Document DMv3o24qYVMe8wvYpBZ8DGk9B

DownloadRandom document
L Rcpo Perflt Sainp and Ser-.ice.% St. 77N*fl4-24 3M LaWratDryRepit LCMSMS Analysisof ixtractsreportedin:"PreliminaryReport Analysisof PerfluorinatedCompounds inEnvironmentalSamples" by P. Jones and K. Kannan Reportnumber.FACT-GEN-008 Tesdng Laboratory 3M EnvironmentaTlechnology& SafetySavices 3M EnvironmentaLlaboratory FluorinAenalyticaClhemistryTeam (FACI) 2-3E-09 935 Bush Avenue, St PaiL MN 55106, LaboratoryContact KrisHanser4Ph.D. Bldg.2-3E-09 P.O.Box 3331 St P&A, MN 55i33-3331 Phone: (651)778-6019 FAX: (651)778-6176 Requester 3NVBattellEexposureTeam (c/oSusanBeach) 3M Company EnvironmentalLab 2-3E-09 St.Pa4 MN PAWIOF5 ILVI*IROV.V/F-%L4,T4.B.OLRLAroRr REPORrivo. FAC7,-(;&V-Ooa :i',,.:,[ntroducdon samplec.<tmcptrse,parebdyP.JonesandK Kannana=rdingtoFACr-M4.0,vmm screeneudsinga McromassPlatforl7lna@singlqeuadrapoLlCeMS. Thesem= c=actswerere-w=nodbyFACR tlc@mag NficromassQuatim 11,a triplqeuadmpole klqnmiem (LCMSMS), wlfichpmides a more selectivaenalysis thana singlequad in@@ Interferenctehsatmay providea faimpositivreesponseinLCNIS arabsiscan be eliminatewdithft LCMSMS. F-xnctsfrom mimles of'seaeaglepbmia, baldeagleplwna, and fishwereanalyzedquantitativefloyr PFOS usingtheLCMSMS. In generalP,FOS levelsdeterminedby LCMSMS were approximatelyhalfof tm determinedusingLOAS. Itislikeldyig ni=x mtcfere= atoraroundnam 499 complicatetdhe on&W LCMS analym& Thisqpe ofmatrixmterfermw near 499 hasbe= dxaved inotherbiological samplosyor theLCWLI%INMana4sLs,quanatadonwas basedon the499 --)99,130 daugbta ionsreq)om Inft LCNfSN4S analys@ low LevelosfPFOS (<5 ppb)w= detecteidnwmal ofthefi& sampim dm valuesaresigmficudlylowerthanthm reportebdy Jonesand KanmrL Itishkdy d= a matrixintcff=mt causedan ano=lously highresponsehitheLCNS anabsi& No PFOS above thelimitofdetectiownas ddwted inthermnawing flshmniplesanalyz@ by LCMSNZ. Agab% thisishico== totheLCNB nabds. Additionallayl,lsunplesofeaglepW= were scremiedfbrthefollowinfglwrochamcals:PFOSA, PFOSAA, M570, M556, POAA, PFHS, and PFDS (9= AppendixB fordeflritioonfsFACR acrorym). Very low levels(< 5 ppb) ofPFOSA were observedintheNorthAmericanbaldeagleplasm =*eL No PFOSAA, M556, POAA, orM570 was detectedinany mmples. PFHS was detectedineveryBalticseaeagleplasm smuple,whilePFDS was prehmmarfly(no standard materiaalvailablfeorconfimiadon)detecteidneveryNorth Americanbaldeaglepbsm mmple. IbLsdatais==mg qmhty only Only2 highlevel(250-ppbP)FOS ma= sp5m mmples (eaglepW=) wo extracteadnd ana4-zed. P. Jonesand K Karman deliveresdamplestotheEnviro=cntd Lab. The sampleswere extracteadnd ana47,edby them usingan EnvironmentaLlab LCM on March 15-19,1999. AfterLCMS analysisf,t am= vn= subimttedtoFACR forLCMSN6 analysisl.b= was no camctionpaperworksubm=ed with thesamples. Itisasaimed thatmmple volume and finacl&act volume were thesame tines There isno holdingtimemtena associatewditli&=e samplesforLC/ESMSMS armlym. PAGE20FS P-V;*IRO,%-.tfF-IIY-TI.B-OIRLATORY REPC)RTNO. F.4CT-GLV-Xa Mdhods -Analyticanld?repa*ory Analytimceatlhods FACT-M-3. 1,Exu-actioonfPotassiumPerfluorooctanesulfoorrtOattheerFluorocheriiiCcoamlpotuids fromSenim orOtherFluidforAnalysiUssingHPLC-ElecuWrayNLI= Spe=nletry:modifiebdy NOrr ej=ctinga rmtrl-ccurveforuseinquandtafiomA pre-exlsfianigm, cc=ed fromrabbisteraw,as used forqja=tationT.lusmodificatiwoinllhavethegreatesetffecotn thefishsamples.Exu=on decie=es ofmostofthetargeftluorochemicaflrsomtheft dsam am likeltyobesignificanltolwyerdw aim fromthepl-ma Forthisrmwn, LCMSMS reportevdaluefsorthefishtime samplesshouldbe consideretdobe miniinurm FACr-M-4. 1, AnalysisifPotassiumPerfluorooctancsulfoonraOtteherFluorochcniicianlSerum orOther fliudUsixWHPLC-Elw=Vray/N4= Spe=mctry: modifiebdy quardmng mmplesversma standard curveextractefdrom rabbistwa,notfromthesamplematrix EIPLC/ESMS and HPLC/ESMMS InHPLC, an aliquootfa== isinjecteadndpassedftmgh a reverspeha--Hquid mrwhic cohmm Basedontheamnityoftheambft forthestationaprhy= intheoolumnmbtiw toiiihquid mobde phase, the x2byw isretainefdora chamcu=c amoum ofum Forcample, m a =Ward solutioPnFOS may clutaet8.0mhdm Rmntion timesbetween a standardPFOS solutionand the analytceamcted fromgmundwaterinthisanalysiwsere matchedon theIHPLC systemtowithin1% FollowingHPLC wpamuon, ESNISW provides a rapidand accuratema foranalyzing a wide rapp of organiccompounds, includingfluorochemicatsE.lecmxpW, an ionizatiotnechniqueusedpdmzily for detectioonfmolecularions,isgeneralloyperatedatreli&dy mildtcmperdum. Moleculesareiontmd, and a primaryion,chamcw=c ofthean*te, isselectecTlhisionisbombarded withhigh-energygas; subsequentcohmons awe mmucr secondaryiomc fragmentsuniquetotheprimaryion,winch are detected. For CMMPIC, for PFOS (CSF17SO@) aM4SiS, ion 499 isselectedasthechuactmisficprimary ion.This ion isfragmented intootherionsmwb as80 amu (conmpondmg toS03), and 130 am (CF2SO3). Each of thesesecondaryf3ragmentiss&iwted and can be used todifferenum PFOS from othercompounds that nughthave thesame chamc=zc 499 anm primaryioA butdifferencthemicalcompositionsand secondaryionfragmcn=oa pan=. 