Document B8pOQKMewaNQyJVoODaYNn4g4

Chlorinated Biphenyls in Fish, Mussels and Birds from the River Rhine and the Netherlands Coastal Area by ). H. KOEMAN Institute of Veterinary Pharmacology and Toxicology, Utrecht, The Netherlands M. C. TEN NOEVER DE BRAUW ft. H. DE VOS Central Institute for Nutrition end Food Research, T.N.O., Zeist. The Netherlands Polychlorinated biphenyls ere widely used in industry, and they ire now making an appearance In the world's wildlife. Besides being a hazard In their own right, they interfere with the detection of organoctilorlne Insecticides such as DDT. Ar tho ond of lOflft a nolo in tho Afav ^senSseS1 mentioned a group of compound* which appoar aa unknown pooIra in nn clirotnatognuiui of tho tisauos of fiah and wildlifo. it Hwodon it. won found Uiat thoao poaJte eoimepoiid to lMiiychlorii)nt4x] binlienyls (PCJJs). PCD* am uwmI in iuduatjy aa lubrioanta, heat transfer inndin and himilatora. Tlwy aro oorapatible with paint*, synthetic rosin*, vamidwa and waxes, and improve euoh proportion of t-hone produota aa thoir choinioal resistance, water rc*i*tnnno, edltosivonas* and floxibiltty1'*. In 1W7, l*CHs wore reported pronent in fish and wildlifo in Groat llritniii and tho Netherlands4-*. In theao studies tho idont ifiont inn wan primarily baaed on the oompariaon of t.lm gan liquid chromatography retention times in the eani|>io extract* with tltOM in solution*-of technical PCB iniitiune supplied by the industry. No Information we* gjvon alMjut the identity of tlio individual peaks. Wo dcsoribo huro tho ooourronoo and distribution of PCIJs in tho Hiver Rhino and tho coastal area in tlio Netherlandn. Tho identification wan carried out by gan chromatography and mane s|>octro>notry. >'or this |>iir|MMii a CH 4 mane spectrometer (Varian Mat Uiubll) whm ooupled to a Varian Aerograph Oven type A /WWi./f. Particular attention was paid to tlio doaign of the intorfaoo between the two instrument* in order to obtain tlio Ixwl operating conditions'. Tho relative rotontion time* (r) were estimated with a 204-1/? Varian Aerograph gan ohromatograph with eloctron capture dolivtion. Pyrex ' glass columns (6 footx 1/6 inoh), filled with 10 pur wnt DC 400 on Gasohrom 0 (80-100 mmli), wore used in lxit.li gas chromatographs, and tlio oolutnns wore ojieral^Hl i 200 C with helium or nitrogen as carrier gim Tho tiswues of tho indioator organisms used throughout this study were extracted with potroloum ether m a Soxhiet extraction apparatus after drying with anhydrous sodium sulphate. Tho sample* wont cloanod up by di- TrpsofasmpU 0-U Oil HottOh(lewtoni mtilM) toUl body HCB ditma 1WT, ISM m (*> 6*{*> e>lt 0-14 o o . *i 0 66 071 *W(4> t(4) t(4> OrrundHaf (OoNsspNsI totol body <+ lUMts INS . 0-71 o-M n 6S4 (ti> 98* (I **S(6> MHl t|| tllTMt* I IS4 (61 rhsncMhlor l>r Arcctilox lteo Gtopbaa AM 994(61 SK4 (6) SCI <t> Ml <&> lt(61 SCI (61 S nwWnitthI*tbOsxexomhpntrlonnnotuTrBuOi.B.AUk1W0 wlrta* sasd*tsJoJmvBpoQunAo*Ca7SiM(9)imMal csOMTOsoOu-tsOaOs tdMohs)tloMolusnnwatouefouraarudb. t*It-oMPOO*BsC.. +c,wArrltiw (1milvXra, (rojt|Wa>timoln./mUttwn>).