Document bya2k2J5jggLyM5VBbjJnJrX0

Screeiiink And Alba 5/8/98 3M EnvironmentalLaboratory-FluorineAnalyficalChemis= Khs Hansen- Sr.AnalyficaClhemist FluorineAnalyticaClhemiwy Team Building2-3E-09 612-778-6018 Team Screeningof PFOS levelsin Eagles and Albatross Summary: Ten samplesofbud sem ofbirdwxa, frm fmmjwi=dc baldeagleand &a from Laym albatrossw@e receivedatthe I-ab.Ile tWe serawas collectefdrombirdsinNorth= M=esota (Isample)t,heUppa PeninsulaofMchipa (2samples)a,nd thelav= Peninsulaof Mchipn (2umples).Allfrm aftum sanwl wereobtainefdrombirdsAmd attheOff= Cb*plot an SandTt]2niwithintheMdway AwU inthenorthcenu2lPacideO=m The s= sampleswereodmcta omam wereanab-adquanttmvelyft p sumnate (]?FOS)by liquid romatogmpk-le==pray mass Rm==wuy coct-m(BPLC-ESMS). Analyu idcatfflcatwiaosn vcdfiedby comparisonofmol=du ion-HPLC retmdon dm ofthecamcted analyt&andstandardmateri-I Samplesvmm quawitadv* viduated2zWnsta fmc-pointsohma cmrm Mm smplcs ofca& =a weredeterminedtocontai3n0M ppb panuamc=c sulfomft (PFOS);noPFOS was dew=d inthearoatma abovethelimitofTmdMdon (10ppb).Specifirccmft and analyticpaalrameterasreamwJW tothisaqpm Mm presenceofPFOS m samplesofeagleserawu venfledusingBPLC-ESNLMWS. This techniqupercividaens adA!f=21 deg= ofcertaintyotheanabftWendficatiobny qmcificanymouftoring ftap== daughterions(ni/z-909,9,130,190,230)cba@@ ofthePPOS pd=u7 ion(miz- 499). The prcs= oflowlevelosfPFOSA, pc&uoroocww&onylam@ offt samplesofeagle=-A was alsoconfirmedincrA F.xperimentdmmmary: Sarnplperepwation:Ion-pairinegxtracdon In a pH controlleedmarowneit,an ion-pairinrgeag=4 ftu-abutaymlmoniiun m,14@aCMA), is usedto=M= theanalytefrom thematrix Amomc comvmnd% likePFOS and (POAA). aresd=uvrly targetebdy thecationirceagmt- Subsequentoft formationoftheIBA-anion pairt,heanalyties=nsfured toa non-polaorrganicsoh=t (ethyalct=), drieda,nd r=nsunted m methanolforBPLC-ESNM analydl HPLC.- Characterisfriectmdon timesforPFOS InEPLC, an aliquotofthe =Waa isinjecteadnd passedthrougha -- CDIUMJL Based on theaffmityoftheanal@ufor%c stwonary-phaseinthecolumn relativteotheliquidmobLIc- phasepassingthroughthecolumn,theanalytoisretainedfora charActmisdc2moi,nofdm For example,ina standardsolutionP,FOS may cluteat10.5minutel Rcmntion tima betweena standard PFOS solutioannd theanalyte=Uacted from scm inthisanabsiswere matched towithin1% on the liPLC F.&W. Detccifonand monitorinogfthemolecular!on AzalysiosfPFOS standardindicatetshattheprimaryioncharacterisotfiPcFOS isMIZ - 499 amu, correspondintgothemass oftheanionicmubctant (C@F17SO3-)T-his ionwas moniu)rcdselecth* tomaximi= sensitivirAy.scanofmlz-100 to 1210 (negativoenly)was alsocouacte& o5/m98 Esum@a. Confirmadoonfonalytledentiflcadon Sava,a=i=piesinthissmwm anab-zbeydESMMA tovct*thexkntitoyfthePFOS anlyto iollES-&5NO isvay si-iit-oF-9oM.,,-;tthaittaddsanadditiodniaml=sioonfCmUilqto compound identmcationA.s inE@, a amnpowd nuffi ioniswkcto& Aftr sdecd theselected ioniscbmacterizedfurthaby emosb2n itapm with higbenau ps. As a rmk ofthem=sbint ionic fragmeam dmrwt=ute ofthemole=lc,aremftd and detscmd Foran le,forPFCX "ysis, ion4" isodamd n the=npoemd Rmcir=Fimn7 im This ionis=nsbad intootberionsmxh as 80 am -to S03).99 a- Cicmwlppm.pondtionPgSC)31 130 -, (convspomilng 10 CF2SO@), 180 =a (C2F4SO3). =d 230 mm (C3FsSOs). IFPFOS is intheamplm awh ofdum moulazy ftap=ts isdouctedatthedaeaw. Q=Mty controlmmmarr. Dw