5.1 QuantitativeAnalysis ForboththeLCMS andLCMSW ambsis,quantitatirveesultasrebasedupon comparisonofanalyte peak area inthesamplewith aralytepeak -areagencmted usinga smrdardscxtmcted from rabbitsera. The c=ction efecimcy of PFOS from seraofotherawnmls hasbeen determinedtobe between 75-950/o atalllevelswithinthermp ofquantitationI.tislikeltyhattheextractioenfficiencoyf PFOS from eagle pbmm isapproxiimtelythesame. 5.2 QualitativeAnalysis Eagleplmm sampleextractwsere qualitativeslcyreenedforPFOSA, PFOSAA, M556, M570, POAA, PFHS, and PFDS. During thearmlysist,heexnm were bracketedby a mirjrnum munber ofstandardsto mor@toranalyteretentiotnime.Otherthanrcl-divceomparisons,no quantitatirvesultasreavailable. No PFDS standardmaterialisavailableP.mUnWiary idcntificafioofnPFDS inthee=cts isbasedupon responseof3 reasonabledaughterions(5994 80,99, 130)ata rea leretentiotnime. PAGE30FS j.&%vv.i,)?otvtizvruL4aoR47*oRr REPORTVO FACr-GEV.008 5.3 Blanks Twocontaibnuenrkswerepmvideadndcxtmctbeyd]oneasndKmum Exuuctibolnankwserealso preparedN.o analytewseredct=ed intheex=ts ofeithetrhecontainbelrmks orthec=ction blu&s. 5.4 Matrix Spikes One PFOS matrixspikeat250ppbwaspreparefdoreachoftwoeaglepbmm samples.Bothmatrix spikesshowedgreatedrm SOO/roecovery. 5.5 Laboratory Control Samples LaboratorCyontrolS=ples arenota componentofft gudy. 5.6 Sample Related Comments Alldataissmvemng qualitoynly Allanalyticraelaftoffishbssuec=xts gx)Wd be consideretdobe vchearrypamchtemruiwzye,& asthecm=on cTldcL-yofthemrgetfluomchmmmisfromdxse matnoesisnot Exwactsfrom mmples ofseae4e pbmw, baldeagleplasma,and ft wereanab7.edquaamawmly for PFOS umng The LCMSNE. IngmeralPFOS levdsdetmmmad by LCKS?VS we= approxm=elyhalfof dum determinedusingLCNB. Itislikeldy= matdx knm*n= atoramtmd ma 499 complicatetdhe LOAS anabm& FortheLCNLSNS anabms,quanftmonwas basedon the499 4 99,130dmi ions responseN.Lvrixiwafin= at499hasbe= obsmvcd inothebriologicsa=ltplel Low levelosfPFOS (<5 ppb)wered&=ted inseveraolfthefishmmples;thesvealuesare4acaudy Iowa thanthm reportebdy JonesandKamam Itislikeltyhatamatrixintmfmcitcausedananomolously highresponseintheLCNZ anabsi& Mm typeofanomaly hasbeenobservedby FACR on othersamples anab=d byLCN4S andLOASW. No PFOS abovetheU= ofdetectiownas detectemd theremaininfgishsamplesan*zed by LCMRA. Again,thisisinco ,;trt,otheLCNS analysis. Additionallayl,lmmples ofeaglepW= werescm=cd forthefouowingfluorochen3icPaFlOsS:A, PFOSAA, M570, M556, POAA, PFHS, andPFDS (seeAppendixB fordcfmitionosfFACR acron3n=). Verylowlevel(s< 5 ppb)ofPFOSA vnn observedintheNorthAmericanbaldeaglepb= sm4ges. No PFOSAA, M556, POAA, orM570 wasdeWW inanysamplm PFHS was detecteidneveryBalticseaeaglepb= smnplew,hde PFDS was pmhmmanly (w gmxl-ard matnw availablfeoroonfim-adond)ewed ineveryNorthAnx:ri= baldeagleplasmammple. Thisdataisscreeninqgualq only.Only2 highlevel(250-ppbP)FOS ma= spikesamples(eaglpelasm) wereextracteadnd analyz@ Samplesand e=wu wiU bemttned forfumm evaluatioizf4necessary. PAGE40F6 JU MV P7RONAIMVrALLABoju 7-0,rR PzpoRr,vo.,FAcr-G,cv.ooo 8.1 Attachment A: Table ofLCMSMS P-esultfsortheAnalysisofEagle PLum and FishTissue Samples 8.2 Attachment B: Table ofFACR acronyms and fomuln 8.3 Attachment C: Data associatewdithLCMSMS analysis 9.4 Attachment D: LCMS reportby P. Jonesand K Kann:tn Hmold hhmme, Adfm- Chemist KrLsHinsM Ph-D,-IiCA-r C=W T Daft Datr. PAGESOF6 toe 3M Environmental Lab - FluorineAnalyticalChemistryTeam FACT-GEN-008 Sample number WrEA-SWE-93-020 WTEA-SWE-93-017 WTEA-SWE-93-012 629-38263 629-38264 629-07411 629-35547 629-36389 629-37030 629-37021 Tissue: Sea Eagle Plasma Sea Eagle Plasma Sea Eagle PlasffBald Eagle Plasma Bald Eagle Plasma Bald Eagle Plasmt Bald Eagle Plasma Bald Eagle Plasma Bald Eagle Plasma Bald EaglePW= Locatioin:@t-ic Baltic Baltic Baltic N. America N. Amexica N. America N. America N. America N. America N. America ns P S mL 125 93 215 165 199 494 1047 226 371 374 PFEES? detectew-d detected detected PFDS? deteacd detected detected detected detected detected detected F980086 F970312 F970310 1998095 F97197 1998095 1998064 1998064 F9&0081 F970181 F97002 1998064 Carp, whole body PineRim, NU BLD Lake Trout whole body Siskiwitb,a BLD Lake Trout whole body Sisidwitb,g BLD Brown Troutmuscle DetroiRtim, 0 BLD ciscowet muscle Lake Superior BLD Brown TroutLma DetroitRiver,NO BLQ Channel Catfishegg Lake St.Claire,NU BLQ Channel Catfi& egg Lake St.CW=, bC BLQ Lake Trout,whole body Pine River,Nfl BLQ Lake Trout,whole body Lake Superior BLD WaUeye, whole body DetroitRiver,14 BLD Channel