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a Enon Tenors 3M Environmental Technology and Services 0 30x 531 PO Box 33331 OR ma St. Paul, MN55133-3331 Sch 612 7786442 LLabaobroarattoorryyRReeppoorrtt AAnnaallyyssiiss ooff FFCCss iinn SSaammpplleess ooff CChhiillddrreenn''ss SSeerraa and LLaabboorraattoorryy RReeppoorrtt NNoo.. FFAACCTT--GGEENN--001111 W1724 Testing Laboratory Testing Laboratory 33MM EEnnvviirroonnmmeennttaall TTeecchhnnoollooggyy && SSaaffeettyy SSeerrvviicceess 3M Environmental Liborstory 3M Environmental Laboratory FFlluuoorriinnee AAnnaallyyttiiccaall CChheemmisisttry Teeaamm ((FFAACTT)) 23509 2-3E-09 993355 BBuusshh AAvveennuuee,, SStt. PPaauull,, MMNN 5555110066 LLaabboorraattoorryy CCoonnttaacctt Kris Hansen, PD. Kris Hansen, Ph.D. Bldg 23500 Bldg. 2-3E-09 PO. Box3331 P.O. Box 3331 St Pal, MN 551333331 St. Paul, MN 55133-3331 Phone: (651) 7786018 Phone: (651) 778-6018 FFAAXX:: ((66551I))777788--66117766 -- Requester GGeeaarryy OOllsseenn aanndd JJeeaann BBuurrrriiss 3M Company OOccccuup3paMattiioConnoaamll pMMeaenddiyicciinnee Ca0aw0s 220-3W-05 SStt. PPaauull,, MMNN REPORTDATE 0219 REPORT DATE: 05/21/99 11558866..00000011 i Exhibit swAses721 3MA00659721 nn nt TE FO -------- Samples were analyzed to provade a quantitative determination of PFOS and PFHS in a small number of eoSes eet 1 or psve id samples of sera collected from children lmtween the ages of6 and 12. Additiomlly, samples were screened ee eis a orem Toon provide qualitative data on the presence of several other fluorochemicals kncludmg PFDS, PFOSA, PFOSAA, Dee Cotson M556, M570, POAA, M463, and M513 (Appendix C contains a list of acronyms). Lan 100i fer vr alo aris. sl ple lun psd arp recto Less than 100 ~L of sere were available for analysis. This mmJ1 ~zmple volume posed analytical restrictions meddoo i ey Bo a and method detection limits for this study are sign~cantly higher than reported in earlier studies. Sopp igse Her met `aaSnneaarlleyyszzaeemddfpfoolerrsPPwFF~OOmSSaeanxndtdraPPcFFteHHdSSuususisniingnggahnhiiiggohhn---ppprraeeissrsisnuurgreelexiliqtqruuaiciddticeohhnrrpoormomcaeatodtguorreag,prhTyah/epdeehc,yxtr~/ocestplsraewyct~tartaennrdqdoeuemsamampfmirataaastsyissvdy rR Te a iy slxctromctry (HLPUESMSMS), arid evaluated versus an c,xtract~l cttrvc. Qualitative analyfis geeed sSao,wml conducted by comparing Ixmk response in the samples to that obti~ined flora _stan@rds, when ix~ssibl~. If DE standard matu-ial was not av'ailabl~, compound idrmfificafion was based on r~sonabl~ HPLC-rctcntion tim~ EEE SE ES and predicted mass spec~meter res~nse. AtlalytJcal details are availahl~ in the Sttldy binder maintained by =FACT. A Ate Saba pres plan Despite the increased detec~on limits that resulted from the small sample size, several fluorochemicals were pe ee BE BeOS. POR ds ct ona es detected in these sera samples. PFOS, PFHS, PFDS, POAA, and M463 were detected in each ofthe samples fons analyzed; for these analytes, the estimated detection limit is 3 ppb. PFOSAA, M556, and M570 were ee i cote mi FOS sd detected in some ofthe samples and the detection limit is estimated to be approximately 5 