATES 1254 p.p'-DDE p.p'-DDT Lipid, % Coho salmon (25 in.) Coho salmor (27 In.) Whllefish 031n.) Bloater (10 In.) AJcwKe (8 In., composite) 6 6 6 6 6 15.2+2.2 13.1+1.3 4. 1+0.2 5.7+0.4 4.0+0.2 7.5 + 0-6 3.5+0.4 0.35+0.04 3.4+0.3 1.1+0.2 3.2+0.6 1.8+0.4 0,56 0.04 2.2+0.3 4.2+0,2 10.0+0,6 16.2+0.9 18.21.3 1.0+0.2 5.7+0.3 NOTH. In columns 3-6, first number represents mean, second repre sents stendurtl deviation. Residues are ppm wet weight. The determinable limit for PCB analysis was approxi mately 0.1 ppm; limits for p,p`-DDT. o.p'-DDT, p,p`TDE, and p,p'-DDE were approximately 0.05 ppm. CONFIRMATION OP MAJOR COMPONENTS Major components of Lake Michigan fish extracts were characterized for a limited number of composite sam ples by standard gas-liquid chromatography/mass spec trometry techniques. In addition, the presence of PCB's in samples from each collection area was confirmed by perchlorinalion of PCB's to decachlorobiphenyl and subsequent analysis of the product by GLC (23). Ali quots of the hexane fraction of silicic acid columns were evaporated to dryness in a 5-mI vial fitted with a teflon-lined screw cap. Antimony pentachloride (0.2 ml) was added to the residue, and the vial was sealed and held at 180"C for 6 hours. Approximately I ml 6N MCI was added to the products to remove the SbCland the solution was extracted with five 1 -ml hexane portions. The hexane was passed through a disposable pipette containing anhydrous Na.^SOj to remove traces of the aqueous solution. The sample was collected in a graduated centrifuge tube and diluted to the proper volume for GLC analysis. This technique also provided semiquantitative information for PCB's to supplement direct GLC analysis of the extracts. For those samples which contained PCB's similar to Aroclor 1254, esti mates of total PCB's by perchlorinalion were within 1 5 percent of direct GLC analysis. Results and Discussion Approximately 850 fish were analyzed for PCB mix tures most closely resembling Aroclor 1254; a summary is presenled in Table 2. Mean concentrations ranged from 2.7 ppm in smelt to 15.5 ppm in lake trout. Larger fish, such as brown, lake, and rainbow trout and Chinook and coho salmon, contained PCB's at mean concentrations two to three times the 5 ppm action level established by FDA (/). Mean PCB concentrations in redhorse suckers, smelt, and whitefish were con siderably less than 5 ppm. Mean concentrations in the alewife, carp, chub, and yellow perch were approxi mately 5 ppm; the range was 4.2-6.0 ppm. As expected. PCB levels increased with the percentage of fat and size of fish. In Lake Michigan fish the mean concentration of total DDT, the sum of p,p'-DDT, o,p -DDT, p,p'-TDE, and p.p'-DDE, ranged from 0.9 ppm in carp to 7.1 ppm in lake trout (Table 2). As with PCB's, fish with higher lipid concentrations contained greater concentrations of DDT. The ratio of PCB's to total DDT ranged from 1.3 in redhorse suckers caught primarily in the northern