Catfa muscle Lake St.Clan--,NU BLD BLQ = below Umit ofquantitatio(n10ppb) BLD = limitofdetection(approxunatelIyppb) 3M Confident-iAatltomey/CliWeonrtk ProducPtrivileg-eDdo NotDisclose 3M EnvironmentalLaboratory-FluorineAnaiXgcalChemistry Team KrisHa=n -Sr.Analydml Chemin FluorineAmlyficalCb=ni=y Team Building2-3E-09 612-77"18 Screeningof PFOS lc,%,eilnsEagles and Albatrm Slimmary: Tea samplesofbirds= ofbirdsem &a fromjwienflbealdca& andfte fim Iaym aroatrossw@e receivedatthe - I-ab lle eagle serawas collectedftom buds in Nartbem Minnesota (I sample),theUpper Peninsula of Mchipn (2 amples). and the L4m= Peninsula of Mchipn (2=Wles). All butno nwics wereobtainefd= birdsfml-naattheOM= CbbpkK an SandTrJ2niiwithin theMdway ftU inthenorthcotml PacifiOcemm Mm seraamplasweremaractedc,amcti wem anab=d quantLaWi*for =Mnate 070S) by biovmm= liquid mmopVby-clecuosprAy man qmcaometry(MC-ESW. Anabftidentiflcawtaisonveriflebdy comparismofmaleculiiron-ED?LrCct=donfim ofthecku-acted an*tr@andsmdardm2t=isl Samplavmmquanduth*cvahatedagairAafiveTaintsobentcm-oMm samplesofeagle=a were determinedtocontain30-77ppb uorooctaneaffanate (:FTOS);no PFOS was dct=ftdm theaV=m abovethelimitofqm=tation (10ppb).Specifircesults and analyticaplarametersare anachad to thisreport The presenceof?FOS in =mpl ofeaglesem was verifleudsing13PLC-EShMA. This w.hnique providesan -'Aitiona&lWw of=taiuty totheanalytoMendf=don by qmdficallymonitoring ftagm=ft daughterion&(m/z-80,99,130, 190,230) characteristoifcthePFOS primaryion (mtz - 499). The presenceoflow levelsofPEOSA, pe&uorooc=emdfonylamide, was alsoconfirmedineach ofthe=mples ofeagle=a FaWrimental mmmary: Sampkprgparation.Ion-pairinagtr=tion In a pH controllecdnvumment, an ion-pairinrgeag=4 =abutyl ammonium mdbw (7rBA),is used to== theanalywfmm thematrix Aniamc comnunds. blw PFOS and -- (POAA), aresdwti,,* targetebdy thecationirceagent Subsequenttothefornmdon oftheTBA-anion pmr, thea=bu is=sfared toa ncm-polarorpluc solvent(c&ylam=), dri4 and reconstluteidn methanolforEPLC-ESMS =ab!dl HPLC. Charactensderetmdon timesforPFOS InEPLC, an aliquotofthe wd= isinjecteadnd passedthrougha chromatographicolumml Based on theafa&ty oftheanalytoforthestationary-phasienthecolumn relativteotheliquidnwbflephase passingthroughthecolumn, theanabu isretainedfora cbaractmistiacmount ofdm For example,ina standardsolutiorPlF,OS may cluteat 10.5-inina Rc=tion tin= betweena smndard PFOS solutionand theanabft extractedfrom sem inthisanabsiswe= matched towithin1% an the MILC qstem EZ?DS. Detectionand monitoringof themolecular!on ArmlysisofPFOS standardisndicatetshattheprimaryioncha=wxisticofPFOS ismtz - 499 amu, correspondintgothemass oftheanionicmuhc= (Wl7S%-). This ionwas monitoredsdecdvely tomaximize sensitivityA.scan ofmtz-100 to1210 (negativeonly)was alsocouectc& 05/019/98 ES4dMC. Confirmadonofanalytledendfication Sewrals=plcsinthisetwereansIPW byESMSM tovu* thekkzdtyofft PFOS analyto iollES-NM?#fS isverysimi'2 toF-SNE. e=cpt thatitaddsan additionadlumandon ofamuinty to compound identir2catioArsLinESBZ. a compound specffliconissdacted Aft= wlectm the selw-W ion ischaractmizedfwrtbaby smasbin itapartwith high-enav ps. As a resulotfthemashinit ionic fimgments,charactamc ofthemol=de, arecreatedand deacted For comple, forPFOS analysisi,m 4" issdactodn theompamd primaryim This ionissm2thed intootbarionssuchn 80 am (-@IpIp @91*- tOS03,199a=(,---- -,-- toFSC)S-H 130,-u(convspondtionCgF2SOs)1,80!an("C,zF4SO3n1d 230un (C3FoS%)U.PFOS isI inthesampkse,wh ofthen==mlW ftp=b isdcmcteadtthedm=L Qualitcyontromlmmary.Dueto=mplcsi=rt-itwondeupliccaxtuewdm nd matri3xp&eanalyswiesrenotcaaw outondum sa=lcs QuanutafiomfPFOSlevewlassdetumin.raddsimtoa sundarmd6m cm inomtoffanacuacte-dtri-cuve.AstheextractcifofnldmqofPFOSis=known.dum results chatib'eAconsidkm-d-- and ofameaningqwft. The swndardm vu nalyzed twhm. beforeaW ancrtbe=mvks One 250-nb=hUationcbe*wmxmdynda&wftowmvlm was acceptablaetV% W--l quditycontrdwas a=odated.vmhthisxmlrk Nmm precision themcwa= my be =6ana4-ze& Limitofquandtadon The low stana*rdambmed vi& then nmpks wu 10 a*; thisisft limitafqnn*atkm nssoci2tewdith theanalydl R)edfu= HPLC system Howl= PackardSam 1100LiqtddCbmmatoggza,nb- Column:T%cyaonc BetasilCis 2 x 100 mm 5 pm particlseim Flow raw: Solv=t A: 3m MI.Ami" 2.0mM Ammonium Ace= Soh,=t B: Niethanol SolventGradient 45 to90 %;B in9.50minl Ebid at90 %B for3.50 minl Remm to45 %B in 1.50 Hold at 45 %;B for3.5 Injectiovnofmw: 10 pL Injection/$ sa I F-lectrosprmaayssspecirometer M=mass PLVformH API Mass Spe=mcW, -ChiW MassLynx 2.4Saftwwc Cone voltv= -60V Mode. el==VrW wpdw sm= tcmpwau= 115or_ Analy= vaclmm prcs== 0.000043mbar,0.000079mbar Ions:499, 413, 369 El=trode: cross-flow 05/08/98 2 FJ*OwpuyAdSW NUMUMN Qosoo]IAPIMm spwuamaw,-maddine MMULYM 3.1Sdtwm congvokq= .6ow CaDisiopns amm 45V It.