Document 9r2V3VpZwgGVgko6dM6LNa1V

HRARG -- 1278 OTHER HALOGENATED POPs OF CONCERN THE FIRST ENVIRONMETAL SURVEY OF PERFLUOROOCTANE SULFONATE (PFOS) AND RELATED COMPOUNDS IN JAPAN Sachi Taniyasu', Kurunthachalam Kannare, Yuich Hori' andNobuyashiYamashita' National InstituteofAdvanced Industrial Science and Technology (AIST), 16-1, Onogawa, Tsukuba, "NatTiooanraalkiF3o0o5d-8S5a6fe9tJyAaPnAdNToxicology Center, Michigan State University, East Lansing, Michigan, USA Introduction havePerrefcleuiovreodocwtoarnledsuwlifdoenataett(enPtFiOonS)duarnidnrgeltahteedlapsetrtfhlrueoeriyneaatresd.cTohmipsoculnasdsso(fe.cg.hePmFiHcaSl,sPiFsBaSl,soPFbeOiAn)g ernefveirrroendmetnotaalsly"pPeCrsBissteonft, tbhieoatcwceunmtuylatfiirvset, caenndtuarrye".potTehnetisaellycohmarpmofuunld. sToaxriecitgyloobfaltlhyesedicshtreimbiuctaelds, enneveidrsonfmuernthtearl diinsvtersitbiugtaitoinono.fpCeorfmlpuaorriendatweidtchocmhploournindaste(dPFanCd) birpoomoirnlayteudndeorrsgtaonoidc.cSoumlfpoonuynld-s,bastheed rTeuloartoecdhceommicpaolusndhasvheabveeenbepernoduusceeddwainddeuvsaerdieftoyr oovfearpp4l0icyaetairosns(1s.ucThhe1sprcoodautcitnsgscofnotratienxitniglePs,FpOaSpearnsd, 5_5 apancdkmagaimnmg,alfsirte-hfrioguhgthinag nfooanm-si,phderrbliactieddesmaencdhapensitsicmiodfes.sccPuRmOalSathiaosnb.ePeenfflouournidntaoteadcccuommuploatuendisn bhiarvdes 52 3 37% ebxeteenntsahnodwnmatgonciotnucdeentorfaetneviirnotnhmeenbtlaoloddiasntdribliuvteironofofhPuFmCasnswaasndunwiklndoliwfne (1). But, until recently, the he S=E Concern over environmental pollution by PFCs has been growing and is a subject of current 2 20 linotcearteisot.ns,Wehxitleensieavrelileorcastiuornv-esypsecihfaivceinmvaedsteigmateiaosnusraermeennetedoefd PtoFCusndeirnsttiasnsduetshefdryonmamsieclsecatnedd fgaltoebaolf rrgy these new classof compounds. Japan is oneofthe major industrialized nations in the world and prior to tfhirisst innavetsitoignatpiroonjeocctcounrrPenFcOeSofanPdFCreslaitnedencvoimrpoonumenndtsalwamsedsitaartiendJaatpAanISwTasunndoetrktnhoewns.uppIonrt2o00f0,Netvhe Energy and Industrial Technology Development Organization (NEDO). An intemational study between eAsItSiTm,atJeapPaFnOaSndinMtihcehbilgoaondSotfaJtaepUannievesresihtuym,aUnsS,Awhwiacshessthaobwleisdhetdheinpr2e0s0e1n,ceanodf maesausruvreayblweaslevmeald(efetwo r{eelnaptaerdtcso-pmepro-ubinldisoni)n(s2)o.mIenetnhivsirsotundmye,ntwael rseapmoprlterses(uhltusmaofnt,hfeisfhirasntdensveiarwoantmeern)taclolslecuterdofvfroPmeFJOyaSpana.nd Materials and Methods SamSpelveercoalllefcitshioannd coastal sea water samples were collected from Tokyo Bay in March, 2002. Live Sfuisrhfeascecoslelaecwtaetdebrywafsischoelrlmeacntewdeurseindgisasescttaeindlaesnsdsltieveelrsaanmdplbelrooadndweornee Ltaokfenwaitnteor pwoelyrprtorapnyslfeenreretdubnets.o maLp)olywparsopaydldeendeibnottotlee.acThobrotetdleu.ceFaisrhesainddualsccahlwoartienre,sa2m0p0laesL woefrseodpilaucmetdhiionsudlrfyatiecesoalnudtikoenpt(2i5n0dmagr/k afnrdom4thCe ftoirmesoefacwoaltleerctsiaomnpluentsilunttrialnasnpaolrytsitso. the laboratory, and then stored at ~30 C for fish samples ORGANOHALOGEN COMPOUNDS Vol. 59 (2002) 31 o OTHER HALOGENATED POPs OF CONCERN RRFERFRR FEF F SO dE PROS (perfiuorooctane sulfonate) | CF SO, | Fed || SEEFLFAVANFVFA,FD | | PFHS CEO (perfluorohexanesulfonate) S5RAFFREL