waters to 7.6 in carp. The ratio of PCB's to DDT in the ma jority of the fish was between 1.7 and 2.8, and only in the carp, redhorse, yellow perch, and while sucker did the ratios fall outside this range. This ratio may become important in future studies to determine the rates at which the chemicals are eliminated from the Lake Michigan system. Mean ratios of o,p-DDT to p,p'-DDT ranged from 0.1 to 0.3; this ratio in the majority of the fish was 0.2. Since technical DDT generally contains about 30 per cent of the o.p'-DDT isomer (ratio, 0.4), data from Lake Michigan fish suggest that degradation, other re moval mechanisms, or both in the lake are slightly greater for the o.p' isomer than for the p,p' isomer. More than 80 percent of the total DDT residue is accounted for by p,p`-DDE and p,p'-DDT. Not only did PCB concentrations vary considerably among the 13 species captured, but the range of PCB concentrations in a single lake species was generally 24 Pesticides Monitokinc Journal DSW 026074 . -- -- ' i i --W--DWIII ^WUl'i'IIM STLCOPCB4010036 greater lhan 100 pcrecnt. The coiuentration range in red buckc;s .is less, hut all were capUued in the same region oi the lake. Although some variation in concen trations is expected because of the notnial analytical error, the much larger ranges in Table 2 are undoubt edly due to other factors that limit usefulness of Ihc mean concentrations presented. Previous research has shown that the lipid content, size of fish, season of cap ture. and concentration in the water mav affect con siderably the observed concentration of chlorinated hydrocarbons in (issue (2). CHLOROBIPHENYLS Reg:onal variation in PCB concentrations and variations due to lipid conlent for each species are shown in Table 3. The wet-weight concentration of PCB's in alc- TABLE 1. Major chlorocarbons in fish. Lake Michigan--/977 Species ' AJewife Hloalcr Brown trout Carp Chinook salmon Coho ulmon l.ake trout Yellow perch Rainbow trout Redhorse sucker Smell White tucker Whiietiih No. Fish ANM Y7TO 85 287 17 42 21 56 154 44 II 16 38 51 43 Mean Fl5lt Weight, g 100 249 3.650 2.160 3,100 2,720 1,620 MS 4,190 902 31 1,130 1,170 Mean Lipid, % 6.5(3.9| V>.0(5.9J ' , 5|4.J] 0.017.01 5.0(3.9] 6.5(2.1| 16.6(4.3] 6.III.7] 18.4(3.3] 8.611.21 5.8(1.8] 5.912.8] J7.6|4.4] Mean PCB's 4-6(2.tI 6.012 2] 7.3(2.81 .4.2(3.61 tl.4(4.0) 11.5(5.7] 15.5[3.3| 5-813 5) 9-3(4.iJ 3.0(0.7] 2.711.3J 39(36] 3.0(1.91 DDE 1.7(0.81 2-5(1.1] 2.7(1.01 0.710.9] 52(1.5] 4.812.3] 5.0(2.8] 1.0(0.6) 3.4(1.31 1.6(0.5] 0.8(0.41 1.0(0.51 0.8(0.31 Mean 2DDT 2211.1) 3.8(2.8] 4-2(1.61 0.9[I,2) 6.8(2.51 6.3(2.8| 7.1(3.71 1.6(1.1) 4.2(1.81 2.610.7] 1.2(0.6) I.611.2) 1.4(0 6] NOTE; Expressions in brackets Represent standard deviations. Residuet Are ppm wet weight. 1 Scientific Dimes Appear In Table .1. Mean PCB/ 2DDT 2.4 2.2 ! .8 7.6 1.7 2. ( 2.5 4.8 2.3 1.3 2.6 3.4 28 Mean Mean DDE o.p<-DDT/ i DDT p.p'-DDT 08 0.7 06 0% 0.8 0.7 0.7 0? 