-g I n mguhv Sao= 115or_ Aadyzw 0.00004m3bia@0.00007m9Bn TftM Im-499.4'98 Dugkw imc 3k ". 130.130,230.78 Eecftft Z-Rxw OSMS/9$ 3 CONFEDENTL4LL REPORT LOCATIONS AND DATA FROM AVIAN BLOOD PLASMA SAMPLES TO-. 3M Corporation :wmneapoiis,wmnewta BY: Jobn P. Giesy and Associates Hghop Place 2355 Bravender Road Vrffmmston,Nfichigan48895 July18, 1994 Avianbloodpis4gismamplescollectefdrom two speciert,hebaldeagle(Haliaeetus leucocephalaunsd)theLaysaabilros(sDiomedeaimmutabilwlesr)esento3M foranalysfiosr C,F,7SOa2ndCIF17CO2- Additiondaaltaforthesebloodsamplefsollows: Laysanalbatrosses AU sampleosflaysaanlbatroswseersecollectferdomtheOfffceCrlsubploton SandTslstnd withitnheNfidwayAtolilnthenorth-=traPlacifiOc ean.TableI provideasdditiodnatlaon the birdssampled.- Table 1. Band number, yearbirdwas banded, age atcollectioonfblood sample,blood nmple number, and datebloodwas collectedfor5 Laysan aflwmsses from Nfidway Atoll,nofth-cent2l PacificOcean. Band Number 121F2747-60080 Nul' 124477-660000c9,5 1367-32659 1137-90880 1067-19156 Year Banded 1993 1993 1985 1987 1978 Collectoin Age 0 0 8 6 15 Sample Number Date Collected LAC 08093 18 May 1993 LAC 09593 18 Nfay 1993 LA 616 13 Dec 1992 LA 607 13 Dec 1992 LA 617 -rl3 Dec 1992 No otherdataon organochlorinepesticidefsrom thesebirdsiscurrentlayvailableh,owever. a seperatesplitsample of each bas been archived. Bald eagles AU samplesofbaldeagleswere coueetedwithintheNfidwest,withone from Mmesota, and two each from theupperand lowerpenkmulasofmchigan (Fi*gur1e).Table2 providesadditonal dataon thebirdsmmpled-. Table2. Band number,locationc,ounty,region,dateofbloodsmnplecodections,ex,weight,and age indaysof5 Minnesotaand Michigan. -7- Band No. Location 629-31740 Devil'Lsake County Menominee Region Date . Coflected U. Peninsula, 1989 Sex Unknown Wei Unkno 629-31748 629-14593 629-39332 629-39339 SlateRiver Falls Steve'sIsland Baraga St.Louis Caulkins Creek Pickerel Channel Otsego Enunet U. Peninsula, 1989 Voyageurs NP, MN 17 June 1992 L. Peninsula, 3 J@ne 1993 Nu L.Peninsula, 5 June 1993 Unknown Male Female Fermle Unkno 2.7 k 4.851 4.25k LW-VMtDrYPieport .AnalysiosfFluorochemicalsinWild Bird Livers LaboratoryReport No. FACT-GEN-010 LR U2392 TeWng Laboratory 3M EnvironmentaTlechnology& SafetyServices 3M EnvirorunentaLlaboratory FluorineAnalyticaClhemistryTeam (FACT) 2-3E-09 935 Bush Avenue, St PauL UN 55106 Laboratory Contact KrisHansen,PliD. Bldg.2-3E-09 P.O.Box 3331 St PauL MN 55133-3331 Phone: (651)778-6018 FAX: (651)778-6176 Requester 3MENVLRONMENTAL LABORATORY REPORTMO. FACT-GF-,VOIO Sixtlyivesranviecsollectferdomvariousspecieosfbirdwserecharacterwiiztehdrespetcotspecific fluorocheniical'sI.hebirdswere classifieadccordingtospecieand geographiclocation.Sixspeciesof birdsarerepresenteidnthisstudy,includingSsintihiClrlanes,D66le-CrestedCormorants,V*Ute Pelicans, Brown PelicansG,reatBlueHerons,and Brandt'sConmrants. The birdwere foundata varietyof sites acrosstheUnitedStateisncludingNebraska,New Mexico,'Flonda,Arizona,CaliforniaL,oulmana,and Florida.Ingeneral,thecmiseof deathtothesebirdsisunknown. Detailsaboutthelocatioenachbirdwas foundand aboutthecauseof death(ifknown) areincludedinAppendixC of thisreporl Liversampleswere hormgmized and extracteudsingan ion-p&ingex=don procedureI.le exmcts were quantitativealnyalyzedforPFOS and PFOSA usinghigh-presmm liquid chmmatography/electrospratyandem mass spectrometryMLPC/ESMSMS), and evaluatedversusa standardcurveextractefdrom rabbitIrver.Analyticadletailasreavailablienthestudybmder mamtamed by FACR inthe3M EnvironmentalLab. Ile presenceorabsenceof otherknown fluorochemical con=iinmts and metabolite(sPFOSAA, M556, M570, POAA, M513, PFHS, and PFDS) was determined by inspecdonof HPLC/ESMSMS analysiosf2 birdliverwsithineachgroup.A fullisotf acrowlim is attachedinAppendix B. With theexceptionofmost oftheSandhlUCranesand a singleBrown Pelicanfrom Californitah,eWM= from thefiverosfallofthebirdswm determinedtocontainPFOS abovethemethod hrdt ofquanfitation WL =10 ppb).Extractfsrom thefiverosfftm of15 San&dU Crmm showed some PFOS; two offfim eamcts containedPFOS levelsveryneariheUDL. Extractsfrom oneBrandt'sCormorant from San Diego,CA and oneWlute Pelicanf,rom Cahpatna,CA showed PFOS levelsingreatexcessofdww determinedintheexumu from otherbuxisvnthm thesame cwsification(>20xfbrthecormorantand nearlylOx forthepelican)I.fthesetwo outlyingpointsare removed and PFOS Imb withina particulacrlassLEcatioanreaveraged,some generalobservationbsasedon thegeographicalocatioonfthebirds'habitatcanbe niaclt With theexceptionoftheSmdhffiCranes,ingenmal liverfrom birdscollectefdrom thewesternUS (San Diego,CA, Calipat* CA,) show relativeloyw levelosfPFOS, withan averageofhm than50 ppb. Livers from birdscollecteodn theEastCoastoftheUS (Nfiam@Naples,andFt Lauderdale,FL) show moderate