Document 91n2aN0Yk5onv8p62NbMxQNOV

PCB Residues in Atlantic Zooplankton by R. W. Risebrouck* In*CUM*e of Marine Retourcrt, Department of A'ulmtonirf Science* (inivertitj of Californio, Berkeley. Coiif. 94720 Valerie Vreelamd** BecHni Marine Station. Pacific Grata, Calif. 94950 and Ceorce R. Harvey**, Helen P. Miklas**, uid Gary M. Carkwnani* Studies of the polychlorinated biphenyls in marine ooeystems that have bean accomplished to date have sheen that these eonpounde are more abundant than the chlorinated hydro carbons of agricultural origin in the majority of ecosystems examined. Data, PCS mla present in higher concentrations than the EOT compounds in marine birds of the south Atlantic (1), In fish fTcm the north Atlantic (2). in the Brown Pelican (Peleeanus occldentalls) populations of Florida (3), in fish and fish-eating birds fran Long Island Sound (4), in marine birds of Amohitka Island In the northern Pacific (5), In same of the marine birds from Peru (6), and in sea birds breeding in Antarctica but spending the remainder of the year In Australian waters (1). Apparently only In the waters of coastal California and northwestern Mexico (7, 8) and in the Baltic (9) are EOT compounds more abundant than PCS. In California the exceptionally high concentrations of COT compounds In marine organisms are associated with the large amounts of DOT residues in the effluent of a COT manufacturing company <10, 11). Moat of the accumulated data refer to fish and fish eating or tube-nosed marine birds. In this paper we present the results of meaauraoenta of PCB and other chlorinated hydrocarbons In zooplankton sanples from the Atlantic Ocean. A traditional doga of pollution ecology has asserted that residues of non-polar chlorinated hydrocarbon pollutants such aa PCB are trophically aceimulated in food chains. Ample documentation is available to support this thesis in terrestrial rood chains or in food webs that pass from fish or other aquatic organism; to manuals or birds, but the data that might support the food chain concentration theory in marine and freshwater food webs consisting only of fish and invertebrates are surprisingly few. Protect address: Bodega Marine Laboratory, University of California, P.O.Box 247, Bodega Bay, California 94923 Present Address. Woods Hole Oceanographic Institution, Woods Hole, Massachusetts 025*0 MS Midi ti EaifewuMml Coalfl-tVs 4 TwhiUp, Vi I, ft* , 1173 W SrriAtfr>VUt N*wr Yarfc 1m. DSW 032688 250 l40y,>' 0.32 99.;>250 11 35* *5.2 ------- 100 fm -------1000 fm 72* 70* Figure 1: PCI concentrations in roopiankton of the north-west Atlantic Shelf, parts per million of the lipid weight T osw 032689 STLCOPCB4016651 MATERIALS AND ME1HXS Sample were obtained during three cruises of R/V ATLANTIS U of the Woods Hole Oceanographic Institution with a 16 mesh plankton net. Station sites and other relevant data are presented In Table I. The plankton were lamdlately transferred to polycarbonate or glass Jara and frozen. - Collection of marine organises fron oceanographic vessels for pollutant analysis requires that precautions be taken to prevent accidental contamination during collection and storage (12). Hexane rinses of the collection Jars, followed by oonoentratlon and gas chromatographic analysis, showed that they contained no PC3. Chips of the marine paint used an fCR/NTlS X were also extracted with hexane and found to be free of PCB. Since PCB has in the past been added to hydraulic fluids to reduce flammability, contamination from leakage of hydraulic fluids on the vessel was another potential source of the PCB (bund. No halogenated biphenyls have been used, however, in the recent past as components of hydraulic fluids on