Document 9JeQ4RgjqpGm2714GvV5r9xMe

-r;SATP-iY, !- RESIDUES IN FISH, WILDLIFE, AND ESTUARIES DDT Plus PCB's in Blubber of Harbor Seals Raymond K. Anas' ABSTRACT Sampler of blubber from IS harbor fals (Phoca vitulina richardii) were collected in 1971 from San Aiiguel Island. Calif : /he Columbia River, Oreg.. Pure! Sound, Wash., and the PribUaf Islands, Alaska. To'ui amounts of DDT plus PCB'\ ranged from 390.7 to 7.3*9.0 ppm in five San Miguel Island seals: 439.4 to 1,620.9 ppm in two Puget Sound seals: 27.7 to 109.9 ppm in three Columbia River seals: and 6.8 to 27.8 ppm in three Phbilof Islands seals. There nj no iadicutlon of loss of total DDT phis PCB's in three samples reanalyzed after 2 years in rm.YH uorage. Iniroduaion Organochlorine pesticides have been found in seals in widespread parts of the world U.21, but few data have been published on pesticides in harbor seals {Phoca vintlinu richardii) from the eastern North Pucific Ocean. Up to 142 ppm DDE. 7.1 ppm DDD. and 2.6 ppm DDT were found in blubber from two harbor seals taken off central California (3). Up to 1.039 ppm total DDT and 145 ppm PCB's (polychlorinated biphenyls) were found in California sea lions V/.alophus californianus cafi/orniunurI from San Miguel Island. Calif. (4). one ol the areas sampled in this study. This report documents the amounts uf DDT and its metabolites plus PCB's in the blubber of 13 harbor seals {Phoca viudina rUhardli) collected in 1971 from four areas of the eastern North VoMhMW 1`iMwws Center. Ntlipnol Marine FisJinie* Service. Na tional Octamc anti Atmonpharle Admlniiiratipn. 2225 Monllake Hnnlrvaril Fsm. Seattle. Wash, enitl. 12 Pacific Ocean. San Miguel Island. Cali!.; Columbia River. Oreg.; Puget Sound. Wash.: and the Pribilof Islands, Alaska. Harbor seals of the subspecies ruhardii are nonmigratory and ocevtr in the eastern North Pacific Ocean from Mexico to the Bering Sea. (f food species preyed on by the seals do not migrate tar. these seals might be used to locate geographical ,.ra- where organuthlorine hydrocarbon levels are high. Harbor seals living off British Columbia feed near shore on demersal fish amt octopus, although -ome migratory Pucific salmon (Oncvrhyncluts sp.) are eaten seasonally |5). Harbor seals feeding off Amchitka Island. Alaska, eat Atka mackerel (/'fcurogrtiwuift mvnopfrrytiim i and octopus (Octopus sp) (6). A study of harbor seals in Washington showed (hat cods, flounders. Pucific herring, and sculpins made up 93 percent of the total diet. Squid and octopus make up another 6 percent f 7>. Harbor seals ap parently feed on both migratory and nonmigratory species. Sampliny Procedures All seals appeared to be in good health at the time of collection, except one sea) from Washington which had apparently died from & deep laceration Irom a previous injury. Samples were collected by taking about 100 g of blubber from the belly area of each seal, near the midline and anterior to the mammaries Blubber was Pesticides Monitoring Journai. muns oaaiio I.--.*.- - ' - selected lor this study because organochlorinc com pound* are lipophilic (/). Samples were placed in new glass bottles uml shipped frozen to the teuinij laboratory, including the drying step. No corrections were made for recovery rales. The lower limits of detection were 0.02 ppm for DDF. DDD. and DDT, and 0.05 ppm WARI' Institute, Inc., Madison, Wis. for PCB's. Pesticide levels were only slightly higher on Ages were estimated by counting layers of dentine in a fat basis than on a wet-weight basis, so results are reported here on a wet-weight basis only. ' tipper canine teeth lS\9). The error in assigning ages to ! harbor seals is not known. Body length was measured 1 from the tip of the snout to the end of the tail, with the j seal placed on its back. Aroclor 1254 was used as the standard for PCB's. Only the peak between DDT and DDD was used for estima tion of PCB's, so the values for PCB's are not`precise. 