Document QxDoNy59y3d5MO7NDGo3k8rE
Aeven: = FA
AR226-C0%0 EN-18
3M Environmental Laboratory- Fluorine Analytical Chemistry Team
MDFoeroncegas3r8i1%c Cores om KrisHansen-Sr.AnalytCihecmaislt
Screeningof PFOS levelsinEagles and Albatross
summy:en pls idses of idse, on vente ld cage1dfe may albatross, wereceived attheEnvironmentLaabl.TheeagleserawascollectedfrombirdsinNorthern
MMinniescotha(2i(1ssagammppalleesn)),.tAhlelUfpipveeraPlbeantirnossusslaamopflMeiscwheirgeaon(bt2asianmepdlfersu)m,bainrddtshfeoLuonwdaertPheneiOnfsfuilceasoCflabrplot `onSandITslhaensdewirtashaimntplheesMwiedrweaeyxtArtaocltleidn; tehxternaocrttswhecreentarnaallPyazceidfiqucaOncteiatant.ivelyfor perfinorooctane `sAunlafloyntatied(ePntFiOfSic)abtiyohniwgha-spvreersisfuireedlbiyqcuiodmpcarhisronoomfmaoltecoulgarrioaa-pPhLmCayrse-stsecpnetciiotnretoimcmetetroyfr(EtoPheLseCx-ptErarScMtaSed)y.
i sdoeanicsmioaf egde oSanmwpeleseer atmilsoyv0aP Shse Bet pErL (`PaFndOaSn)al;y5t0icPaFlpOaSrwamaestedertseacrteedaitnacthheedatlboatthriossrsaepboorvte.thelimitofquantitation(10ppb). Specificresults
techniqu`eThperpovriedseesnacneaodfdiPtFiOoSnialndesgarmepeloesfocefrctaaginlteysteortahweaasnvaelryitfeiieddeuntsiifnicgaHtFioLnCb-yEspSeMciSfMicSa.lTlyhmionsitoring.
fragmentsdaughterions(m/z=80,99,130, 180,230) characteristicofthe PFOSprimary ion (m/z =499).
ErperioTehaetpmcamsmatroyw vsof ROSA, omnes sb oh `ofthesamop fcalgle eses ra.
Samplepreparation: Ion-pairingextraction
HPLC: racers renton tne fr 20S In apHcontrolledenvironment,anion-pairingreagent,tetrabutylammoniumsulfate(TBA),is
`used 10extract theanalytefrom thematrix.Anioniccompounds, likePFOSand perfluorooctancate
-
(POAA), areselectivelytargetedbythe cationic reagent.Subsequenttotheformation ofthe TBA-anion.
pair,the analyteistransferred to anon-polarorganicsolvent(ethylacetate),dried, andreconstitutedin.
`methanolfor HPLC-ESMS analysis.
.
InHPLC,analiquotoftheextractisinjectedandpassedthrough achromatographiccolumn.
`Basedontheaffinityofthe analyteforthestationary-phaseinthe columnrelativetotheliquidmobilephasepassingthroughthecolumn,the analyteisretained for acharacteristicamountoftime. For
EHmSAt:RDientecttaionoaTndFmOoSatsoronni,tnFoOfSthe alayeesctoeul1eaornphiab BceatrotsBol e EOS ls Tt= 9nt9 PFOSsolutionandthe analyteextracted fromserainthisanalysiswerematchedto within 1%onthe
`amu,correspondingtothemassoftheanionicsurfactant (CoF17SO5-). Thisionwasmonitoredselectively
tomaximizesensitivity. Ascanofm/z=100to 1210 (negativeonly)wasalsocollected.
000530
osouss
:
ESMSMSSe:veCroanlfsirammaptlieosnoinftahniaslsyettewdeernetafncaaltyizoznbyESMSMStoveritythe ideatityofthe PFOSanalyte
icoonm.pEoSu-nMdiSdMenStiifsivceartiyosni.mAilsaritnoEESSMSM,,aecxocmepptotuhnatdsipteacdidfsiacniaonddiitsieloencatleddi.meAnfstieornsoeflceertactinhtteysiteoloecnte,d
ifornaigmsecnhtarsa,cchtaerraiczteedrfiusrttihceorfbtyhesmmoalsehciunlgei,atarpeacrrtewaietdhahnidgdhe-teencetregdyg.as.As
result ofthe smashiniogni,c: .