WHOI vessels. Chlorinated paraffins were added in 1969 to reduce flarambility, but this use was discontinued in 1970 (Mobil Service Dept., personal camunicatlon). Hexane extracts of the tab of new plankton nets were free of PCS, but PCB with chlorine composition similar to that of Aroclnr 1254 could be extracted from nets that had been in use. We conclude that the source of this PCB was the water, with associated organism and petroleum droplets, througi which the nets bad been towed. A fraction of the PCB in the plankton may therefore be second arily derived from the net. Relatively high PCB concentrations In fish livers from the seme localities Indicate the presence of PCS in the ecosystems examined (2). Plankton aanples obtained cn ATLANTIS II cruise 52 by J. H. Ryther were analyzed in Berkeley. They were placed in a 65* oven overnight for determination of dry weight, grand with anhydrous sodlim sulfate, and Soxhlet-extracted with 2:1 hexane :acetcne. All materials extracted by this procedure were defined to be lipids, although various amounts of carotenoid plgnanta were also present. Because the latter confounds are ocngmratively non-polar, it 1s likely that PCB dissolves readily in them. The comparative efficiencies of extraction with hexane alone and with 2:1 hexane:acetone ware not determined. Lipid samples were dried overnight at 65 for lipid weight determinations. Cleanup was acconplished by passage through a celite: sulfuric acid:toning sulfuric acid colimn (13) or by shaking lipid extracts In petroleum ether In a 500 ml erltrneyer flask with 2 volume of toning sulfuric acid. The flask was placed on dry ice, causing the acid mixture to freeze, permitting the removal of the liquid petroleim ether fraction (14). Aliquots M7 DSW 032690 STLCOPCB4016652 TABU I Kl and HIT raildoes la zooplankton. Parts par Billion wat weight 00, 4rjr wa&^it (D), nr lipid weight (L). * Station, Sanpla Position Oapth (notars) p,p'-aor P.P'-OW PCB VCB/Totnl m Nuaber, Date Tina Out North-aeat Atlantic Shelf A* ten as 12-71 12/10/71 . 4l*30*N 70*40'W A-II-S2-149S 9/7/69 39*43*H 70*40'W A-IJ-S2-1499 9/7/6J. 40*04'll 70*40'Y A-11 .2-1512 9/11/t - 39*57'N 71*40'h A-11-52-1S1S 9/12/6f 39*13K 71`50'b A-II-52-1514 9/12/&9 39*37ip 72*25'N A-I1-S2-1520 9/14/69 3S*S9'N 72*SO' 0-12 30 nin 0-30 15 ain 0-2S 7 nin J-10 10 nin 0-10 15 ain 0-10 13 ain 0-85 13 ain N.D. ,' 0.007 a) 0.0015 (0) N.D. N.D. 0.035 ft) 0.010 (D) 7.0 a) 23 0.) 0.32 00 0.071 (0) 250 <u N.D. N.D. N.D. ` " _ jfi.D. 260 '(!) 250 ( N.D. N.D. NJ. N.D. 144 1.9 99 3.0 (L) m (1*3 (D) r Jt mm * 7.* 36 >50 a. so >50 >50 STLCOPCB4016653 c CO X. o O' vO TABLE I (Continued) Station, Supli Position Depth (netere) p,p' -DOT p,p'-DOC PCI PCB/Total DOT Maher, Onto Tlue Out North-eest At Untie Shelf (continued) A-I1-S2-1S21 9/14/69 38*32'9 72*25*9 1800 1 hr 38 ain .08 (L) 0.21 (L) 5.2 00 18 A-U-S2-1S22 9/16/69 3B*35*9 73*90*9 0-20 IS ain N.D. 0.54 (.) 30 (L) 0.016 (O) 0.87 (D) SS A-11-S2-1S2S 9/17/69 A-II-S2-1S27 9/17/69 S8*39*N 74*59*9 37*30'N 75*21'9 0-20 11 nin 0-20 13 nin N.D, N.D. 2.4 0.11 (L) (D) N.D. 11 (L) 0.S3 (D) 57 00 4 S0 A-II-S2-1S32 9/20/69 37*S6*N 76*10*9 Surface 10 ain N.D. N.D. 2.4 (L) 0.10 (D) A-II-S2-1S39 9/23/69 36*35*9 74*51*9 0-20 13 ain N.D. 0.090 (1) 0.003 fl>) S.3 <L) 0.18 (0) 60 c in A-II-S2-1S41 9/23/69 37*04*9 74*25*9 0-20 20 ain N.D. 0.34 00 0.01S (D) 13.6 (L) 0.6S (D) 40 SE O Open North Atlantic N> O' sO A-11-59-22 11/70 23*41*9 34*29*9 0-100 00001 (9) <0.00001(9) 0.30 (9) >30,000 fVJ STLCOPCB4016654 TAILS I (Continued) Station, Staple Iknbtr, Date Position Depth (meters) Tine Out p.p'-DOT p.p'-DOC PCJ ' PCi/Totel DOT Open Herth Atlantic (continued) A-IIS9-36 12/70 30*S2'N 47*30,N 0-100 60 ain <0.00001 W N.0. 