0.8 0.6 0.7 07 _07 0.2 0.2 0.1 0.3 0.2 0.2 0.2 0.1 0.2 0.2 0.! 0.1 0.2 TABLE 3. Mean concentrations oj PCB's and DDT in fish, Lake Michigan--1971 Location Michigan City Beoiun Harbor Waukegan . Saugatuck ' Sheboygan J.udington Franklort Mnnitou Island Rock Island St. Manln Island Capture Date No. Fish ANALY7F0 10/15 9/2 8/23 4/1! 10/15 7/3 10/5 9/10 9/11 9/11 10 10 2 12 4 16 to 3 3 6 MIchlgan City Sheboygan Cilia Rock 10/15 7/13 9/(6 1 5 10 Michigan City Siugaluck Shebovgan Penaaukee Bar Manhou Island 11/29 10/15 7/23 ll/I 9/16 2 15 11 9 5 Beotcva Harbor Naugatuck Saugatuck Saugatuck M llwaukee Sheboygan Sheboygan 9/2 6/16 6/18 6/19 9/19 7/13 7/22 fContinued next page) 10 18 24 15 11 13 1J rcB's Percentacc Fish Above 5 PPM PCB's PCB's, LIPID WEIGHT P.P'DDE ALEWIFE fAtosa pifuJohartngus) 4.4[2.0] 4.811.1] 2.510.1] 5.3[2.2| 5.511.4] 4.4(1.41 3 711 2] 3.812.2] 8.9(12.0] 3.511,31 40 164 1.4 40 <0 1.8 0 47 J.O 41 51 1.8 50 79 2.2 18 207 ND 20 62 1.3 33 51 3.2 66 ip: 1.1 16 tz 1.0 Brown trout (Saimo \rutto) 11.9(0.01 1.913.01 6.712.5] 100 100 70 51 3.7 42 2.6 ?< 2.8 Carp (Cyprinus carpio) 11.0(0.2] 4.6(4.81 17(0.8] 42(1.4] 5.810.8) 100 26 0 33 80 72 3.3 71 0.6 30 0.2 30 0.8 30 ND Bloater (Coregonm hoyi) 5.011.1] 60 24 . 2.5 8.1(1.9] 88 46 1.9 7.812.21 95 4 > 2.4 69(1.8] 86 18 4611.2] 36 It 3.4 S.ttt.5] 61 31 1.3 6.1(1.81 76 21 3.4 P.P'TDE P.P'DDT o,pDDT 0.19 0.23 0 18 0.22 0.20 ND 0.16 0,33 0.11 0.14 0.5 0.5 0.5 0.8 0.7 ND 0.4 1.3 0.3 03 0.08 0.08 0.07 Q.10 0.07 ND 0.06 0.16 0.04 0.05 0.70 1.7 0.22 0.46 1.2 0.18 0.48 1.0 0.14 0.81 0.20 0.07 0.19 ND 0.3 0.1 0.0 0.0 ND 0.14 0.02 0.01 0.01 ND 0.31 1.5 0.19 0.47 1.8 0.19 0.63 2.4 0.25 0.47 2.5 0.31 0.36 2.0 026 0.40 2.2 0.24 0.34 2.0 0.24 Total DDT Percentace Fish Abovh 5 PPM DDT 10 2.7 0 1.6 0 2.7 11 3.2 0 ND ND 1.9 0 0 30 t .5 0 1.5 0 P4 100 4 4 25 4.4 <0 4.6 50 0.9 0 0.3 0 1.0 0 ND ND 4.3 30 4.3 37 3.7 64 5.1 66 6.0 88 4.1 50 5.9 81 Vol. 9 No. 1, June 1975 OSW 026075 25 Wifi < T" a. :. Aid ,, ./ . _ .Y-v.-v .-/ TABLE 3 (corn'd.). Mean concentrations of PCB's and DDT in fish, Lake Michigan--1971 Location Sheboygan Sheboygan Sheboygan Ludington Frankfort Manilou Island Washington Island Rock Island Rock Island Rock Island St. Martin Island Manisiique Gapiu*e Date No Fish AS I.LV7LD 8/19 8/27 10/15 7/3 10/5 9/10 9/9 9/11 9/14 9/16 7/19 5/27 f> 7 6 4? ft It* 6 6 g 9 9 Milwaukee Manitowoc Strawberry Creek GUIs Rock 10/15 10/21 10/21 9/16 1 1 8 10 Michigan City Michigan City Michigan City Sheboygan Ludington Platte River CiUs Rock 4/17 9/27 10/7 10/21 8/28 10/7 9/16 * 8 6 9 4 in n Michigan City Michigan City Saugatuck Saugatuck Saugatuck Milwaukee Milwaukee Milwaukee Sheboygan Sheboygan Ludingtcm Ludington Grand Traverse Bay Green Island GUIs Rock - Michigan City Waukegan Milwaukee Ludington Frankfort Pcnvauke* Bar 10/15 9/8 6/21 7/10 10/t 9/14 9/19 10/15 7/1 7/15 7/1 7/4 10/19 7/21 9/16 10/15 8/28 10/13 7/5 10/12 8/2S 4 3 14 7 9 1 7 12 1 :>& it* 8 8 ) 1C u 9 ini A 10 Michigan City Gills Rock 10/15 9/16 1 9 Rock Island St. Martin Island 9/M 9/11 7 9 Michigan City Sheboygan Green Island Kock Island St. Martin Island 10/15 10/15 7/21 9/11 7/19 15 } 5 8 4 Michigan CJty Saugatuck Saugatuck Peosaukee Bar Grand Traverse Day Green Island Rock Island 10/15 10/15 10/18 8/6 10/19 7/21 9/M (Continued next page) 6 3 5 7 14 1 14 rcB\ 3.8(0.6} 5 0(1.?) ? 