ppb. PFOSA and BT Tn M513 were not detected in any sample above the estimated detection limit of g ppb and 12 ppb, respectively. Srn a r Se Femara The average PFOS concentration was 54 ppb, covering a range of 3 I-I 15 ppb. These values are slightly im Isoril. higher than the averag~ values observed previously foradults and some part of that (up to 10%) may be due ett m i to improvements to the modified method used to extract these samples. he avrg PE ied eva 5p ge of 00h Tenge The average PFHS level determined ia these samples was 35 ppb aa,oss a range of5-i00 ppb. This average lies ttihshooasspeepssmaammxpilpmeleasst,,dttyhheeIh0hiigtgihhmeeseststvhvaailgluhueeedrdetethteaernrmmtihineneeldediviennlsaa npnrooennv--i3o3MuMswlwyoororbkkseeerrrwvwaeadssin1133apppspbmb.a. IllIttseiistuuonfnlaikdluellyttishteharaktattsthhaeememmlpilnienyso.orrIn eeto Abe modifications made to the amlytical method could account for this dramatic difference between the two gglorupsoooffussaammpplpelsess.. a ea eeroent aplotl, AAltlthhoouugghhririggoorroouussqquuaalilittyyccoonnttrrooll mmeeaassuurreessa~ nd33MMEEnvnivriroonnmmeennttaallLLaabboorarattoorryySSttaannddaarrddOOpelXrarattiinngg `PPrroocceedduurreess wweerreeffoolllloowweedd,,tthheeaaccqquiusisiittiioonnoofftthhiissddaattaa wwaassnnoottnneeccesessasrairillyyccoolllleecctteeddaaccccoorrddiinnggttooaapppplliiccaabbllee Good Laboratory Practices. This data is not suitable for dism~ufion to any government agency in defense of product suitability or safety.. Data presented here is the highest quality ,~ar~ available at this time. E A of Std IOE ilmE a btn e On 4/27/99, Jean Bun-is of 3M Occupational Medicine delivered sera samples to the Environmcmlal Lab, Bei. Environmental Lab personnel initiated a chain-of-custody upon receipt of the sample~ m Te on binge er si wih eR esis LESSai. There is no holding time criteria associated with these samples for LC/ESMSMS analysis. ReroRTOATE 5219 RETORT DATE: 05/21D9 11558866..00000022 suntensorn2 3MA00659722 AR moT. FLAiCDOGReATnOaRY 4 Me-tAnalhyticoalandd sPreparatory Ansysmethodison ofPotasium erucroucanesafoec of OleForherss Compoundsfom An.,dytical methods ETS-8-4.0, Exlraction of Potassium Perfluorooct,'mesuifonate or Other Fluorochemical Compotmds from SimSoErOvetryPsfoAvnisanoUsingrHpPeLeSCBeecRmeesperrayvMolausmseSswpeecrtorcd nd scous xracts Serum or Other Fluid for Analysis Using HPLC-Electrospray/Mass Spectromet~ pi neti MABE Thesemodificationsmay res in lhlbeterrly recoveries an MODIFIED to accommodate small sample size. Reagent volumes were reduced and aqueous extracts were triple rinsed with MtBE. These modifications may result in slightly better analyte recoveries than Er ose ahseovoetdyusionf 0PosregsalPeTchroodcinesilfosie orOtherFiche on SerumorOdor those achieved using the original metho:l. ETS-8-5.0, Analysis of Potassium Perfluorooctaaesutfonate or Other Fluorochemical on Serum or Other FSlHuiOdDUIsFinSgAHDPLoCrPElYecrdosaprraiyhaasns Sbpectoopmieenyg EISsaps spree o FOScues2670 Fluid Using HPLC-Electro~pray/Mass Spectrometry TAPaE s alSae. Thssksinonis ly estna SightUNDER estimationofPFHS MODIYIED for