0.4S 00 >45,000 Open South Atlantic A-II-60-4-13 4/71 34*0S'S 42*40'K A-II-60-4-33 4/71 32*S0'S 26*24* A-II-60-S-PT-106 6/71 14'02'S OS*55 'E A-II-60-S-PT-89 S/71 32`49'S 15*09'E 0-200 20 Bin 0-200 20 min 0-203 -3 min 0-200 20 min 0.50 CD 0.003 00 0.61 0.001 (10 00 0.068 00 w0.0002 0.132 00 0.0002 (Q N.D. 120 0.64 0rw0j N.0. S3 (L) 0.12 on 0.023 (10 7.3 (L) 0.00007 (W) 0.021 on N.0. 10 (-) 0.018 (W) 0 K3 63 SO N.D.: Not Detected of the extracts were injected i-t- a Microtek 220 (gas chranatopept) equipped with a nickei-uj electron capture detector. The OQlum used was 32 QP-l cr. Ou'cmosorb W, 30-100 mesh, acid washed and CMOS treated. Nit 1 ten was the carrier and purge 90. Plow through the colurm was 95 ml/min., and flow through the purge was 45 ml/taln. Column temperature was 190, i2n5j0ec. tion port temperature 23`and the detector temperature Die remaining sanples were analyzed in Woods Hole. They ware extracted three tines with redistilled hexane in a Tlrtif homogenlzer. The dried extract was concentrated In a BidenW-Oaniah apparatus and was partitioned three tines with aoetcnltnie to separate the chlorinated hydrocarbona tan tha fat. The acetonitrile solution ms diluted with brine and axtraoted twice with hexane. T?>e dried and concentrated extract was applied to the top of a 10 x 2.5 cm coiwn of . activated florisil. The chlorinated hydrocarbons were eluted With & ethyl ether In hexane (v/v). An 81 QF-1:22 OV-17 ooluwi on Gas Chrcra Q was used. The presence of p.p'-DCT was confirmed by saponifies* tion U5). The profile of PCB peaks matched closely that of Aroclor 1254, vhlch was therefore used as a standard. SSSULtS Att> DISCUSSION The results of the analyses are presented In Table I. Tha station locations of ATLANTIC II cruise 52 from which plankton aanples were obtained or> shown In Figure 1, together with the PCB concentrations k>;- In the lipids of the aooplankton or each station. Expressed on a lipid basis the concentrations are relatively high and are ccrparable to the PCB levels in fish tan Long Island Sound. PCB in the lipids of 8 fish species obtained In tha vicinity of Groat Gull Island, Long Island Sound, ranged tarn 10 to 180 ppn, with a median value of 60 ppm (4). K8 in the zooplankton from the stations on the cntlhental shelf and slo^c -ar,. .1 tan 2.9 to 260 ppn, with a feadlan value of approxir.<ituv v. ,'adhn -ci-cent lipid ight of dry weignt was j. ... . . a dry a;.u wot weight basis, Sth the assumption that dry weient oonstltutcs 102 of wet lght, representative concentrations In zooplankton from the Whelf and slope areas would be in the order of 1.5 ppn and 0.15 respectively. Median . Eis of the fish tan fenr 1 ppn (4). concentration on a wet weight Sound >*.33 in the order of osw 032694 STLCOPCB4016656 In all samples the ratio of the total PCS to the total COT concentrations was comparatively high, considerably higher than that found In marine birds of the north end south Atlantic (1) or in marine fish (2). Th reasons for the discrepancy are not clear. EGB concentrations have been shown to be linearly related to PCS concentrations among the Brown Pelicans of Florida (3), among several species of aquatic birds In the Qulf of California (8), and In aquatic birds of several California ecosystems (8). PCB-DDE ratios, however, were not determined In fish or Invertebrates of thjse ecosystem, but the data suggest that the mechanisms of accumulation and excretion for both groups of compounds are comparable. Clarification of this apparent inconsistency would require determination of the relative solubilities of DOT and PCS compounds in sea water and of the partition coefficients between concentrations in sea water