7 to M 74(1.8) 4.710.7] 4.6(UJ 4.1[0.6} 5.8C.5J 5.611.6} 4 0(0.7} M(0.6J 4.8(0.7} Percent age fish Above 5 PPM PCU`5 rcB*, Lipin WMCMl 0 15 57 23 0 21 93 41 12 28 30 24 O 16 66 97 57 23 12 18 0 16 33 26 r.p'DUE 2.6 3.2 2.4 2.0 2.2 3.1 3.2 2.8 2.7 2.8 2.2 2.9 r r'TDE 0 ?S 0 4" -i ( ,.<s 0 :3 n 50 (* 34 0.?6 n 42 0.29 0.34 0.42 Chinook salmon (Oncorhynchus tschawytscha) 24.0(0.01 11.5(5.11 9.9(2.81 12.7(0.7) 100 117 6.6 !00 209 6.3 100 373 4.5 100 278 3.5 X 67 0.62 0.39 0.44 Coho salmon (Oncorhynchns Msutchj 5.6[I.7J 12 5) 0.8 17J[g.4) ' 87 255 5.3 34 0(4 0) 100 349 4.5 I2.IC.SJ 100 276 6.6 1I.2J5.5J 100 108 6.6 12.9(1.3] 100 226 5.5 12.6(4.1] 90 166 4.9 0.17 0.46 0.41 0 c7 0.39 0.48 0,45 LAKt taour (Sahelinus namaycmh) 14.9(2.0) 100 89 2.9 U 8* 21.2(6,8) 1W 121 9.5 M2 11.9(3.8} 100 70 4.7 0 65 15.512.4) 100 78 6.9 (*.70 18.7(4.7) 100 M3 6.7 0.84 21.2(0.0) 100 90 10.1 0.96 21.1(6.0) 100 114 10.6 l.nf 10.4(3,6) 100 127 2.3 0.-U 14.9(0.0) 100 58 ND ND 12.5J5.2] 100 82 4 3 0.51 8.1(1.gj 100 51 3.3 0.52 *5(1.7) 100 58 3.2 0.6? 11.3(5.3] 75 56 6.0 0.73 9.011.7) 100 48 3.8 o.ro 34.7(6.4) 100 83 5.5 0.62 Yellow peach (Perea jlaveseens) 4.2(0.7} 14 72 0.8 0 15 61J1.5] 88 78 ND ND 10.9(3.1) 6 2|1.3) 90 203 1.1 100 139 2.2 0 *0 0..-0 5.4J1.8J 50 69 1.7 0.43 2.7(2.1J 10 49 0A 0.10 Rainbow THOU7 (Salmo gairdntri) 12 0(0 0] 8.8(4.3) 100 77 66 ND 47 3.1 ND 0.34 REOHOitse (Moxvstomo sp.) 2.810.9! 3.2(0.51 0 33 1.7 0.30 0 37 1.5 0.J5 Ratnow SMELT (Osmerus tperlanus modrax) 2.210.9] 0 45 0.9 O.M 0.710.2) 0 18 0.6 0.12 2.611.1) 0 57 0.7 0 12 2 9(1.7) 25 49 1.0 o.u l.?[0.JJ 0 31 0.7 0.09 WHfTE Sucre* (Catostomuj commenonl) 10.6(4.01 100 100 i.S 0.32 6.012.9) 66 149 0.7 o.u 2..M0.4) 0 40 ND ND 3-213.1) 14 37 0.3 0.15 2.MOT) 0 66 0.4 0.31 2.110.0} 0 20 0.7 0.19 2.5(0.9] 0 46 0.9 0.20 r.CDDT 1.3 It H IS 19 " :o ' ' l.i 1.8 4.7 1.2 1.0 1.2 0.6 12 1.4 1.4 0.9 1.4 1.2 31 39 2.1 20 2.6 3.0 3.3 1.3 ND 1.7 1.6 20 2.0 1.5 1.9 0.4 ND 0.7 0.9 2.2 0.0 ND 0.9 0.6 0.8 0.4 0.3 02 0.5 0.2 1.8 0.2 ND o.: 0.4 04 01 o.p'DDT 0 16 0.26 0.17 0.28 0 16 0.26 o.ts 0.08 0.22 0.14 0.17 0.14 0.*3 0 *! 0.17 0.20 DOS 0.20 0.18 0-27 0 19 0.24 0.20 0.35 0.45 0.27 0.24 0.27 0.47 0.45 0.1 5 ND 0.24 0.22 0.30 0.30 0.21 0 24 0.04 ND 0 08 0.13 0.14 0.01 ND 0.16 0.09 0.09 0.04 0.03 0.02 0.05 0.04 0.08 0.03 ND 0.04 0 03 0 08 0.04 Total DDT 44 6.2 45 5.0 3.8 5.6 56 44 5.4 4.5 3.8 5.2 Ppalpm i7 AGE Fuh Ahovp 5 PPM DDT 20 Rf) 42 46 0 50 6U 20 50 40 0 80 M 6- 7.3 too 16 7.2 6.5 60 8 8 100 8 3 100 7.6 100 6.7 87 7.3 14 9 7.6 9.8 10.6 14.5 15.4 4.2 ND 6.S 5.6 6t 9.0 68.0;< 100 100 88 100 100 100 100 20 ND 64 60 66 77 72 62 1.3 0 ND ND 21 0 3-6 0 4.5 0 0.5 0 ND ND 4.5 40 2.7 0 2.7 0 1.4 r 10 c 1.0 c 1.6 c 1.0 0 4.6 66 t.o 0 ND ND 0.7 0 2.1 0 1.3 0 14 0 26 Pesticides Monitoring Journal DSW 026076 i.i.l .