PFOS levelsa,pproximately105 ppb. Extractfsrom birdEversCollectefdrom theCentralUS (LA and NV) were ddm-mmed tocontmn thehighestlevelsofPFOS, approximately300 ppb. Itisunlikeltyhatthedffmumm associatewdithPFOS levelisntheliverasrepm* a functionof species.In more than me instancet,hesame speciesofbirdlivingina diffmzamwndnment showed slgmficanfly diffmtntWOS levels.Forexample,livercsollectefdromwhitepelicanisnCaliforniwaereddmumed to containan averagePFOS conomw&on of 58 ppb,whde livercsollectefdrom Whft PelicansinNevada showed averagePFOS lvmlsofover 350 ppb. Saa&M Crmm arean exceptiontothisobservationa,sthe liverfsrom ftm birdswere detmmmed tobe imifonnlylow inPFOS, regardlesosfthegeovapliiclocation ofthebirds. With theexceptionoftheSandhilClranes,liverextactsfrom atleastoneofthetwo birdssavened within each classificatwieorne detmmaned tocontainPFDS. Liverexftxu from severaslpeciesi,ncluding1 SancftU Crane,were debmmmed tocontaina mmU amount ofPFHS. Neady 20*/ooftheliverO&aM were determinedtocontaina smallamount ofPFOSA. No POAA, NO 13,W56, M570, orPFOSAA was detecteidnthehm ewacts from any ofthebirds.AppendixA odnt= theseresults. Thisdataindicatetshatpwntml popapluc trendsassociatewdiththemrvimmmtal dl=-butionofPFOS and otherfluorochermcalmsay be traceablbey chamctmimm oflow-levelofthesecompounds inammal tism samples. 3MEMMONMENTAL L4BORATORY REPORTNO. FACT-GENO]O Althoughng=us qualitcyontrolmeasuresand 3M Envim=mtal LaboratoryStandardOpm"atmg Procedures w= followed,the acquisitionof thisdataww not necessawy collectedaccordingto applicable Good LaboratoryPractices.niis dataisnot suitablefor &qffl@on to any govmmerit agency indefense of product surtabihtyor safi:tyResultsshould be consideredto be senu-quanft=ve. Data presentedh= isthe highestqualitydata availableatthistime. On 5/5/98,Jean Burrisfrom 3M O=ipational Medicine deliveredthebirdhm sanVIes to theBwkmmental Lab; samples were receivedfrozen. The samples were originallsyenttoGeary Olsen (3M OccapatLonal Medicine) by ScottP Hm= ofthe NationalWildlifeHealth Centerin Madison, W=nsm There isno holdingbm aitena associatedwith thesesamplm forLCT-SMSMS awlym Analy&W methods FACr-M-1.0, Extr=on of Potassium Pmfluooctane@onate or Other Amomc Flu=chenucal Surfacl= from I"a forAnalysisUsing HM@DESNE FACr-M-2.0, Analym ofFluorochcmicalsin LrverExtractUsLng BPLC-ElectrosprayMm Spectrometry Sample preparation - aqueous samples,BPLC/ESMSMS: ion-pairingextraction Armlyte isexftactedfrom a sample matrix with ion pa&ing reagent[teftabutyalmmonium hydrogen suffate CIBA)] in a pll-wntrolledenvuorument The catlomc reagentselectrveltyargetsmncnuc rochemical& Once the anion-TBA pairisformed, the analyteismnsfmted intoa nm-polar organicsohtzlt(ethyl accm), dried,and rownstibiw inmethanolforN% m*m. RPLC/ESMS and HPLCIESMSMS: for detailedqualitativewo@k In EPLC, arLaliquotof ex= isinjectedand passed thmugh a reversephase liquidcbmmatographic column. Based on the affinitoyf the analytefor the stationarpyhase in theoolurrm relawm tothe liquid mobfle phase,the analyteisretainedfora charactmisticamount of tirm. For example, ina standard solutionPFOS may eluteat 8.0minutes. Retention fim between a standardPFOS solutionand the analytecmmcted from hver inthisanalysiswere nmtdied on the EPLC ristmn to vnthm 1*/o. FoUo" BPLC separationE,SMSMZ providesa rapidand accuratemeans foranaly2inga wide range of organiccompounds, including:Iluorochenucal&ElecUospray,an ionizationWbmque used primarilyfor detectionof mol=ilar ions,isgmierauy operatedatreltivdy mild tmnpwaures. Molecules are ionized, and a pnmary ion,chmactmutc ofthe analyte,isselected.Mu ion isbombarded with lugh-enmgy gas; subsequent ooummis awe unauer secondary ionicfragmentsunique tothe primary ion,wluch are detected. For MMPle, forPFOS (COF17So3) MWYSIS, ion 499 isselectedas the dwactmistic primary iorl Ibis ion isfragmented intootherionssuch as 80 anm (contspondag to S03), and 230 airm (C3F6S%). Each of these secondary hagments isdetectedand can be used todiffmtnfiatePFOS from other compounds that nugbt have thesame dmctmioc 499 amu primaryio4 but dffmmt chermcalcomposibm and secondary ionfragmentationpan=. 3MD;W,R0,VMENTA L"ORATORY REPORT.VO.FACT-GEWOJO 5.1 Calibration A nud-leveelmactedmatrixcahbr&onc.'