and the various lipid fractions of marine ar^mlsms. The collections fran the continental shelf and slope waters show a north-south gradient, with the highest concentra tions at the latitude of New York City and northern New Jersey and lower concentrations east of Virginia (Figure 1). The ample obtained from surface waters at station 1496, where the depth exceeded 1,000 fathoms, contained very low concentrations of PCS, leas than one part per million on a lipid basis. At station 1521, also a deep-water station, the samples were obtained below 200 meters and also had low amounts of PCS. High concentrations, however, were recorded In surface sooplankton over the mouth of the Hudson Canyon, where the depth exceeded 1,000 father'",. The collections firm the North Atlantic contained surprisingly high concentrations of PCS, ranging from 0.007 to 0.45 ppm on a wet weight basis. On the assumption that the dry weight constitutes 102 of the wet weight, these concentrations are equivalent to those recorded from shelf and slope waters. In the south Atlantic, a pronounced west-east gradient Is evident (Table 1). A possible source of the PGB la the highly industrialized area In the vicinity of Sao Paulo, Brazil. Na assitm that the PCB levels In the zooplankton aanplts are In physical-chemical equilibria with those In the Vbiant aqueous environment and can be used to indicate levels of contamination In the water Itself. Stalling and Mayer (16) have shown that levels of PCB accunulated by fish from ambient water are related to the PCB concentrations in the water. Other workers (17, 18) have shown that fish exposed to chlori nated hydrocarbon insecticides will lose them to the ambient water system when the contamination la removed. These experiments suggest that chlorinated hydrocarbon levels in flab are In equilibrium with the considerably lower concentrations In the surrounding water environment. Hamelihk et atl. (19) SS2 osw 032695 STLCOPCB4016657 found that Off residua* in ftvshwater Invertebrates under experimental conditions were a direct function of DOT concentrations in the water. The partition coefficients between lipids and water and between , fresh weight and water wire respectively In the order of 10b and 2 x 10*. Stalling and Mayer (16) report partition coefficients for PCS between Ipt weight of fish and invertebrates with water to be In the order of 5 * 10* and 2 x 10* respectively. FCB residues acquired by trophic accur.ulatlon in food webs could therefore be released into the ambient media to satisfy equilibrium onditions. The relative amounts of PGB present in solution in aaa em&fP, associated with organic particulate materials, and in few planktonic bianass are not yet known. If the amount in the baiter ware substantially greater than in the plankton, the FCB itions in the plankton would not depend upon the total Lc biomass. An Increase in plankton density would not It In lower residue levels in the plankton. Under experimental oonditions, ho..-ever, dot residues in algae ware Inversely proportional to the density of algae (19). In this System, the major iY-ctio.-. of tr.j DOT residues was not in the bater reservoir. Before concluding that equivalent PCS levels in zooplankton samples inply equivalent levels of local PCS contamination, it would be necessary to know, therefore, whether the sea water is a virtually infinite source of PCB far the planktonic blcnass. Aerial transport of dot appears to be the major route f entry of these ccepourds to the marine environment (20). U.S. PCS production figures are lower than COT production figures (21) and a large fraction of the PCB is not released to the erirlronment. PCB was detected in all saoples