* pHMwhm mtalsUoM SM boss* os 01-96. ^Ttas sssssltat fists* * tMtatoC Is Ttf. *. HCB-Heuchloroboimr.-, tok*tln-1.9l4>6.9.T,M-otaMnn> HONS 034919 mothylfermnmidc partition* and column chromatography over activated C'oluum chromatography wan performed in two atop*. Dirst iJjo a polar compounds including (.lie PC'Rm worn eluted with hexuno and thon a 10 per cant diothyl other in hexane solution was used to chile dioldriu anti endrin. Only tin' results of the first frm-lion analyses aro reportod hero. In Tables 1 and 2 the nrintivo ntA-idion limes (relative to dirldrm us M>0), thn mass numbers and tin' munls'i" of ohlorino ntoms/molcoulr uin given. Miikx hjkm'Iih were |.akoii from all peaks present in tlio total ion current chromatogram obtained with thn double ion source of the (1)1 4 iiuifw spectrometer7. In Fig. \A and Hi gim chromatograms are. given of an cider extract ami u tech- niea) PCR mixture (J'hcnoohlor 1)1'0). There' in a strong roHenihluhoe liotween the electron nnpturc chromatograma mil1 the ion current elu-nmatngi-ams. . .. s Relit from (he muss numbers and the mitnlicra of chlorine at nms/mnleculn we .conclude that moat. of flic, compounds present in the extract* can bo identified aa l'(lJtH. Tin- relenlion times iucnuiw in proportion t.o the inci-caw in the nnnihcr of chlorine at ouwfmoh'Qnit*. A remarkable resemblance wan found in tho chromatograms of Phennehlor 1 >J * <(, ('lo)ibrn A 00 mid Arochlor 1200. (-)thci' chlorinated oomjsmmls found ure tlie fungicide hcxnehlorolK-nr.ene (11(111), p,;/-DDK and the insootUiido b'lndrin. 11(111 occurs in all places where imficut-m* orgunism* were collccD'd, and has aIho l.wun* delected in aoed- eating and predatory birds in the Netherlands*. Jl d<h-s not w<nn likely (hat tho widcHproud distribution in the aquatic environment in caused merely by tho small scale uho of (he eomponnd in sml drcHHiiig practice. On the other hand, if must be cmphnsiKcd (hat 11(111 in a very inert compound whirl) hIiowh a strong lendeney to iiccmmi* lalinn in animal tissues. Of the 1 >J*1' derived tyjKi of compounds only 1 >1 >10 w* detected, although one PCD interfered with its determination. In a former study DDT and DDD were dctootiod in seals from tho Wiuldcn Ken1*. Tclodrin wiih only found in sea birds, and from other HtudirK we cun coneludo that this insecticide must have originated from a pesticide producing plant, near the month of tho river*-*1. I kith in tho ronch and the birds a comjHinml with r,c 0-71, mass number 37(1 and B Cl was dclei lcd. Further studies concerning Ok* identity of this compound arc in progress. Te( rnohlorol>en-/.ono and ponta- chlonilM-uxeoo wei-e detected in t.he roach by the mass H|H*ctrnmefcr at relativo retention times shoi-P-r lkan 0-2(1. There is a marked r<'semblance Itclwocn the three Mimpling an-as in the identity and pattern of the POJJ* wiih relative retention times longer Ilian 0-71. It seems hkdy therefore that, most of the PCD material present in tho (ish and sou binls living in the Waddell S<*a originated in tho Kivor Rhino. The coastal water chiefly flows northwards. If has b(*on olworved that, dumpings of chemicals on' diluted to a low degree in the littoral current. Min Ktg. 1. 