=ks=iud isanabad every5-10mmles tomomior msmmienw drillCahbmtLoncheckzu&,xds = comphm ifulsmmmtal responsiesvntbm+/-300/of theotwted value. Quanttadonofthemrgelanalytwisbasedon linearegressioanrmlysisw,eighted1/x,oftwo extracted matrixcm@m brackedngeachgroitofsamples.Quandtatimofeachanal@uisbasedinft responseofa specifidcaughterm usmg themwtiplermponse-momtmmg mode ofthemsuument The secondcurve was notusedforPFOS ddammation, bmdxting cahbratiocnheckswerealloDmplimi4sothisexchlsion doesnotWvmsely affeathedataqmW 5.2 Blanks Two exwacftonbl-mksu,thnng waterassurrogatmeamx, areodmcted vatheachbatchofmmples. Adchtionanyt,wo samplm ofblankmamx, usedfortheodmcted cahbraton=ves, arecomcted along witheachbatchof=Wles andcurves. Blanksarecomplianitfno targeatnal@UisddectedabovethehrmtofdeteclaofnoraspecifiacnalyteI.n tlustudya,llblmks wereanwhant 5.3 Surrogates Tetra-hydprmoflwmoctanemmnate isusedasa mmpte m ft ambw. momtoredto confirpmm mzummtal failuriefn,ecessary Sumpte mspom is 5.4 Matrix Spikes Duplicatmeatnx spflm=*ses utlhmg alltargeatmlyteswereprepareadndarmlyzedfromSandhdl craneliverR.ecoverieosfPFOS and PFOSA were withintheacceptablreangeof70-1300/o. 5.5 LaboratoryControlSamples LaboratoCroyntroSlmplesarenotacomponenotfthissh*. 5.6 Sample Related Comments I&tnx spikewserepreparefdora smglesp=e ofbad Itisa%umd dmtspikerecdwneswouldbe mnilu forallspeciesN.o =dard materiaflorPFDS isn-akle. CmVoLmd idmtificahiosnbasedan masmlablmet=on bm andmmnable daa&a iong)ecinm UnW =dard materiailsmmwle identificatoifotnhisamlyw shouldbe consideretdobepreliminary. QuantitafifoonrPFOS was conductebdy monitorinfgt transiti4o9n9 4 99.Some posifiwirltmf@r= was observedwhen monitorintghe499 4 80 tansitioinnthebirdUm matrixTransitioPnarameterfsor theota targeatnalyteasrelistebdelow 3MEMMOMMM@TAL L4BORA TORY PF,PORTNO.FACT-GENOI 0 Table1:AnalytTeransitifoonrsBPLC-ESMSMS Analysis Compound Primary Ion Transition Monitored PFOS 499 99 PFOSA 498 78 PFOSAA 584 169 M556 556 169 M570 570 169. PC)AA 413 169 N013 469 169 PFM 399 99 PMS 599 99 With the=ovdm ofmost ofthe qwtibillCrmm and a singleBrown Pelicanfrom CaMrnia, theocft= from theIrversofallofthebirdswere detmmmed tocorgmn PFOS abovethemethod limitofqumt=on WL =10 ppb).E&acts fromtheliverosfftm of 15 SandhM Cranesshowed some PFOS; two of these cxuwm containedPFOS levelsveryneartheMDL Fxft= from one Brandt'sCormorantfrom San Diego,CA and one WlutePelicanf,rom CahpatriaC,A showed PFOS levelisngw excessofthosedeterminedintheadractsfrom otherbirdswithinthem= dassificatiCm>20x forthecormorantand nearlylOx forthepdican).Ifthesetwo outlyinpgointsare removed and PFOS levelswithina particulacrLimficatLonareaveraged,some generalobservationbsased on thegeographicallocatioonfthebuds'habitactanbe ma& )Vlththecc=PtionoftheSandhffCiranes,ingenwa liverfrombuds collectefdrom thewesternUS (San Diego,CA, Cahp=A CA,) show relativeloyw levelosfPFOS, withan averageoflesstm 50 ppb. Lners frombirdscollecteodn theEastCoastoftheUS (Nfiam4Naples,and Ft JaudmWe, FL) dm moderate PFOS Imels,approwaalely105 ppb. Edr@ fmm birdlivercsollectefdrom theCanhalUS (LA and NV) were ddmmined to contaitnhebigiesltevelosfPFOS, approximatel3y00 ppb. ItisUnM* thatthedffcm= associatewdithPFOS Irmlsintheliverasrepurelya fimctioonfspecies.In more dm one mzmce, thesame speciesofbirdhvmg ina dffmmt mvimmnent showed apfficandy dlffmaaPFOS levelsF.orexample,livermsilectedfrom whitepelicanisnCabfoniiawere detandned to containan averagePFOS concmuation of58 ppb,whileliverosdilectefdrom White PelicansinNevada showed averagePFOS levelsofover 350ppb. qmAiH Cranesarean acceptiontdthisobservationa,sthe lhw from thesebirdswere &ftm2ined tobe mufomily low inPFOS, regardlesosfthegeD&M*C of thebirds. location With theocmpfim ofthe&ndbiu Cranes,liverw&d= fromatleastone ofthetwo bu-dsmmened within eachdassificatlwoenre dewmuned tocontainPFDS. Law o&,ids from severalspeciesm,clmbm 1 SmftU Crane, were detmnmed tocontaina swU mnourd ofPFHS. Nearly200/ofthehm o== were dewrmfiiedtocontaina mmU amount ofPFOSA- No POAA, M513, M556, M570, orPFOSAA was d&=W intheliverexftactfsrom any of thebuds. 3MEMMONMENTAL LABORATORY REPORTNO. FACT-GENOIO TbLsdatamdl=csthaptotcntlgaeiographfitcm& asso=tewditttlhemviromnentda=lblitonofPFOS and otherfluorochemicalmsay be traceablbey charactmizatiomflow-leveolf &= compounds inanimal tissuesamples. nitsreporrtcne=themost accuratedatavmmle atthistlme.AR numbers sliouldbe consideredtobe serm- qumtt3t@m. ThisdataindialtesakitpoWW geogaphic Mm& &wmted withthemvironmental dlstnbutionofPFOS may be baceableby Oflow-levelflUoroChenliCailnS:inimalfiSM Samples. Samples and ewacts willbe retamedforfiium emuation, ifnecessary. 