Document KGjOo9QgdNaRx424LXBjK0QaN

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evSna: - - AA'TI'I'TOORRNENYE/CV~IECN`LbToIWWNEOOoNRRrKTKcPPoRRpOOyDDUUCCTT PRIVILEGED PRIVILEGED DONDOGTNODTisCcOLPOYSE 33MM EEnnvviirroonnmmeennttaall LLaabboorraattoorryy-- FFlluuoorriinnee AAnnaallyyttiiccaall CChheemmisisttrryy TTee~amm KisFan Sr.Anaya]Chemis Kris Hansen - St. Analytical Chemist Ferns raChiy nas a Tam Fluorine Analytical ChemisuT Team Buling 13.05 Building 2-3E-09 smn 612-778-6018 Se~rreeeeaaiinngg ooff PPFFOOSSlelevveelbsiinn EEaagglleessaannddAAllbbaattrroossss SSuummmmaarryyT:"ensampleofbidsrof i ser. ive hom veil bud ngafv romLys Ten samples of bird sere ofbird sera, five from juvenile bald eagle and five f~om Layson bass,ve recived a he EvinLb.Th ges vas colo rom bis norte aibaU'o&s, w~ l~ived at ~ EIIvilonm~nt~ ~. The eagle ~ was coll~g:d from birds in Nozthem MMiiscshe2(sisgumpalp)n.,tAeliUpvpeelrPaeonsnsaamopflNeiscwheigeant(3indplfeo,aindtthoLuowneas tPheOsftfos.Cloplo Mi.n~sota (I sample), the Upper Penln~ula ofMichigan (2 samples), and the Lower Penlnx~ia of Michigan (2 samples). All fiv~ albatross ~amples were oblained from birds found at the Offer Clul~plot onSand "lTanodswaisaimptlheesMeidrweaeyxAtrialctisn tcxe om wceeentarnaallPyczied quGoaannt,i foc peroorocians On Salld lsl:md within the ~ldway A/oil ill ~ llorth ~elltral [~:ific ~ sAuAlufanoaillnyeattteaednid(edePnsnFitOicafSitc)nibatoyiodnhnivawgahas-rsipvavrdeleers.riisffuSiireeaeddmblbpiyylquecciosodmmcpwpaehrarrieirssqoononuoomffimmaoovtlleceoaulrgrariri~onnaE-BpLIsnmCh.Cagysersec-steponealtcintoerraoeGctmigemetteertyoro(fsboEtohPolesLveeCpxs-trErcaSciaMtveeSddy). "Th ple ofcles wer deed 0 coin 20-77po peacoat The samples of eagle s~. w~ del~m~ned to co~t~in 30-77 ppb perfl~ suffonat~ (2PFS)s,i50yaFpOSrwetaedretroascnthhdesohioserebpoerv. hi Ltofquan (10 po). Specie ress (PFOS): no ~OS was detecu~ ill the albaffo~ ~ove the limit ofquantitatio. (10 ppb). Specific results {en coiqu"TTphchraeoa pupvrgrieeids~ccsestancscneeoaoosdf~(iPs PiFF3oOOn0SSalii,ndses5ag5im,rep1c3loe0fs,coo8ff0cae,aggl7tlee5s)seectrnhehavewraaassscvh~iee~eoddfewpui~hinncggtPiHFPoPOLnLCCbp-yeEEsiSSpcMMeceSSiMSaeSlh..l(yTTahhoi~swi49n9g). fi'ag~euts daught= ions (m/z=80, 99, 130, 180, 230) characteristic of the PFOS prlm~ry ion (m/z = 499). otes"aTompropfecclageeo5fmso.weels of PROSA,pearosanealoyamid,wis ln cond ch The pt~umc~ ~low levels ofPFOS~ l~-,'fluorooctanesu~onylamide, was also confirmed in each of the samples of eagle sera. Experimental mmary: A -- ~mple preparation: Ion-pairing extracffo. 