0m rhromnbigrnma of A, on ritlir cxtriu-t. II, a trrtiniral ren nilKdim <i`lwtK<<(lo[ UV 0) mid 0, a ((Hull lin-r * brain rxtns-t (lur an Cxjilaiinlkin, nrr Clie text). Jn IH0r> a clandestine dumping of cop|H<r sulphal** was displaced over a rnngo of 100 km in a northern directmu within a fortnight. R was diluted by a factor of live1-. As can Ik* wen in the tables, tin* lower chlorinated 1'Ols occur more frequently m (la- tissues <l the much than in the sea birds. This may indicate (hat the lower chlorinated ]'(llls are less pei.MsIeiil, and ibis bus ! n coulinried by an experiment unit Japanese quad winch wen* fed a diet, voiifnitiiiig 2,000 p.p.m of plit-iinchhu D1* G of which the chromatogram is given in Pig. 1 H. All birds (n r.-20) died lictween fl and 5f days after dosing started. A chromatogram represent mg the residue m (latissues (liver and brain) of these birds is given in I'lg. 1C. It can be seen that a number of tho noiii|MHmds present iu the original mixture were metabolized, particularly (lalower chlorinated ones. Residues in the brsitiH and livers nf the i|imil were monsured on a winujuant it at ive wule by |a-ak lieiulil comparison of peak r, = l-4f> using (he riieias-bloi- DPti mixturo as a st.andnrd. Residue levi'-ls t-nletilaled m tins way were about twenty times higher in lie- quiol tissues than iu the livers and brants of the eiders. The quad Tutilr 2, a*HK niimmrhh am svsassr or eaiomss atonh/mci.koi'I.s Os t*AHKKTiiRski.) or rKAKti with itn.Arnr iiSTrsties -roots (kki-atuk to lllKI.DMlN - I) or I'KAKH UlNtir.H THAN 1-00 Hhai|ittnR Aren Tyi* of wuiiptc lUstrti (Iswiarn* mlilva) total ImmI.v extrarta Jt7. lbftH 101 T>1>K 81Ui nm u.) 117 36S(0) 1-29 9f.S (0) 8f.B(t)) 3fl2(7) 100 302 (7) 10(1 802(7) 2 27 902(7) i 07 902 17) :t ?ii 80-J(7) -i r,s 4-JAlHl ) (IniHii'lltng (flMn gohio) tcUl IkhI.v r*lr*cla a loos 2 Mhmm-I iMi/lilnt rdtJit) 100S A 9 Nimil eel Hmmorfvfr/<rNre>tolH*) 1000 a- 9 RiiihIwIkIi li'in (Slrrun $anAvirrntit) IIhut and DDK OKS rxtrsrta 100b. 100A 810(4) ' , . S24 <R) 8 Klili-r (tfnmnfriin mot/ifivml llaAiim and ffW DDK rxlracla IftOfl. 