9.1 Attachment A. Tablesof Qualitativaend QuantitativReesultsfrom theAnalysisof Liver Sampl es 9.2 Attachment B: Defttions ofFluorochcmicaAlcronyms 9.3 Attachment C: Sample descriptioannd sample receiptdata 9.4 AftwJ=ent D: Exftactioannd Analyticadlata Hamld Johnson,And;i& Chemist Y@fislbnsmPhD.,hhxip& Anabdol hwesfip= Date f7 Dte 10/07 '99 08:43 ID:3M ET&S 42-2E FAX:612-778-4468 PAGE Analyalsof Wild Bird Liver&. not detected NA notanalyzed x detected LOQ- Lin-iiof QuAntitation Sample ?4o. I 2 3 4 I s 9 10 II 12 13 14 is 16 17 Ia 1920 21 22 23 24 23 26 r7 28 -r9 30 31 32 33 34 35 36 37 Species -SandhillCrane SandhilClrno Sandhill rane SandhilClf"o SandbillCnme San&illCme SandhilClme SandbillCnme SandbillCrane SandhillCmne White Pelican White Pollcm White Pelican Mite Pelican White Pelican Bmndes Cormamot Bmndrs Caimomt Bmdft Cormarint BrandesComomat 13mdes Comorat 12bi.Cre!ttedC;-momnt I)blC.restedComarant Dbi.CrestedCormomat Dbi.CglitedComomnt Dbl..SfesteCdormomnt R= Pelican Brown PCIICIA Brown Pelican Brown tell= Brown Pellcin SbandhoLcme SandbliClrue SandhillCmne SandhillCmng SandhillCrane Dbi.CrestedCormorant Dbi.CrestedCormorant 38 39 40 41 42 43 44 46 47 48 49 50 st 32 f354 ss 56 57 -ro 59 r06' Dbl.CrestedComorant Dbl. CrestedCorm-Om-nt__ Dbi.CrestedComorant Brown Pelican Btwwn Pelican Brown Pelican Brown Pelican Brown Polic= GreatBlue He!E Great lutHomo GreatBlue Heron GreatBlueHe= GreatBlueHer= WhitePelit" White Peucan While Pelican White Pelican WhiteP )!can Brown Pelican BroWtk Pelican Brown Pelican Brown Pelican Brown Pclican Location Kearney,NE KcammNE -.:Eu Ke &glMtvLNE botm" CoChochist go.,AZ -Chochls*Co., AZ chgebisl Co.,AZ ChochistCo.,AZ CalicatriC&A ClkiloatllCjAL CallipauCi&a@L CativauixCA Callystd-CL& San Dielto,CA San Dieto,CA San Ditto,CA Son t)IeLoC.A San Diesto.CA St.MartinvillLeA, St.ManinvilleL,A St.ManinvUle,LA St.MartinYllIgL.A St.L4&ninvilleL,A Milm_i.FL Miami, FL Miami, FL Miami, FL Miami, FL ValeniesCo.,NM VatenicsCo.,NM SocoffoCo, NM socoffoCo.,M ValenicaCo.,NM NatilesF.L Naples,FL PFOS oob 41 -CLOO < 00 - -!qto-o <LO--0 -ii,22 <LOO <LOO 35 1293 29 Is 153 53 46 46 so 2055 59 14S 333 6 170 106 134 125 159 -49 <.00 <= @4.00 <-00 4-00 212 10 PFO A imb <LQO <LOO 00 clooLoo <LOQ <LOO SM cLOQ <L2Q <L 00 <LO-IQ so 31 34 13 94 20 7 1 23 I<LOO<Loo so 11 to 47 1 11 I -CLOO <LOO <LOQ -<LOO <LOO 9 CLOO FFHS NA 0 -NA NA 0 0 NA NA NA x x NA MA 0 NA MA NA x x 0 NA MA MA 0 0 NA MA NA 0 0 NA NA MA is 10 PFDS N NA 0 KA MA I NNAA I TMNIAAAN NNAA I A NA I .-NA x MA NA 14A x I x x NA-NA NA ix x NA NA NA NA NA x .1 -14aplc3F.L 52 _Naples,FL 100 No lea,FL 152 CA A 16 CillPatriaC.A 36 A <LOO Calle4t?iCaA, 6 c alipawi&CA. 32 St.Manitivilte.-LA 188 St.MartinvillLeA, 39 St.MaKinvilleL,A 1061 SL Martinville,,.LA 26f- St.ManinvilleL,A 173 FallonN,V 141 FallonN.V 362 Fe-tionN.V 927 Fallo NV 133 F a-IIo-n.@NV- 291 Ft.Laud erdaIs,FL 194 Ft. auderdateF.6 ?S FL LatiderdaleF,L 71 Ft.Lauderdale,FL 131 @IIFLauderdale,FL 191- <LOO 33 24 -CLOQ <LOQ <LDO cLtW_ <LOQ <LOQ <LOQ 1 19 I 12 <LOQ-<LOQ <LOO <LOQ <LLOO 11 a -<LOO I<Loo 8 I NA NA- 1-WA- NA NA NA x x 0 NA NA NA NA NA N -x 0 x NA NA NA -1-NA NA I NA N x x x NA NA EA tt@@. NA kLA x x 0 1X 1 NA ___[PNAA LNA P4 3M EnvironmentLaalb -FluorinAenalyticCahlemistrTyeam l4 Semi-quantits e resultsof the analysisofwild bird livers SAMIPLE NUMBER 4291001 SPECEES undhiu LOCATION Kc&mM NE Liver Liver Avg. [PFOS) ppb lp!2@iP)Ph-E!2E2pb 41 4291008 undhiu 4291009 undEU crane 4291021 undhillcrme 4291058 &Wd-h-a@-i=ll _ 4296009 4296009 42%014 4296017 4296018 nndhih cmne sandhihcmne undhih cmne unam cran-c sandhiucram 4337001 whitepelican 4337003 4337004 4337017 4337018 whitepelican vhdtcpelican whitepolicm whitepelican 4306020 4306021 4306022 4306051 4306056 brandra bnmdrs-connorant bmndt'scormorant bmridt'scormorant bmmtls cormorant 4312001 4312002 4312005 double-cmw ;7malu . double-cregedCof=onknt 1 double-cmtedcormorant 4312006 4312007 4360020 4360021 4360022 4360023 double-crestecdormorant double-aestedconnomnt brown pebean brown pelican brown pelican brown pclicmn 4360024 brown pelican 4295007 4295009 4295014 4293-017 4295018 4392003 4392004 4392005 4392006 sandhiucmne sandhiucrane sandhw crane sandhiucram undhir mane double-crestecdorrnormd double-crededconnorant double-ercswconnonml double-cr=tcd 4392007 4336003 4336006 4336010 4336012 4336013 double-cratedemmonmt brom pelican brown pelican h-mm pelican brovm Pelican brown pelican 4311003 4311005 4311006 4311007 4311009 4328007 4328053 4329054 4328056 4326057 4378005 4379011 4379013 4378014 4379016 gmatbhichum p=t blxihiumgmt bhicham greabtl@@hamgmt bluehe= whitepelicim whitepelican whitepeli whitepelican whitepelican k-m peti@canbrown l@ihc@an brom-palican ln.w velican brown pelican Av-Sc when mtlicnareomiuded K-may, NE Kcamev. NE Kearney,NE K,,,y, NE CochiseCo.,A -Cachiw Co.,AZ CochiseCo.,AZ CochiseCo, AZ CochiseCo..AZ CalipatriCaA, Calipab* CA Calipwa,CA CalivabiaC.A Calipab*CA_ San Diego,CA San Diego,CA San Diego,CA San Diego,CA San Diego,CA SL MadimiUc, LA SL MarfinviUaL,A St MarfinviUcL,A SL h4artbiviUaL,A st hintirrviLnAt, MianiLFL Miani@ FL MiaZtkkFL NfianiLFL NfianiLFL Val=.ca Co., ValeniesCo..MM Smorro Co.,NM Somm Co.,NM ValeniesCo.,NM a ctiF6L lc;F,L Naples,FL Naples,FL Naplim FL Calipab* CA Calipab* CA C&Iipab* CA CA * * CA CalipaU* CA St Madin%ine,LA -St hfar6nviULcA, St hfattkrviuLeA, -St. LA St Mu6nviBe, LA FallonK.V Falloi%NV FaUcei6NV FaBon,NV Fallm NV -FL lawicr&leF,L FL L4udcrWa, FL