PFHS determ~ation by comparing PFHS samples response to PFOS curves, as no standard PFHS was available. This substitution is likely to result in a slight UNDER estimation of PFHS ocls levels. Sample preparatieont- oaqmuaeoussplpenlt, EiPtLhCoEnSpMaiSriMnSg:aigoerpsai extraactnioon n hydrogenste Sample preparation- aqueous samples, HPLC/ESMSMS: ion-pairing e~trac-tion ono amine.Th ao atlively retan orochemicals Amlyte is exacted from a sample matrix with ion pairing reagent [tetrabutyl ammonium hydrogen sulfate hbo pie formed, ea i ane nanngli rac sont(meer (TBA)] in a pH-contmlled environmenL The cationic reagent selectively targets anionic fluorochcmJcals. Once the anion-TBA pair is formed, the analyte is transferred into a non-polar orphic solvent (metlvl-tert- oatle,die,an eo in etal fo MSsls butyl ether), dried, and reconstituted in methanol for MS analysis. "BAPPLLCCS,MaSnMlS:ofnoroef etxadctqujalateivewnodreksehougharovers hse iid hromologrhic. HPLC/ESMSMS: for detailed qualitative work mooairyof oly fo heSaraypie beclu clive oebd In HPLC, an aliquot ofextract is injected and passed through a reverse plmse liquid chromatographic eth nat sine for characte amount of ume.Foscaminaspandsard coltatm. 13ased on the affauity ofthe amlyte for the stationary phase in ~ column rehtive to the liquid Te Pr rycht 5mms. Reem es between sanardPOS sluionand be mobile phase, the analyte is retained for a characteristic amount oftime. For example, in a standard solution PFOS may e.lute at 8.0 minutes. Retention times between a standard PFOS solution and the eedforse in is raysweemich on HPLCsystem o wii 1% anatyte extracted from sera in this analysis were matched on the HPLC system to w~thin IA Folliowing HpPoLuCnsdepnaroattiionng,EBSVrSoMSaprnov.idesEacruaoppidraenyd,aicunnmeaanscfoiagslycuiodgpwiindearyanfgoerof FollowingI-IPLC separation, ESMSMS provides a rapid and accurate means for amlyzing a wide range of loan, erly cpr a elatheymil empertrs. MOkaeenisze, organic compounds, including fluorochemicals. Electrospray, an ionization technique used primarily for ay fo, charac of he say, s lect.This oni bombarded with high eae)635 detection ofmolecular ions, is generally operated at relatively mild temperatures. Molecules are ionized, so rotesalesecondary oe mens nique 0 hepry on, whieha and a pfiau~ ion, characteristic ofthe analyte, is selected. This ion is bombarded with high-energy gas; subsequent collisions create smaller secondary ionic fragments unique to the primat3' ion, which are Gast detected. Fborecanmpi, oortoPoReOSr(onGs 5ma0ch)a8r0ay,(co4r9mp9oinsdiengl0eSa0s7t)h,eanhd 23a0 ass(GtF.ySon0ET;xhi)cs.lon For example, for PFOS (CsFtTSO33 analysis, ion 499 is selected asthe characteristicpfima~ ion. This ion iy ment deedan an edo dilatePFOS romor compoundshat is fragraeuted into other ions such as 80 ainu (corresponding to SCh3, and 230 ainu (C~FsSO~'). Each of vei in haces 49 am primaryoc,bot een chica composiions and these secondat3, fragments is detected and can be used to differentiate PFOS from other compounds that might have the same charactex~c 499 ainu primary ion, but differeat chemical