F % %d 0 #785 (porfuoCrrosouOt.ane sufonate) Extraction procedure bmuifxfOeedrne(f0om.r2L5exMot,rfa(cpt0Hi.o5n1M.0)) Awtfeereterraabtduadtte,ydlfatiomvmoeonnmeiLmumLoohffymdberlotoghoeydnls-sutalemfrpa-tlbeeustsiyonllu@ttihpooenl,ryap(rnModTp2yBlmEeL)ne oufbseodainudmthcoarrobuognhaltye was added, and the mixture was shaken for 20 min. Afer centrifugation, MTBE layers were transferred into another "pTohliys perxotpraycltenweastubpea.ssTehdetshorlovuegnht awanysloenvampeosrahteidturnd(e0r2nuitmr)ogienntoaHndPLreCplviaacle. d Fwoirthth0e.e5xmLtorfamecothtfainvoole.nr s{raamnpslfeesr,teodnientoof lpiovleyrprwoapsylheonmeogtuebnei,zaendd weixtthraS ctedoam fcdciosrtL diilnlgedowattheer.saOmnee pmrLoceodfutrheisdhesocmroigbeendastbeovwea.s mL;Fo(rC1s8eacawrattreirdgseasm,plWeast,erSs0)0wmhiLchofwwaastecronsdaimtpiloensedwawsitphas1s0e0d mthLrooufghmeCt1h8arSoPlEfcoalrltorwieddge5(010m.8L, 3o5f dTirsatcitliloendwwaasteerl.utTehdewictahrterxiadcgtelywSaOsmtLheonfmweatshhaendolwiatnhd cSoOllmeLcteodfi4nt0o% pmoeltyhparnooplyliennewatutbee.r TThhies ltauragnett was evaporated under nitrogen gas to O4mL and transferred into a HPLC vial, Aenqauli'ypHspiPesLdCw-iMtSh/MLSCQmea(TseurrmeomQeunetstw;asFinpneirgfaon)r.medTwuesnitnyg abnL Aogfilfeinntal HsPo1l1ut0i0onliwqausid icnhjrecotmeadtoognrtaopha Ca A2PmCMELaLmmPoAnKi.uCm18acceotlatuem/nme(t2h0amnoilnaisdm.oSbi0lmemphlaesngeths,ta3rtmin,g SatH3I0SE%IDmeOthFaInNolE.CHMESM/IMCSApLaSr)amewtietrh oWpeerreatoepdtiimnitzheedetloecttrraonsspmriatytnheeg[atMivKe]io(nnmzod:e4.99l)onfsonwefrore PmFonOiStourseidngusaitnmgosSpehleecrtiecd piroenssmuorneitioorniiznagtifoonr ions 499 and 99fo quantitative determination of PFOS, yz 399 for PFHS, and mz 299 for PFBS. 312 ORGANOHALOGEN COMPOUNDS Vol. 59 (2002) OTHER HALOGENATED POPs OF CONCERN Results and Discussion Concentrationsof PFOS, PCDD/DF concentrations in PFH and PEBS in fishes are fish samples are also shown. shown PFOS in Table 1. was found Finorevceormypafriishsosna,mpPlCeBssfarnodm the Tokyo Bay, ranging in concentrations from 30 to S58 ng/g, wet wt in liver and from 2 to 448 ng/L. itnheblloiovde.rofPFFlHaStwFaisshaalsnodd5e5t8ecntged/minLsionmtehefibslhoaonddotfhCeomnagxeirmEeulm. cHoonwceevnetrra,tinoonPwFaBsSfowuansdefdou1n9dnign/ganiyn fish. Concentrations of PFOS in Japanese fish were relatively higher than those in some fish samples fPrCoBmstahnedGr1e0,a0t0L0atkiemsesrehgiigohnerotfhathnethUoSseAof(1)P. CCDoDncsenatnrdaPtiCoDnFsosf(P3,F4O).S were comparable to those of `Some Japanese human blood were also analyzed for PFOS and the concentrations were greater than 20 ng/ml in some samples. concentration of PFOS was The values 28 ng/mL in are similar human sera to or less than (5). In general, those PFOS icnontcheentUrSaAti,onwshienrefisahvebrlaogoed was approximately 10 times higher than those in Japanese human biood. PFOPSFOinSsuwrafsacealsseoafwoautnedr irnansguerdfafcreosmea16wtaote8r7 anrg/oLu.ndThtehseeTcooknyceontBraaytio(nTsabwleer2e).coCmopnacreanbtlreattioontshoosef othfePcAonHceanntdramtuiocnhs minorfeishhilgivheerratnhdansePaCwBastearn(dmPeaCnD:D4S2/PngC/DL)F,sbiiocsoenacewnattreartfiornomfaTcotokryso(BBaCy.)oBfasPeFdOoSn in fish were estimated; Common sca bass (883 ~ 3,147); Conger eel (13,214); Flat fish (3,73-6 