0caacihecoantproyledfreo vth rmaar.nAneiopnaringproaugneds, In a pH controlled ~Lmnme~ an ion-pairing reagent, itestraFbtumOytSylaa~nmmdmoonfniuumssmuftte~ ((sTTBBAA)),, i~ used m exwac~ the ~e f~m the ~n~c Anionic compounc~ like PFOS and pe~l~moctanmte (POA) aroseicively peta he cationic reagent. Subsiuet te fom of teToA-4sion (POAA), axe selectively targeted by the cationic ~agen~ Subsequent to the form~on ofthe TBA-anion it,haentafortAPLaOElSMrS am1a0vi0s pola cpa vt (il cet,di, decal b! n pair, the ~r~lyte is lran~er~ to a non-polar o.~.i solvent (ethyl acetate), dried, and reconstituted in m~tbanol for HPLC-ESMS ~-~lysis. BHaPsLeCd:onCthhHoPaaLfCfr,i1yaolfcrteohutentaienotnafrtttaeeifscosfrtothrcPiOnciScotnndsahndapishdtcroouugh lcartioveeminpherapiicdcolumlne. pEChFaaOmspSeips,usiiinoagntashurndodahe stshneuicoolnuc,muPa,FttOeeSdmaarysmctsitret1n0.d3mniorao3yc.shaeRsreBereschiadmmaufsoabtwetiowieeie13.9SoFoaomrdhnard HPLC em. Ea~ mSsAS ,Sc::omDDAseepanttloeacynlctysdffsioioisnsnnaogoaffnnPPdtRFmmOOeoSoStnsom~itaraaosinnrniddnogaefgorrtdofsshfitihhnneieddmoiimcocnaloeitelescecsctmtuhhaluaartritiheooaenntpprrii(mmGaaErryy5i0oon1n1chC.ahrTaarchaticetr~firsoistndiyccaoosffFPmFFoOOnSSoriisemd/zl==o44v99e99ly 0maiaiz sev. A amoae100 fo ainu, on'esponding to th~ mass of tl~ anioni~ to n~in~ sensitivity. A sc:m ofm/z=100 to 1310 (ego ou va loclied surf~t~t (CsFx~SO~-). This ion was monitore~l 1210 (negativeouly} was nlso ccll~d. selectively osm 05108/98 11550044..00000011 1 1 Exhibit I MAOI0434 E15x04hibitI 3MA0 J 404~34 ESASS:eveCraolnsafmpilresmoiaftahniisloyetntewiedeentainfaiclaytzieondbyESMSMSt veriytheidentity ofthePFOSasayte icoonmpEoSu-ndMiSdMeaStiisfivceariyosni.miAlsairnwEESSMMSS,,3ccxoemeppotuhnadtstpeacdidsainonadidsistieolneaclteddi.sAnfetnseirosnoeflceemictarhtyeitoeolecntn,d ifroangimcehnasr,acchtaerraiczteefruirstheorfbtyhesmmoalsehciunlgei,taraepcarretwaitetdhabngdhdoeteerctgeydg.as.Asaeultofthesmashinogni,c . fonssmaFsohreedxiamnpoloeb,efroiroPnOsSoacnhaalsy80,aimona49c9orireescpotnedidnags1thSeOc)o,m9po9uanmdasp(eccoirfriecsppornidmianrgytconF.SOTh)i,s in1t3h0aemsaump(lceso,cmacehsofpthoteosneCFds:eicSoOan,d)ga,ry1f8r0aagmmeant(si CdeteFcted1.0a4t2tS3h0edae0tmect5(oCr.F),SO,;). ITPisFprOesSnt QuQauliatliy~Dccuoonenttrtrooollssaummpmlaesryz:limitations,duplicateexracton and mtr spikeazalysiswero not carried ionosuuttteooandttohhfeeaseenes~amx1 pl~ ers.amQaucannittixtcaeutriovdne.oAfsFtOhSeleexvtrealcstwioansedfeftieircnmciynoedfFeFltOiSviestuonknsotwannd,artdhseolerveesnutcltasr|ve