compositions and Secfoon mgnmctdatiaonrteys. secondary ion fragm~tafion patterns. P Se E SR S E E 51 Calibration 5.1 Calibration For qeuaenitaoimvoenditeortmemrusm,eridaivlk.eC,leaxncchmecaksacnalidbrsataiosn ccohemcpklsanidsernsrelsy very For quantitative determinations, a raid-level, ex'tmcted matrix calibration check standard is analyzed every 5 ~amples to monitor inslrumental drill Calibration check standards are compliant if instrumental spor i itn. 10ofbe xpd ve. response is within +/- 10% of the expected value. Gpaenseioensofrtchhetatrgnegtaaychegsroiusposfsdumplens.aQrueagneiszisoonnoafyasch n(aiytsdbused oofn wheoreetpcoinesde of Quantitation ofthe target analytes is based on linear regression analysis (weighted I/x) oftwo ex'tracted to ove spf. ought ors ugbe ple esporsmooin mod fe nS matrix curves bracketing each group ofsamples. Quantitation of each analyte is based on the response of one or more specific daughter ions using the multiple response-monitoring mode of the instrument. REREPPOORRTT DDAATTEE:: 0035/2211/899 11558866..00000033 re ont FA 52 Blanks 5.2 Blanks TAi eoxratci.oan olarmk,pliiofnbavnokimraSrTOsumogMeEleLm,tan,EsRdCo wielhs5thebdtchaliobfrastigonl.uns Two extraction blanks, utilizing water as surrogate matrix, arc cxtractcd with each batch of mmplcs. Additionally, two samples of blank matrix or surrogate matrix, used for the ex-wacted calibration curves, are uscdaloo wil xc bach of sles nd unc. extracted along with each batch of samples and curves. Blanksare compliantifntargetskye s detctdshove the intof detection forapif ant. In Blanks are compliant ffno target analy~e is detected above the limit ofdetection for a specific analyte. In us dy, Bawrere ckomplisant. this study, all blanks were compliant. 53 Surrogates 5.3 Surrogates Terbycinpeforancane sulfoneiswed 3 8Sogn hs nhl SoerssiS Tetra-hydro perfluorcoclane sulfonate is used as a surrogate in this analysis. onorsdto con gros msrumenarle monitored to confu'm gross instrumental failure. Surrogate restxmse is 5.4 Matrix Spikes 5.4 Matrix Spikes Duplicatematiseaosizing arg ays fox hich quan das presi were Duplicate matrix spike analyses utilizing all target analytes for which quantitative da~a is presented were a an rly ot oecontr ail.Foren rly,eoverisweeviiUeapable prepared and analyzed for one control animal. For sera amlysis, recoveries were within the acceptable Taal BgAIeS range of g5-115% 55 Laboratory Control Samples 5.5 Laboratory Control Samples LaboratoryConrol Samples are caconponent of is cy. Laboratory Control Samples am not a component ofthis ~tudy. 56 Sample Related Comments 5.6 Sample Related Comments ue omit spevolume, i was otpossible o con matspike dis on any of hsspl. Due to limited sample volume, it was not possible to conduct matrix spike studies on any ofthese samples. inhthe retunderpinof oesry elbodsnici at bi ser 3 ule Although the current understanding ofthe analytical methods indicate that rabbit serum is a suitable SH06Ymeiren.tamvdabtloesporkcSomupes focniis maatoenre reetcommmeeonfdaeldy.sSiasd. aCormmpoauntddeefsoirsSFaiEtDolSnainssd surrogate matrix, matrix spike studies for