*>***! Aif-*--v. v- *** '***" -1 *fr' ,ii*ad*;ii AjLWi4A. n^'.'Mrt^. 'm^\ uLv I.OCAIIUS TABLE 3 (cont'd.). Mean concentrations of PCB's and DDT in fish, luikc Michigan--1971 Percent* -- ... agf. Fisk No. Above PCB's. Capture Fish Da re Analyzed PCB'a 5 PPM PCB's LIPID >a trcuT r.p' DDE n.p' TDF. />/ DDT O.p'DDT Total DDT Laice whitefish (Cortxonus chipeaformis) Michigan Cr.y Siuc(uek Saufamck Cm and Hi% rn Cm and Traverse Bay Rock Island 10/15 6/19 6/21 9/6 10/19 9/11 4 7 7 13 10 6.11091 2.710.5) 3.1(1.51 5.8(0.91 l.8|0.3] 1 3[-21 100 0 0 71 0 0 15 0.5 15 0.6 18 NO 25 0.7 13 1.2 9 0.7 0.32 0.21 ND 0.38 0.25 0.16 0.5 04 ND 0.8 0.4 0.4 0.06 0.08 ND 0.10 0.08 0.05 1.4 1.3 ND 19 2.0 1.4 NOTH: Expressions in brackets represent standard deviations. N D ~ not determined. Residues are ppm wet weight. I'l Kt I N ! age Fish Above 5 PPM DDT 0 0 ND 0 0 0 wives was greater in southern Lake Michigan than in the northern regions, although anomalies arc apparent. Most alewives captured south of a line between Saugatuek and Sheboygan contained between 4.4 and 5.5 ppm PCB's. whereas those caught north of the line con tained between 3.5 and 4.4 ppm. An interesting excep tion occurred in alewives from Rock Island just off the Door County Peninsula in Wisconsin: mean PCB con centration was 8.9 ppm. Analysis of brown trout suggested similar trends: those from Michigan City at the southern end of the lake contained 11.9 ppm PCB's, whereas those from She boygan and Gills Rock contained 7.9 and 6.7 ppm PCB's. respectively. Carp from Michigan City also had higher levels of PCB's than had those from the northern region. In contrast to the 11.0 ppm found in (he Michigan City carp, those from Saugatuck and Sheboygan contained 4.6 and 1.7 ppm, respectively. PCB's in bloaters in southern Lake Michigan ranged from 4.6 ppm near Milwaukee to 8.1 ppm near Sauga tuck. In general, bloaters from the northern regions had concentrations below 5 ppm. The concentration of PCB's in the five groups of bloaters collected near Sheboygan during a 3-month period varied from 3.7 to 6.1 ppm. although the mean was below 5 ppm; no trend was indicated. The variation is somewhat less when data are expiessed on a lipid basis; for example. PCB concentrations in the August 27 and October 15 bloaters were 5.0 and 3.7 ppm wet weight, respectively. In contrast, (he concentration of PCB's in lipids was 23 ppm and 21 ppm. respectively. Thus much of the observed variation is caused by the variation in lipid content of fish. All chinook salmon captured in Wisconsin contained more than 5 ppm PCB's; mean concentrations ranged from 9.9 ppm in Strawberry Creek (Sturgeon Bay) to 24 ppnt at Milwaukee. In concentrations of PCB's among coho salmon, autho.s observed little evidence of a trend dependent upon