of rain water analysed in an extensive study in Great Britain (22) and its preaapoe In fish in remote Arctic lakes (23) also suggests that Serial transport is a significant dispersal pathway. The. proportion of the PCS residues recorded in the zooplankton that derives from aerial fallout, and the chlorine percentage of this FCB, remain to be determined. Moreover, as discussed gbove, the exceptionally hl^h rC3;DOT ratios in the dooplanktan, as capered to those in the fish, require further dpvMtigation. , The chlorine curpositi.' cf the PCB detected in the aorolankton wis approximately U.S. production of Areolar lc* lg 1970 amounted to 12 million pounds -- only one quarter flf tbe'proAjfition of 49 million pounds of Aroclor 1242. It l^tt be expected therefore tliai Dlor.enyls with fewer chlorine tens would predominate in planktonic :dimples unless these compounds were selectively legrau <1 Alternatively, since the iv OSW 032696 STLCOPCB4016658 solubilities and partition coefl icients with orpaniania of the Individual PCS compounds in a complex mixture present in an aqueous system can be expected to show e.io..-luble variation, the compounds detected in plarJarn would preferentially be those with lower solubilities in water and hi (->her partition coefficients. The FC8 conpound3 recorded in the plankton might not therefore reflect the overall KB composition in the marine environment. Nevertheless, it Is surprising and as yet unexplained that the relative amounts of PCB compounds should match the 54? mixture so closely. ACXNCWLEEGEMENES Research was supported by National Science Foundation International Decade of Ocean Exploration grants GX-28743 to the Bodega Marine Laboratory, and GX-2&334 to the Wood3 Hole Oceanographic Institution, National Science Foundation grant OB-11649 to the Institute of Marine Resources, H. S. Olcofct, principal investigator, and the Bodega Bay Institute of Pollution Ecology; ship time was supported by NSF grants QA-1298 and QD-27251 to WHOI arri by the U.S. Atctnic Ehergy Ccnnission under contracts AT(ll-l}-3564 (Ref. 000-3564-1} and AT(ll-l)-3563 (Ref. 000-3563-2). We thank John H. Ryther for his assistance. This Is contribution No. 2666 from the Woods Hole Oceanographic Institution. REFERENCES 1. RISEBROUGH, R. W. and CAWHGNANI, G. M., Proceedings of the Colloquium Conservation of the Seventh Continent, . Antarctica, in press (1972) 2 HARVEY, G. R., BOWEN, V. T., Lk US, R. H., end GRICE, Q. D., Proceedings of the Colloquium: Tie Changing Chemistry of the Oceans, in press (1972) 3. SCHREIBER, R. W. and RISEBFJOUGH, R. W., Wilson Bulletin, In press (1972) 4. HAYS, H. and RI3EBKXJGH, R. W., Auk, In press (1972) 5. WHITE, C. M., RISEBRDUGH, R. W., and CARMIGNANI, a. H., . manuscript in preparation (1972) 6 RISEBROUOH, R. W., CARMIGNANI, 0. K., ANEERSCN, D. W., and McQAHAN, J., namacrlpt in preparation (1972) 7. RISEBROUCW, R. W., Chemical Fallout, p 5 (196S), Charles C. . Thomas, Springfield 8 RISEERDOffl, R. V., REICHE, P., PEAKALL, D. B., HERMAN, S. 0., and KIHVEN, M. N., Nature 220, 1098 (1968) 354 DSW 032697 STLCOPCB4016659 9. JENSEN, S., JOHNELS, A. G., OLSSCN, M., and OTIERUND. 0., Nature 224, 247 (1969) 10. RISEBROUGH, R. W., MENZEL, D. B. ; MARTIN, D. J., and QLCOTT, H. 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Soc. 7Yar.s. *00, 207 (1971) 20. Chlorinated Hydrocarbons in the Marine Environment (1971), National Acadenjy of Sciences, Washington, 0. C. 21. Monsanto Chemical Company, December 7, 1971 22. TARRANT, K. R. and TATTON, J. 0'G., Nature 219 , 725 (1968) 23. RISEBROUGH, R. W. and BERGER, D. D., Manuscript Reports, Pesticide Section (1971), Canadian Wildlife Service, Ottawa QSW 032698 STLCOPCB4016660