1 Values for total DDT undoubtedly include some PCB's. Analytical Procedures To avoid possible errors, total DDT and PCB's were | Samples of blubber were analyzed by gas-liquid summed. j chromatography for the following organochlorinc com Because of high laboratory cpms. only one sample was pounds: aldrin, chlordanc. endrin, hcptachlor. hepta- analyzed by the silicic acid method to separate DDT chlor epoxide, methoxychlor. toxaphene. dieldrin, ben from PCB's (12). The blubber from this seal, a 176-cm zene hcxachloride (BHC), PCB's, and the o.p and p,p* male from San Miguel Island, had 2,110.0 ppm DDE, isomers of DDK, DDD. and DDT. Only BHC. PCB's, 3.98 ppm DDD. 96.1 ppm DDT, and 572.0 ppm und the p.p' isomers of DDK, DDD. and DDT were PCBs. Total DDT plus PCB residues were 18 percent detected in 1.1 samples analyzed in 197! and in 3 samples higher from the silicic acid method than were results rerun in 1973. Confirmatory tests by use of thin-layer chromatography (10) on the rerun samples confirmed from regular analyses. This difference is within the limits of analytical variability. DDE. DDD. DDT, and PCB's, but not BHC. Levels of BHC will not be reported because of the negative confirmatory test. Glass bottles used to store the samples had paper lidtiners. The amounts of organochlorinc compounds found in a sample of unused lid-liners would have had a To determine concentrations of the various organo* maximum effect of 0.086 ppm total DDT plus PCB's. chlorine compounds, the entire )00-g sample of blubber Because the additions, if the}' occurred, would have was cut up while frozen, run through a hand food little effect on the observed values, data were not ad grinder, and transferred to ether-rinsed 4-oz glass jars. justed. A random 5-g portion was placed in a tared 100-ml beaker and the weight was recorded. The sample was then dried at 40C for 3 to 5 days, weighed for moisture Results content, and transferred to a 100-ml volumetric flask Levels of total DDT plus PCB's ranged from 380.7 using petroleum ether. The blubber consisted almost to 2,350.0 ppm (geometric mean 610.7) in San Miguel entirely of fut and dissolved entirely in the petroleum Island seals; 459.4 to 1,620.0 ppm (geometric mean ether. No weighablc amounts of insolubles were found. 862.7) in Puget Sound seals. 27.7 to 109.9 ppm Cleanup was carried out on a Fiorisil column following (geometric mean 62.5) in Columbia River seals, and 6.8 1 standard procedures (//). Next, the resulting solutions to 27.8 ppm (geometric mean 11.3) in Pribilof Islands were concentrated to 10-15 ml and made to 25 ml seals (Tahle I). Geometric means were computed be with Itcxauo. Sample solutions of to fx\ or less were' cause of the skewed distributions of the organochlorinc injected into a Barhcr-Coleman Model 5360 gas chro compound residues. The organochlorinc levels over matograph with an Sr90 electron-capture detector and the following instrument conditions: lapped in Sun Migticl Island and Puget Sound seals, and in Columbin River and Pribilof Islands seals. Levels in the Columbia River and Pribilof Islands seals did not Column*; - jtlftM pocked rtih 1 petcem DC-200 w ns cliinm Q 00/>00 (packed *)ih > percent OV-17 on fat chrem Q 100/120 for BHC1 An 'DV*I7 1 0>M column wai added in I9TS. overlap the levels in San Miguel Island and Puget Sound seals. A one-way ana(ysi*-of-variancc test shows that the mean total DDT plus PCB levels differed signifi Teniprratute; Detector JJO'C; fnfector 2J0*C: column 210*C ni*C for BHC). cantly between areas (P<0.01). Center gat; Nlfiigrn m (In* rale that gate p.p'-DDT a re tention t>me of S-S iptnuie* nJoa minuir* for anc>. The Pribilof Islands arc isolated from areas of high population and industrialization: the Columbin River drains large agricultural area* m Oregon, Washington, Peak heights were measured to quantitate organo and Idaho; and San Miguel Island ami Puget Sound chlorinc pesticide residues. Recovery rates ranged from are close to highly industrialized areas. Harbor seals HO to 90 percent for all organochlorinc compounds. taken near heavily populated and industrialized areas Recoveries were run through the entire procedure, had the highest total DDT plu> PCB levels, and seals Vol. 8, No. 1, June 1974 13 gy T* mons oa^wi. i& It.