this matrix are recommended. Standard materials for PFDS and M463 were not available for compound identification at the time of analysis. Compound identificalion is iid on eaenabl renieandmsspect da onion with compound STR b~l on reasonable retenlion time and mass spectral data consistcaat with compound structure. a a Sr EE TE E EEE DGDdeeeletsesypcittieteeddtithifnhneottiehnhbecnesereseccaeseseeaerrdaadaasdateyimtsepe,clteit.osh.nelPlPieRmiFsOOuisStnSs,i,tthhPeEatdFFteHdrSeiSls,c,uPttPlFtiFeoDdDnSffSr,o,oPPnmmOOtiAtAhhAeesAs,s,mapaananbllddl.MssMPaaGmF4m6pO3p3lSleewAessArieizer,eee,,Mddss5eeeevt3vcee6ecrirtaaedlaldDfildiununsroeMroaoShccchThooefmwfethihrceeealsrsavwmeperpxslsees adneSeat1elyc3rtzweedden;infoassrooetmmheceesofeifathnhdaelystanemps,peytlhseessaeasnpd'fdlmethhmeeaeddAbeoedtveeeccttteihcooetnieolisnitmiilitmimtatiistesdeissitd3inmpeapatbee.dnPttoFibObrceiSsaAppoAppfrr,ooMxpii5mmb5aa6ent,elaldyyn1d52pMpppb5pb7..,0PPwFFseOOprSeSeAAcianendd MTTihh5nee1eva3vewearreagrgeeenPhPoeRFtOvOdSeiStcencocogtmenndcsteiamnnbttareinatsoyiconsnhamewarapssvle55d4a4pbpproppvobe,v,tcichoouevvyeeersrfitiLonnrmggsaaatlerrdaasnndggeaeeteodocfftmi31oa1n-y-11lbi11me55ipdtpoolpefb.8.0TpTphmbepsarehnodvvaael1lnou2e<eespasptaabsrsr,e0resllsiipggehektctltlyiyvely. ThmT{mhiohogedsedhivieaifrpveieetedrhdrraamgmgneeaeettPhtPhheyFFoaHd1SvvSue0lrsdlaeevgdmveeeeotlovcsdadexlexeugtteerhesraemcmotibentsheeaedesdrnseveienShdstaehnpPmeesrsepeeSevlselisas.oasm.umppsrllpyeelvefsisoowrwuasaasldsyu33lGt5sippaspnbrbdovmardcaoroynsbaseasadmaruaanenlgglteoetoiofomffp55r-a1o1dv00ue0l0mtppsepnb.rt.sTaTthomhiptishslseaeveseraaTgsne eitEsheanmspepopsraormxlipmmloeadsteiflrbryoocmm1a0iaatodinmculemtessa,hdtihegehhheoiirgghthhheeeasasnttvtvhyaeelueleescvdetelmseteepmrtrmiehnvioniedoedducsiolnayuanodnbaooscnencro-v33ueMMndtwiwfonoroaskrUksemiersrvadwlalsamsseta11o33pfppapbddbui.lftIessteeiasracuuesnablmikoepewlleysUst.htaIhnt e ththoe mrinoor mouofdaifpmicpatssio.ns made to the analytical method could account for this dramatic difference between the Tseport elloste two groups of samples. This report reflects the cst most accuaccurate daa data avaable available aat istiffs time. F 7 R SanE e ReesoT r TT EEEE SaSrapmlpelessaanndd oxtoct extractswillwill bereine retainedffoorr re future vali,essary. evaluation, ffnecessary. RREFP_AO~RRTTDDAATTEE::00552/21I5D99 11558866..00000044 we sroOR eLisasonn EE A 85.121 AAAtatttcaachchhmmmeeennntttABA:::QQQuuuaaanlniataiittavitveiveSeRuRemsenusaulrlttyss oofoffPPFEFCOOsSSaidanendntdifPPiFFeHdHSSDneSDtaeetmrepmrlmineianstoaitfiooCnnhildren'sSra 8.2 5311.3 8548.4 AAAAAAutttttttaaataccccthhhhtmmmmeeeesnannnttttCDBDCEc:c:::::CTAQTChhanauhabahbaaliymllieeninitoocaooftfemaffiFClvFCueAAnusDSCCeatsuttoTTomtadAdmyAfycnocrarrProoyEnntoyOyfmmSFssaCnsdidFenHtSifidedecinmiSanmapiloesnof Children's Sera 8.5 Attachment E: Analytical Data for PFOS and PFHS determination atfochmers E E E E R e Re Re TimDGeone,eAAi(llChreri. Lisa Clemea, Analylical Cheraist Ay -- `To Hansen,PRD. SudyDrcor Kris Hansen, PtxD., Study Director sDluaeils Date shilgs DDuatce RREEPPOORRTTDDAATTEE:: 052199 05/2IF)9 11558866..00000055 we