sehfoourldbaendcaofntsridtheeresdasrapeiems.Oinqe2u50a-20n0pbdctaolfiisbcrtraeteainointncghiequcvaklwietays.Tanhaelyszteanddaafrtdrciurvveeswuapsesa;nraelcyozveetsiyce, `rewqausiarecd,ctchepexatartbac$lt7s%emaMyibneirmoalaqluyalzietydcontrolwasassociatedwiththisanalysis. Imoreprecisioin LiofQmuantiitattion `asTsThwoheietlclhootiwwhsesatataantnnaddlaaeyzrsdddiasanmallyyzzecddwwitithhtthheesseessaammpplleesswwaass I100pppplr, thhiissiiss tthhe~lilimmiitt[ooffq~uamntni~ttaatfiioonn HTnPsLtrCasmetaetamlspecifics: HIHe-I~PmLleCe~PCPaoacclkkuaarmrddnSK~eerxiyie~sstso11n11e0~0B0LeLiaisqqiuuliiddCCiCharhorommatnomgrgarapphh. 22Spx1m10p00Oamrmtmmicilzee FFSollobowvew1an3t1A:0:: 33~0200I00~mmu9MLpLia/Amrrtmaiiicmnnl.oensiizeum Accite SSSSoooolillvvvve~eenana~tttGBBAr::a: dient:2M.0etmhaMnalAmm,wium Acetate SolventFG4o45ml~dd05i29e.0~9%1%08%,~B2i0l.~f9o9.r..95,~030m.ri5a00nimnsi%.ns. FRRoBetol~uladdrrn2aatt409o54045X%5%B%Bf8Bfooirirnn33..113~..m55000imnisn.s. InIIjnejnecctj~ioeonacvHv/ootoshllaaduimmmaope~t:l:n4e511s00|%B for 3.5 mi~a Injections / mmple: 1 MiEcrloemacsstPlmratafosorsmsspIepTcAirProImaMeatyesrsSpecrom"eCthizc,k" `CMoasnseLvoylutxag2e.s4:S6a0tvvare A. Mode: electrospray negative ASnoaulryczeetrevamcpueurmsp:ressures1:01.500C0.043 mBar,0.000079 mBar TElector4od5en9:, 4cs1o3s,e:36l9ow osusss 05/08/98 2 11550044..00000022 33MMAA0011440044853355 `EMlieccrtormoassprsaQyuMaEtrSo.IlAP MassSpectrom"eMatdeelrin,e" C`onMevaolstagi3e.s1L:SoOyfwvnarxe MoCdeo:lelgelactsreoinsperrsagyyn:oe4g5antVi/ve `SAonuarlcyezteesmvpaercaatmurpree:ssures:1103.0C0.0043mar,0.000079mBar `PDarngeilriomown:sa4:933r0;,49y398,130, 180,230; 8 Electrode:Zepaay. oss 05/08/98 11550044..00000033 <a 33MMAA0011440044553366 : FFlluuoorriinnee AAnnaalylyttiiccaall Loum ChCehmeimsitsrtryy TTeeaamm an SpparrmpeertRaieeenmtnd piroiw1n9n8 . AmGiCraiarnCture:10m595o Lcatos: oe LOQ/LODS: tO pp6 Analy PROStnsersof ngssad barons [s oonponwees n [re oam ETBaoeigaenorcmroomr]|] ~ 3:~9-31740 [robert FJ~Io 4:~)-31748 Bein Ea~le 5:(~9-14593 mikednmaei?n uak~ mira ernie usdm, m i 82 ~y. M 2 a H7 UP. Mi au UP.M] ~ Voyageurs. MN s 7S Crisos so[o~ o rwaorpp]b pnneirresc]e b.d.L viab.l.q. wforttb.d.L Anaseaos sia Analy ofPROSAInsecsofsagessnd albatross FPRROOBRAAwta teio ieteshmnn 8minstn en. 1-10D10Q~ListofDock ofQuin AA~rTORTNEWOCRUEDNNTOWWEONORRTVKKCPPIORRPOOYCDD.UULCCTTIPPRRIEVIVIILLNEEGGETEDD. DO Nm" ~py . [DONOT DISCLOSE Ma3Men~ nolma oniiI~eb 11550044..00000044 aMA01404S7 3MA01404537