- im. & m * TABLE 1.--Toinl ODT : plus PCB's in blubber of harbor wait eollrctrtl in 1971 ' DDE - DDD + DDT. Canine leetb loit. June May June-August August 153-176 112-126 95-1IV IJ5-17J 0.9-1 4 1.5-3.6 2.4*50 2.6-6.2 96.2-100.0 90.5-9S.I 62.5 >62.7 27.7; B0.4: 109.9 439.4; 1.620.0 6 8; 7 1. 27,8 token front the most isoluted ureu, the Prihilof Islands, had the lowest levels. However. larger samples are needed to verify these results. Variability due to -sex. and age could not he evaluated for these data because of the small sample sizes. Maximum residue levels oc* curred in male seals in each area, hut the oldest seals did not have the highest total DDT plus PCB levels within an area. After 2 years of frozen storage, two samples from San Miguel Island and one from the Pribilof Islands were reanalyzed. Total DDT plus PCB values were + 18 percent, --16 percent, and --3 percent, respectively, of the original values. Results from the original end rerun samples are within the limits of analytical varia bility and indicate no significant changes in residue levels. Acknowledgments Thanks are due to T. C. Newby, College of Fisheries. University of Washington. Seattle. Wash., and to the Staff of the Division of Marine Mammals. Northwest Fisheries Center, National Marine Fisheries Service, Seattle, for collecting samples for this study. Thanks arc also due to Virginia F. Stout, Pacific Fishery Prod ucts Technology Center. National Marine Fisheries Service: Seattle, Wash., for suggestions that improved the manuscript. LITERATURE CITED U) Holden, A. V., and K. Maeuten. 1967. Organochlorine pesticides in seals and porpoises. Nature 216(3122): 1274-1276. (2) Siadrn, W. J. L.. C. M. \frnzie, and IV. L. Rrtrkef. 1966. DDT residues in Adelie penguins and a crab* eater seal from Antarctica. Nature 2I0f5037):670-673. IJ) Shaw, S. B. 1971. Chlorinated hydrocarbon pesticides in California sea otters and harbor seals. Calif. Fish Game 57(4):290-294. (4) DeLong, R. L., IV. G. Gilniartin, and J. G. Simpson. 1973. Premature births in California sta lions, associa tion with high organochlorine pollutant residue levels. Science 181(4103): 1168-1170. (5) Spalding, D. J. 1964. Comparative feeding habits of the fur seal, sea lion, and harbor seal on the British Co lumbia coast. Bull., Fish. Res. Bd. Can. 46. 52 pp. (6) Kenyon, K. W. I63. Food of harbor seals ut Amchitka Island, Alaska. J. Mammal. 46(11:103-104. (7) Scheffer, T. H., and C. C. Sperry. 1931. Food habili of the Pacific harbor seal, Phoca richardi. J. Mammal. 12(3): 214-226. (8) liscus, C. H., C. A. Baines, ami F. Wilke. 1964. Pelagic fur seal investigations. Alaska waters. 1962. IJ.S. Fish Wildl. Serv. Spec. Sci. Rep. Fish. 475. 59 pp. (9) Law.r. R. M. 1932. A new method of age determination for mammals. Nature 169*4 >10) 972-973. (10) Mulhern, l). M., E. Croniartie, If. L. Reichel, anti A. A. Belisle. 1971. Semiquanlitnlive determination of polychlorinated biphenyls in tissue samples by thin layer chromatography. J. Ass. Offlc. Anal. Chem. 34(3): 548-550. Ill) U.S. Food and Drug Admimstration 1968. Pesticides analytical manual. Vol. 1. Sec. 211.15. Washington, DC. (I2t Armour, J. A., and J. A Burke. 1970 Method for separating polychlorinated biphenyl* from DDT and its analogs, i. Ass. Offic. Anal. Chem. 53(4):76l-768. HONS Qa^l7^ 14 Pesticides Monitoring Journal