sam pling region. Except for coho caught early in 1971 near Michigan City, mean concentrations of PCB's ranged from 11.2 ppm in salmon near Ludington to 17.3 ppm in those near Michigan City. Among lake trout PCB concentrations were greatest in those from Michigan City, Saugatuck, and Milwaukee, where mean concentrations were generally between 15 and 21 ppm. Trout from the northern areas such as Sheboygan. Ludington. Grand Traverse Bay. and Gills Rock contained considerably less, and mean concen trations ranged between 8 and 15 ppm. Mean concentration of PCB's was unexpectedly high, 10.9 ppm, in the 10 yellow perch caught near Milwau kee. Perch from other regions averaged less by a factor of two, and those from lower Green Bay contained 2.7 ppm. In seven Rock Island rcdhorsc. PCB residues averaged 2.8 ppm. In nine specimens from St. Martin Island, mean concentration was 3.2 ppm. Rainbow trout were caught only near Michigan City and Gills Rock. The Michigan City rainbow trout had 12.0 ppm PCB's, whereas those from Gills Rock aver aged only 8.8 ppm. Concentrations of PCB's in white suckers and smelt were generally between 2 and 4 ppm. although the average concentration was 6.0 ppm in the three white suckers from Saugatuck on October 15 and 10.6 ppm in the six from Michigan City the same day. Except for whitefish caught at Grand Haven and Michigan City, the PCB concentration in whitefish was less than 3.1 ppm. DDT AND ANALOGS Concentrations of p.p'-DDT, o,p -DDT. p,//-TDE, and p.p'-DDE aic presented in Table 3 along with the total DDT and percentage of fish that contained residues above the 5ppm action level established by FDA (/). Total DDT in alewives ranged from 1.6 ppm near Wau kegan to 5.0 ppm near the Manitou Islands. There was no trend in the variations according to region. A brown trout from Michigan City contained 8.4 ppm total DDT, whereas those from Sheboygan and Gills Rock averaged 4.4 ppm. Except for the carp from Michigan City, which averaged 4.6 ppm total DDT, average concentra tions in Lake Michigan carp were 1.0 ppm or less. Voi. 9, No. 1, JuNr. 1975 DSW 026077 27 f. v'*..'' . Pim.' r. f A- -j STLCOPCB4010039 y y>-; i j'i.g* l *1 -s'*k"\ * ' 'fc" "s, s Toial DDT in bloaters ranged from 3.8 ppm at Frank fort and St. Marlin Island to 6.2 ppm at Shohoygan. There are no trends for DDT in chuhs (Table 3). Except for eight coho salmon caught near Michigan C ity in the spring, which averaged 1.6 ppm total DDT, total DDT in this species varied I,tile throughout the lake. Mean concentrations ranged between 6.5 and H.K ppm. Lake trout from Michigan City averaged 14.9 ppm total DDT on September 8. 1971; those caught October 15. 1971. averaged only 7.3 ppm. The discrepancy is likely due to size differences. For example, the lake trout caught near Milwaukee in September also contained a mean concentration of approximately 15 ppm; how ever, the smaller trout caught near Milwaukee in Octo ber averaged only 4.2 ppm total DDT. DDT concentra tions in lake trout from northern areas of the lake were, less than 8 ppm: approximately 60-70 percent of the lake trout contained over 5 ppm total DDT. Yellow perch from Pcnsaukee Bar in lower Green Day had the lowest DDT content. 