1007 910(4) 824 (6) 8f.S(fl) 308(0) 824 (C) 9fiR (8) Sr.B(0) 324 (D) 3t.H 1(1) -.802 (7) 302 (7) S0`:(7) 302 1.1 ?' o 3r.H(0) H02(7) 302(7) 302(7) 302(7) A2lt(i l-lii in.t'tilor Dr 0 Ari.rlilur 120(1 CI<i|ilS' A Otl 368 40) 968 (A) 869(0) 868 (A) 302 (7) 868(0) 802(7) 392 CM 802 (7) .868 (1)) 368 (0) 868 (0) 868 (0) 802 (7) 368 (A) 802 (7) 382(7) 802(7) 368 (A) 968(0) 868(0) 868 (0) 802(7) 868 (0) 802(7) 802(7) 802 (7) Willi Dipcxra-pUnnof D1>Kall oompoundaldoRfltlod arc conformable Ui ITJta. A .At t!iclvpu n-b-ndiiii this-a (H-nfa (Miri'M-iidnitii-ifmiiiMtoiiraiii. Bet- neU'A iniilrr Tiit.li-1. SONS 0U4920 <1 ) 'J'lm poyuliar physical proportion uiwl chcmtcitl sliibjlifv of PCI is make it. likely that. the nppliriilioti will mervuHo mid tlmt. thoir release into the environment will ooninnir. Although fatal concentrations are probably ant devrli>|>cil yot along tho Dutch coast, wo suggest that monitoring of the environment should bo curried out regularly in order to keep an oyo on tho further trends in the level of con tamination. Apart from being n potent ml im/.ord in the natural onvironmout, these Pt'lts also represent an mo portent source of interference in the detection of maccti cidm HiicOt as DDK, o,p'-J )| >T, p,j>' J >1 IT and J >D11. Wo thunk Air J. It. Ponnings, Miss .1 llocvink mid Mr J. M. Eyndhovcn for thoir technical uhmihIiiiioi\ Autopsy of tho quiiil was carried out. hy Mr J. (!. Vos. The technical P(!]i mixtures were supplied ly Prodeler in Kruncc (phonochlor), Monsanto in tho US (m-oehlor) and Payor in Dcrmnny (elophen). Pish IVnm the IMiine were supplied by the Depart ment of Sport Hulling and Professional Inland Finding in Utrecht llcoeivod bcomniicr 24,1068. <)ovoIo)m1 hydroiHtricarda with a do*o of 2,000 p.p.in. 1'|irk cl nl.'1 also disenvered hydrojioricards in White l<eghorn cockercla dosed with 400 p.p.m. in thoir diet. No liydroj>nrieardK wrro olworved in bird* which died in Mm Wtuldrn Son un*n. Detail* of thin Blndy will bo published Hopimil-oly. ' A'nr Xcl.,n, 612(1060). Afimmmlfl Company Verb- Hull- A'#. f/.-AOO (IWHO. ' finepctoptiui of Chtmiral TtchnahtQH (Mil, Iiv Klli f Klfk. It , Hint Otlimrr, 1). K.), rcond rev, ml., 6,286 (1604). * Holme*, 1>. O., Simmon*. J. 11., nimI TalUm, J. I CM. A'/ifmr.C10. TV7 < 1607). * JloMon, A. V.. ami MrdhIi ii. K.. Xatw*, 216. 1274 (1607). * Kociimu, .1. II., ()nkani|>. A. A. 0.. Veen, .1., Jtrmnver, I-:, lluoili, .1.. Kwitrl.. V . y.i. llrnek. 1. . hmiI van ......Ire. . )l . Afrrfr,/. hattdhoutnfttfnmhttpprn (.Ytif. 22. 841 (1607). 'ten Kncver dr Brmiw, M. (*., nnd Jirumitc, (1607). f. Anal. (.'Arm., 226. :i"l dr Fnubcrt Maunder, M .1Kgan, ft., (Jixllv. K. W.. IlnMimcnd. K W,, Hokum, .1., nml Tln>iuw`. .1., Analyl. 66. MS (I Ofli). ' Von, .1. 0., llrmnan, llrlty A., mu) llrnm lioji, II., Mrlrd. J*H4bouuurtfnchnt')>r>t Oonl, 66 (In Um |>nm). nth it " Kuomii,3. II,,mtd vaniirmlmm,)!.. J. App1. Kri4..l(8wv)iV)l661HUM), '* Knrmnn, J. H., Vqmi, ,1., Unitnm, K , lliilammi dr |*rmiir, I. . kihI Koolrn, J. I,., JMgot. Il'iiarntrA. Mcnfiunlrri., 17. 270 0608). ' llfwkam, H. Tti., Intonahumtl Canftmtrt an Oil l,nllulii>n nfthr Nv. Hunt?, OrUAx* r Jl, mr,K. ?l "Flick, 1>. F,, O'Dell, It. 0., nml Ct.IMn, V. A . I'mllry Srirnrr. 40. 11IHI (160f). Primed In Omni Britain by Piihar, Kniahi it Co. Ltd . Si Atbani M0NS 084921