. ionissmFasohreedxianmtpoloet,hfeorriPoFnsOsSuacnahlayssi8s0,aiomnu4(9coirsrseeslpeocntdeidnagstthSeOc)o,mp9o9uanzdnspe(cciofrircepsrpoinmdairnygitoonF.STOh)is,
in13t0haemsaump(lcoersr,ecsapcohnodifngttheosCesFe,cSoOnyd)a,ry18f0raagrmaue(ntCsiFs.dSetOe)c,te4da0dt2h3a0daetmect(orC.FS05). ILPisFprOeseSnt
QualityDcuonettroolssaummpmlearsiyz:limitations,duplicateextractionandmatrixspike analysiswerenotcarried ionusttoeandtohfesaenseamxplets.rQmauaatcnrtiixttcauetrivodneo.fAsPtRhOeSleexvteralcstwiaosnedfeftieciremnicnyeodfrePlRaOtSiviestuo naksnaonwdna,ntdhselsevreeastuclatrsve sbehfoourledabnedcaofntseirdtehreesdasmpelems.iO-neq25u0-aapnpnbdcotafliisbcrrtaoteaiaointncghqieuacvlkiwteya.sa`zTahlesytzaendadfatnedrcfuirvveeswamapslsensa;lryezceodvtewircye, r`ewqausaircedc,tehpeetxatartabct7ls%em.aMyibneimrae-laqzuaallyziotdy.controlwasassociatedwiththisanalysis. Hfmoreprecisionis
.
LiofQmuantiitattion Thelowstandardanalyzedwiththesssamples was10ppb;thisis thelimitofquantitation
associatedwiththeanalysis.
i
IHnPsLtrCusmyesntteamlspecifics: `HewlettP`aCcoklaurmdnS:eKreiyessto1n1e0B0eLtiasqiulidCuCshromatograph
2Sp21m0pa0rmtimclesize FSlolovwematteA:: 320.00muMmAnmm.oniumAcetate SSoollvveeaattGBr:adieat:Methanol
`4 Hold a5t9%0B1 %iBnfo99.r530m.0 5i0nmsi.s. R`Feotludrantto445 5%B%fBoira31..5m50imnisn.s. IInjnectjioen cv/otslauimmpoel:en:1s014L. Electmrasossspepctrromaetyer Microma`sMsasPslaLtyfnorxm2.I4TSAoPfYtMwaasresSpectrome"Ctheicrk," CMoondee:voellteacgterso:sp6r0avynegative S`oAunralcyezteervmapceurautmuprree.ssures1:105.0C0.0043 mBar,0.000079mBar Lous: 499, 413, 369 Electrode: cross-flow
;'
000531
osiouss
2
Electrospray MSMS
`Micromass Quattro IIAPIMassSpectrometer, "Madeline"
`Mas3s.1LSoyftnwaxre
Canevoltage6s0:v Collgai sensergiy:4o5nV/
Mode: electrospexy negative
Sourssperm:+ 113C. + APnalryzierlvomua:c4au9u9mr;p4rye9s8sures:0.000043mBar, 0.000079mBar
.
loads: Zepray . Daughterions:80, 99,130, 180,230;78
.
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000532
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LOCATIONS AND DATA FROM AVIAN BLOOD PLASMA SAMPLES
TO:
Minn3eaMpoCloirsp,oMriatninoensota
BY:
JohnP. Giesy and Associates
:
Hilltop Place
-
`Will2i3a5ms5tBonr,avMeincdheirgaRnoa4d8895
July 18, 1994
000533
Avian blood plasma samples collected from two species, the bald eagle (Haliacerus
leucocephalus)andtheLaysanalbatross (Diomedea immutabilis) were sent to 3M for analysis for
CyF,;S0,and CF,,C0;. Additidoatnafaolr these blood samples follows:
Laysan albatrosses withinthAeMsiamdpwlaeysoAtfoLlalyisnatnhaelnboarttrho-scseenstwrearlPeaccoilflieccOtecdefanr.omTatbhleOef1fpircoevrisdCelsuabpdlodtiontdSiaantodaIonsnlatanhlde birdssampled: `Tnaubmlbeer1,.anBdadnadtemubmlboeord,wayesacroblilredcwteadsfobran5dLead,ysaagnealabtatcroolslescetsiofnoofmbMliodowdaysaAmtpollel,, bnolrotohd-cseanmtprlael PacificOcean.
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losT.19156
Nootherdata onorganochlorinepesticidesfrom thesebirdsiscurrentlyavailable,however, aseperatesplitsampleofeachhasbeenarchived.
Baldeagles
two caAchlflrsoammtplheesuopfpbearladnedaglloewsewrepreencionlsluelcatsedowfiMtihcihnitghaenM(iFdiwgeusrte,1w)i. tThaobnleef2rpormoMviindneessaodtdai,toannadl dataonthe birds sampled:
000534
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egion, ae
of odspl collection,
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esng bdeagesiom 8
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