0.5 ppm: perch from other areas contained between 1.3 and 4.5 ppm total DDT. None of the perch contained more than 5 ppm total DDT. Concentration of DDT in smelt, whitefish. and white suckers averaged approximately 1-2 ppm. although white suckers from Michigan City averaged 4.6 ppm total DDT. Summary Concentration of PCB's ranged from le?s than 2 ppm in small fish with low lipid content to over 20 ppm in larg er fish with higher lipid content. The concentration of PCB's in l.akc Michigan coho salmon is two to three times greater than in coho from Lake Huron, approxi mately 1.5 times greater than in Lake Ontario coho salmon, and approximately 10 times greater than in coho from Lakes Erie and Superior. Essentially 100 percent of Inrge salmon and trout, both popular food sources, and 50-80 percent of bloaters from Lake Michi gan contain PCB concentrations greater than the 5 ppm tolerance level set by FDA. Additional monitoring of this watershed is needed to determine whether tissue concentrations will reflect restrictions in domestic PCB sales and possible decreases in PCB usage in the water shed even though U.S. production of Aroclor 1254 has remained essentially the same as in 1969 (24). Acknowledgments Fish for this study were collected by the Bureau of Sport Fisheries and Wildlife Great Lakes Fishery Lab oratory, U.S. Department of Interior: State agencies from Michigan, Indiana, Illinois, and Wisconsin; and numerous private research and commercial fishing or ganizations. Their assistance, essential to this study, is sincerely appreciated. LITERATURE CITED (/) Haitian, D. C. 197?. A review of PCB's in the Great I.akcs area. Pood and Drug Administration, U.S. DHEW. Governors' Great Lakes Pesticide Council, Jan. 30. Chicago. 111. (Mimeo.) (2) Reinert, R. E. 1970. Pesticide concentrations in Great Lakes fish. Pestic. Monit. J. 3(4 1:23 3-240. (3) Vrith, C. D. 1970. Ensironmenial chemistry of the chlot obinphenyls in the Milwaukee Kiser. Ph. D. thesis. Univ. Wisconsin, Madison, Wis. 180 pp. (4) Zitko, V., and 1\ 21. K. Choi. 1971. PCB and other industrial halogenated hydrocarbons in the environ ment. Fish. Res. BJ. Can. Tech. Rep. 272. 55 pp. (5) National Institutes of Health. 1972. Environ. Health Perspecl. 1 ( 1): I -185. (6) Qiiinhy, G. E. 1972. Polychlorobiphenyls (PCB's) and related ctilorophemIs: Effects on health and en vironment, I. Bibliography 1881-1971. Oak Ridge Na tional Laboratory, TIRC-I. ORNL-EIS-72-20. 140 pp. (7) National Technical Information Service. 1972. Poly chlorinated biphenyls and the environment. Inter departmental Task Force on PCB's. Springfield, Va., COM-72-104 19. 