FL L4uderdale,FL FL L..k.Wo, FL FL L-sud=Wc, FL <.OQ <.00 <A)Q <-OQ <IOQ <LOQ <IOQ <LOQ 35 1293 29 is 155 53 46 46 so 2055 59 145 333 76 170 106 134 125 159 48 <.OQ ILOQ <100 <.OQ <.OQ 212 10 52 100 152 16 36 <IOQ 6 32 IRS 59 1061 261 173 141 362 927 133 291 194 75 71 31 91 <IOQ <OQ --@@LOQ <OQ <IOQ <IOQ <-OQ -<LOQ <-OQ <A)Q <LOO <DO <,()Q <.00 :Loo 305 80 31 34 13 94 456 7- 7 23 <.OQ <LOQ 157 58 11 10 47 11 115 <IOQ liOQ <Do <-OQ <-OQ <LDQ 9 <IOQ <-OQ 35 1 24 105 -<[-OQ <DQ -<A)Q <OQ :Lw <22 1 <IOQ <LOQ 19 8 12 348 *= 1 aOQ <= <-OQ 371 11 9 CLOQ 1 <= 1 8 1 W-Sandhill Crane 77% 96% LOQ -limiotfquantitatio(napprm 6 ppb) MSD-SandhiU Cmne 64% 64% Avg. <100 <IOQ 58 56 157 115 105 22 349 371 99 QuaHtatairveesulotfstheanalysoifswilbirdlivers SAMEPLIE NUM33ER 4 1001 4291008 4291009 4291021 4291059 4296009 4296009 4296014 4296017 4296019 4337001 4337003 4337004 4337017 4337018 4306020 43D6021 4306022 4306051 4306056 4312001 4312002 4312005 4312006 4312DO7 4360020 4360021 4360022 4360023 436DO24 4295007 4295008 4295017 4295019 4295014 4392003 4392004 4392005 4392DO6 4392007 4336003 4336006 4336010 4336012 4336013 4311003 4311005 4311006 4311007 4311009 4328007 4328053 4329054 4329056 4326057 4379005 4378011 4378013 4379014 4378016 X detected SPECIES umdhih of undbillcrmc undhiu crone umam or$= IM&M =MC[hiua undhiu ermw sandhih sutdhihcram undhiu Grow Whitepelicm whiterelie4m whitepelicm whitepouem whitepelican bran&'scormorant brm&s cormorant brm&ls cormorant brandt%connaront brandescormorant double-ovdcd connorazd doublo-cr=tccdornmrad double-avdadconnorazd double-cresleodmmormt double-creBWammwrot brown Pelican brom pclic4m kown peliom brown pchcmm brown pcHc4m sandhihcrane umdhillcram umdhillcrane smdhfllame undhiu cn c double-ovdcdcormorant double-avdadconnorant double-a=tedcormorant double-cresw double-crcftd bro@ polialm bmwn Paiibrownpolican bm" pelibrownDeficim greatblueham Vvd bluehe= gratblue-hcron py4it bluehcren Westblueham whitepeliom whitePeHom whitevalican whitepahom whitepelican brownpeliam brownpahcm brownrefiem brown peliew brown poliem notdetected LA:)CA17ION Kcanwy, NE Kearney,NE Kumey, NF- Kearney.NE Kmmcy, NE Cochin Co, AZ CochistCo.,AZ CochiseCo.,AZ CochiseCo.,AZ CochistCo.,AZ Calipab* CA CaUpW* CA Cal4mt* CA Calipab* CA CalipatriCmA, Son Diego,CA San Diego,CA San DicM CA San Diego,CA San DiaM CA St MutinviDe,LA SL NintinviUcL,A St b4aTtinviULcA, SL MufiuvMc, LA SL MailinvMc,LA hfininFlL hfiam@ FL hfi=,LFL NG&ML FL hfi=3@ FL ValenicaCo.,NM ValcnicaCo.,NM Soomm Co.,NM -ValenicaCo.,NM SODOM Co.,Nm Naplm FL - NapleFeL, Naplcs.FL Nsplm FL Naples,FL CalipstriCaA, Calipab*CA Calipab*CA Calipb*CA Calipah*CA St MwdnviUe,LA SL MwfinvMc,LA SL NiartinviULcA, SL MwtinviUaL,A SL MwtinvillLeA, FallonN,V F&Uon,NV FaliMNV FallonN,V FalkwkMV Ft LAuderdaleF,L Ft.LwidcrdaleF,L FL LauderdaleF,L Ft.LAudardaleF,L FL Laud=%Wc, FL Uver [PFOSI ppb PFHS? PFDS? 41 x eLOQ notmeasured riomttuured <LOOQ <IOQ notmcaxared, not menurcd <,OQ notmenumd- not measured <.OQ <.()Q <.OQ <LOO <LOO 00 not--wumd not measured notmeasured x x not measured not measured not measured 35 -- x x 1358 .'- X -k 30 notmeasured notnwjuwrd 17 notmeasm-ed notmeamrad 167 notmeasured not measured 57 *0 ---T x so notmeasured notmemured 46 not measured not measured 85 notmenured not We-um-ed 2176 x x 61 x x 149 x 336 not measured notnmumvd 78 not-cam-ad not measured 179 not mmmn-cd notmcuumd 115 x 149 x 126 not measured notmeaurod 166 not measured notmeasured 49 not measured notmeasured I1 00 9 <-OQ <LOQ <-OQ 226 II 54 103 154 16 37 <IOQ 7 33 202 61 1143 274 178 Lotmeasured not measured notmeasured Inotnmasured notmeasured Inotmeasured x notmeasured notmeasured notmeasured 1x notnicanved notmeasured notmeamn-ed notnw4on-ed notmcmured notmeasured notmeasured notmcuumd notmeasured x x notm:,;;;_ notmeamnod' Mt measured x x notmeaured notmcamuvd notmeasured 146 x 368 x x 941 notmcuured notmeasured 141 notmeasured notmoumvd 294 notmeasured notmeasured 212 x x 76 0* x 72 notmeasured notmeasured 32 notmeasured notmeasured 94 notmeasured notmeann-ed PFOSAA,NBM,M570P,OAA.andM513wamnotdetedIendthelhvnofanybird& 14 3M EnvironmentalLab -FluorineAnalyticalChemistry Team W4 PFS's PFHS perfluorohexanesulfonate C6Fl3SO3- 14, PFOS perfluorooctanesulfonate C8Fl7SO3- PFOSA C8Fl7SO2NH2 14, PFOSAA M556 C8Fl7SO2N((CH2CH3)(CH2COo))C8Fl7SO2N((H)(CH2COo))- M570 C8Fl7SO2N((CH3)(CH2COo))- 14, PFOSEA perfluorooctanesulfonyletahmyilde CBF17SO2N((CH2CH3)(H)) ET-FOSE-OH C8Fl7SO2N((CH2CH3)(CH2CH20H)) PFDS perfluorodecanesulfonate C10IF21SO3-** IN PFCA's POAA M513 M613 M463 M563 M363 perfluorooctanoate perfluorodecanoate perfluorododecanoate C7Fl5COOC9Fl9COOCllF23COOCBF17COOClOF21COOC6Fl3COO- PFS = perfluorinatesdulfoante PFCA = perfluorinatecdarboxyfiaccid no standardmaterialavailablfeorconfirmation;