4,698); Table 1. Concentration*sofperfluoroalkane sulfonates, PCBs and PCDD/DFs in fish samples. Location species Gis on PROS PFS PRBS PCBs PCDDs PCDFsrel. TokgoBaylip Commonseabsss Congereel Fl fish Jpsnesesingeh Rockish Michigan waters,USAChinoolslmon LBarkoewwnhirtoeuftish NoMretdhietmerPraacniSeOaecnaean Yellowfin una Bluc-fin una Tokyo Bay, Japan Common seabass Blckrockfh BaOrliavielfeodunadheerad SeSatibnagrsasy Gray mallet ver 3 3-44 NDAO ND... - bloerd 3 30-6 1S ND4 08 NND Do .o .. . bod 1 3 ND ND ler 2 IS198 719 ND... B-s bood ln 2 2 749% 2638 30092 ND. ND. ND. : oo bloedr 23 248 6078 ND4 NDS ND... ND... - ood 3 6476 NDS ND. - - fee 6 30... oo. () 0F< E2... om oa... ow sas... Lm edible issue 5 Sam oo wholebody | = = =~ Ll 41 @ IE oemARE] o oe e eu s s0 wo@ Lee em 9 # Consenrtions ofprfuoroaikans sulfonates in lveandbloodar shown as ng (wet wt.)an nm, respecivels PCB andPCDDSIPCDFs are expressaedsng/g(net wt) apng dwet we. respectively. ORGANOHALOGEN COMPOUNDS Vol. 59 (2002) 313 " OTHER HALOGENATED POPs OF CONCERN Tsualbfloen2a.teC(oLnAceSn)tarnadtiPonCsDoDfpSe/rPfClDuoFrsoailnksaunrefascuelfwoantaeterss,aPmCpBlse,s p*yrene, acenaphthene, linear alkylbenzen Locaion 0 FOS PMS PIES PCBs pyrene cemphibene LAS FCDDs CDR cet TokyoBay, Japan PETE EY A TemesseeRiver-Upstream TemesceRiver,Downsiam 22 18 17-58 75-144 = == = + +--+. +. - - .@ -@ TokyoBay, Japan Coastalarea,Japan i 30...o .038.0s70emooo. s 26-e 3113-e 22 ) oe ee ee e TamaRiver, Japan Bee 30-180- - () e#xCpornecsesnetdraastinogn/Lo.fPpCerDfDl/uoDrFosalckoannceesnutlrfaotniaotness,arPeCeBxp,repsysreednea,s afgc/eLn.aphthene and LAS (total LAS) are Japanese in fish in stingfish (713 4,551); Rockfish (1,425 field conditions and these are similar 10 1,860). Thisis the first report about the estimation from laboratory test (9). BCF of PFOS. These results provide the first evidenceofoccurrence concentrations are comparable to those of PFOS in sea water and fishes in the U.S.A. The environmental from Tokyo Bay and that the concentrations of PFOS may be similar (0 those of PCBS in Tokyo Bay and a comparative survey is underway. Bioaccumulation of PsuFrOvSeyionffPisFhOfSroamndseraelwaattedercoismspiogunnifdiscainnt JianpTaonkaynod Btaoyu.nIdterisstnaencdestshaermyetcohpaenrifsomrsm ocfotmrparneshpoerntsiavned chemodynaomf PiFcOsS in the environment. Acknowledgements. `This study was carried out with a financial support by NEDO, Japan. References 1. GiesJy. P, KannanK. : Environ. Sci. Technol., 35, 133-91342, 2001 2. YamashitNa. : NEDO project report, 2002 3. 4. Environment Sakurai T., Agency, JAPAN : Chemicals in the Environment Kim J. G., Suzuki N., Matsuo T, Li D. Q., 2000 (in Yao Y., Japanese), Masunaga 2001 S., Nakanishi J Chemosphere, 40, 627-640, 2000 5. 6. Hansen K., Clemen L. A., Ellefson M. E.,JohnsoHn. O. : Yamashita N., Imagawa T., Miyazaki A. : Organohalogen Environ. Sci. Tech3n5,o76l6-.77,0, Compoun3d9s, 389-392, 1998 2001 7. HanseKn. J, JohnsoHn.O., EldridgeJ. S., ButenhoffJ.L.,DickL. A. : Environm. Sci. Tecnol., 36, 1681-1685, 2002 8.NisNh.,Tisusyimaa Y,,ImkedaaY.:Jpn. 9. Moody C. A., MartinJ. W, Kwan W. C., J. Toxicol. Muir D.C. Environ. Hea4l1,2t34h-23,7, 1995 G., Mabury S. A. : Environ. Sci. Technol, 36, 545-551,2002 314 'ORGANOHALOGEN COMPOUNDS Vo59l (20. 02)