181 pp. (8) Kernett, L. 1970. Rainbow and brown trout---Take Michigan 1970. Rep. Wisconsin Dep. Nat. Resour., Green Bay, Wis. 6 pp. (Mimeo.) (9) Great Lakes Fishery Laboratory. 1972. Annual prog ress report--1971. Ann Arbor, Mich. 318 pp. [10) Burdick, G. E,, E. J. Harris. H. 1. Dean. T M. Walker, J. Skea, and D. Colby. 1964. The accumula tion of DDT in lake trout and the effect on leproduction. 3 runs Amtr. Fish. Soc. 9312): 127-136. [11) Macek, K. 1. 196ft. Reproduction in brook Iron!, Sahelians lonlinalis. fed sublethal concentrations of DDT. J. Fish. Res. Bd. Can. 25( 9): 1 787-1796. [12) Johansson, N. S., S. Jensen, and M. Olsson. 1970. PCB indications of effects on salmon PCB Confer ence, Swedish Salmon Institute. Stockholm, Sweden. Pp 59-68. (Mimeo. I [12) Hartsottgh, G. K. 1962. Great Lakes fish now suspect as mink food. Amer. Fur Breeder 38( 1);25, 27. [14) Anlerich, R. J., R. K. Ringer. p, J. Schtiihle, and H. L. Seayran. 1970. An evaluation of processed Great Lakes fishery products for feeding mink. Fccdstuffs 42(3) :48-49. [15) Anlerich, R. and R. K. Ringer. 1970. Some effects of chlorinated hydrocarbon pesticides on mink. Amer. Fur Breeder 42(1): in-11. [16) Anlerich, R, J., R. K. Ringer, H. L. Seagraa, and W. G. Youatt. 1971. Effects of feeding coho salmon and other Great Lakes fish on mink reproduction. Can. J. Zool. 49(53:611-616. [17) Ringer, R. K,, R. J. Anlerich, and 21. Zuhik. 1972. Effect of dietary' polychlorinated biyhenyls on growth and reproduction of mink. Presented at the American Chemical Society, New York. Division of Air, Water, and Waste. Pp. 149-154. [IS) Ratcliffe, D. A. 1970. Changes attributable to pesti- 28 Pesticides Monitoring Journal DSW 026078 STLCOPCB4010040 cides in egg breakage frequency and eggshell thickness in some British birds. J. Appl. Ficol. 7( I ) :67-113. (19) Anderson, D. IF. 1970. Chlorinated hydrocarbons: their dynamics and eggshell effects on herring gulls and other species. Ph.D. thesis. Univ. Wisconsin, Madison, Wis. 166 pp. (20) Lufschow, L. A. 1972. Lake Michigan Pesticide Con ference pesticide report. Final report to U S. Environ mental Protection Agency by Wisconsin Department of Natural Resources, Madison, Wis. 139 pp. (21) Veith, G. D., and G. F. Lee, 1971. PCB's in fish from the Milwaukee River. Proc. 14th Conf. Great Lakes Res. Pp. 157-169. (22) Armour. J. A., and 1. A. Burke. 1970. Method for separating PCB's from DDT and its analogs. J. Ass. Offic. Antil. Client. 53 (4): 761-768. (22) Berg, O. W., P. L. Diosady, and G. A. V. Rees. 1972. Column chromatographic separation of PCB's from chlorinated hydrocarbon pesticides, and subsequent gas chromatographic quantitation in terms of deriva tives. Bull. Environ. Conlam. Toxicol. 7(6): 3 38-347. (24) Popageorge, W. B. 1974. Testimony on behalf of Monsanto Company, Transcript of Proceedings, U S. Environmental Protection Agency. In the Matter of: Toxic Pollutant Effluent Standards, Washington, D C., May 8. P. 2756. Vol. 9, No. 1, June 1975 DSW 026079 STLCOPCB4010041