to sample si= livmt-ationdsupu extmcd= =d matem w-ke amdysiswm not cmxied outon dum =mptm Qundtadon ofPFOS WveJs wu dcwmdn.ed rdatm toa noxind soh=t = Wstead of an cmamd cmw- As tM c=cdm dBck=7 cjfPPOS is=bxmn. tbm =soft -thm,Wbe c=ddcmd semiqwwdmd" and ofommodn quaft. The dendad car" wu =alyzed.twice. bdm and ter the=mwo one 2%)-po cdftxdm checkwu =alymd atw fta onolm was a=qgable atwM Nfimzal quaw coutml wu au=ated vmh thisnab=L Mmmawa@mn *d-- is ft c=a= my be m-nab-zal LimM ofQuandtadon Ile low standardanab-md withtbow 2ssocintedwith the analysil vu 10 pp&, thisisthe limitof Lutmmental speciriec HPLC s)atem Newled Packard Series1100Llqmid Column:Kci=ne BCMSilCis ffmh 2 x 100 mm 5 pm pardcle size Flow rate: 300 Wmin. Sotv=t A. 2.0mM Amrwnb= A=tac Soh,=tB: Niethanot SolventGrmiie= 45 to 90 %B in 9.50 minl Eloldat 90 %B fai3.50 M'ML Pjm= to45 %'B in 1.50 miul Hold 3145 %B for3.5 minl Injecdonvalmr. 10 pL Injadons / samplc 1 Electrospraym= specftmeter bd=nt2cc Platform11API Mass Spc=mcter, "OdW MassLynx 2.4 Saftwm Cone voltq;= -60V Mode: clactrospranyqpdw sow= WMPWAMM 115 ea Analy= vacm= pn=lm: 0.000043 mbar, 0.000079mbar Ions:499, 413, 369 Elw=&: cross-flow 05/09198 2 Mmmum QUMO 11APIMm Specu=naw-,M"dine MMLY= 3.1Saftwm cow vokag= .6ow Collisiposnemm my'. t, Sam= Analy2w 45V ngpdvo 115or_ 0.000043mbar,0.00007=9Bar ?mbnm I= 499-.498 Dm*w bw Sk ". 130,180,230-.78 MCCUODL- Zqpmy 05/0819S 3 LOCATIONS AND DATA FROM AVIAN BLOOD PLASMA SAMTLES TO* 3M Corporadon NfimeVoUs, Nfimmta BY: Joba P. Giesy and Associates Mhop Pb= 2355 Bmvender Road WMLimsw% bfid4m 48895 July18, 1994 Avianbloodplasm samplescollectefdromtwo speciest,hebaldeagle(Haliaeetw leucocephalaunsd)theLaysamaft=ss (Diomedeaimmutabiltwse)reSento3M foranalysfiosr C,F,7SOa2ndCSF37CO2- Additiondaaltaforthesebloodsamplefsollows: Laysanalbatrosses Alls=VlesofLaysanaletrossweesrecollectferdomtheOfEcerCslubplotonsandTsian-i withitnheMdway Atolilathenorth-centPraaclifiOcem TableIprovidaedsditiondaltaonthe birdsampled-. Table1. Band number,yearbirdwas banded,ageatcollectioofnbloodsampleb,loodsample number,anddatebloodwas collectfeodr5 Laysanan=sses fromNlidwayAto]Lnoftb@-centmi PacifiOc ean. BandNN umber 1211 2F477-60090 1224477_-660000595 136@76_032(6@ 13216377_-930286i59 1137-90880 1067-19156 YearBanded 1993 1993 1985 1997 1978 CollectiAogne 0 0 8 6 15 SampleNumber LAC 08093 LAC 09593 LA 616 LA 607 LA 617 DateColl,9-e9,cIteejdd 18 May 1999923 992 18 NUy 1993 13 Dee 1992 13 Dec 1992 13 Dec 1992 No otherdataon o%mwchlorine pesticidesfrom thesebirdsiscurrentlyavailableh,owever, a seperatesplitsample of each bas been archivecl Bald eagles Allsamplesof baldeagleswere collectedwkhin theMdwest, with one from M=esota, and two each from theupper and lower penkmlas ofnfichigan(Figure1).Table 2 providesadditonal dataon the birdssampled-. Table2. Band number,locationc,ounty,region,dateofbloodsamplecohections,ex,weight,and age indaysof5 Minnesotaand Michigan. Band No. 629-31740 'LlLeovoccaqatTti_7iRoointne. County Devil'Lsake Menominee Region U. Peninsula, Date Coflected 1989 629-31748 629-14593 SlateRiver Falls Steve'sIsland Baraga St.Louis 629-39332 629-39339 Caundw Creek Otsego Pickerel Enunet ----Channel----- U. Peninsula, 1989 . Nu Voyageurs NP. MN 17 June 1992 L.PeninsuK 3 June 1993 Ne L.Peni ula, 5 June 1993 Sex Unknown Unknown Male Female Fenmle Weig Unkno Unkno 2.7k 4.95 4.25