Document Rj0EEZo4k22Q8GaG3MLXNyG9n

Jean 8. Sweeney am CERTIFIED MAIL 30 Environmental, Health and 31 enter uling0224.0PiTs 651737 3569 327085 FECHQ-. 05NGQ8-00373 447 2222-63933939 i NO CBI EPA East - Room 6428 Attn: Section 8(c) Office of Pollution Prevention and Toxics Washington, D. C. 20460-0001 Re: TSCA Section 8(e) Substantial Risk Notice: Sulfonate-based and Carboxylic- based Fluorochemicals, Docket SEHQ-0598-373 - Fluoropolymer Generation On February 26, 2010, 3M provided to the EPA a TSCA 8(e) submission summarizing data generated by 3M on behoaflthfe Fluoropolymer Manufacturers Group (FMG). This information resulted from Generation Test Method Development experiments aimed at developing a method to test whether fluoropolymers arc capable of"generating" perfluorooctanoic acid (PFOA) when heated to just below the onset of its melting point. As 3M indicated it would do in that notice, we are now enclosing the recently finalized third report which details the method development work carried out from May 2008 through July 2009. Although 3M does not believe that these results satisfy the "substantial risk" reporting exposure pathways, and therefore, are placing a notificationof these results in the $(e) docket. Ifyou have any questions, please do not hesitate to contact Jeanette McCauley at S=e Sn 11{ pu) Staff Vice President, Environmental Health and Safety Operations CONTAINS NO CBI p2 2009 Annual Report on Method Development for PFOA Generation Testing David Ehresman -- 3M Medical Department Jeremy Zitzow -- 3M Medical Department Venkateswarlu Pothapragada -- 3M Materials Resource Laboratory George Millet -- Dyneon p3 Table of Contents INTRODUCTIONummm' Page IL KEY ASPECTS OF METHOD DEVELOPMENT EXPERIMENTS. .............4 A. Accelerated Solvent Extraction. 4 B. Thermal Test Apparatus 4 1. Single Reaction Flask and IMpinger TEN... 2. DualReactionFlask and IMpinger Tait... 3. Standard Conditions. ............. 5 C. An4.alyticOatlheArppCroondaicthioannsd: PRO. GIESS.......rrrrssS5 I InstrumentMinimum Detectable Limi.......vreS 2. 3. Minimum Detectable Limit (Method) Lower Limit ofQuantitation (LLOQ) ver verre 6 4. Values between LLOQ and the minimum detectable limit A 5. Blank Corrected Totals - mmm------6 6. Analyte Description. smm--0 a b. OPterhfelruopreorofcltuaonrooiccarabcoixdyl(iPcFaOcAi)ds (r PFCASn ).....s ..vnT Do T1.eStSUBTSeKsAtNCSE uor bs|=t"AaS RnECEIcVE"e... semen] ] 2. 3. CTesrt SyuobTmessi2ttS~UlB"aSRlIeAnmNeCicExed2ed..".Test SUBSANCE| orn T T 4. ASE Solvent-Washed Test Substance2. ns Il. AR.ESULAcTcSelOeFraMteEdTSoHlOveDntDEExVtrEaLctOioPnM(EANSET)EXPERIMEw NTSmms--ne--s I. ASEextractofiToesnt Substa|nacned 2.......... 8 2 100CASE teste smn00 B. 3. ASE solvent-washingof Test Thermal Test ADPAT.a.tuS Substansc2esmmm--s--cm_L I. Single ReaFlcasktTesitingo. n .... mmm i pe a Stepsto Optimize Test Apparatus. 12 b. Evaluation of PFOA Standard Curve Recovery 3 Results after ManipulationofTest Substance 2 14 (1) TAhSeErmSaollvTeesntt-EWxapsehreidmeTnetsstoSfuTbesstatnScueb2st.a.n.c..e..2..and14 (2) Washing with methanol, acetonitrile and 1.0N Formic Acid cnn 1S (3) Cryogenic milling 16 (4) SuVbasctuaunmceO2v.en Results For Cryomilled Test - 16 d. Results for Thermal Test Periods Exceeding 24 hours ..17 PReEsruflItsOTfOotCrAPDiFOOXoAY,InCWiAtChISOt.h.e.r Homvolmogrousnmnnns20 2. Dual a ReacFlask Testing .... Thermal Test Apparatus "Re-design ......o..nnnr:2233 b. PReesrulftlsufOorrOPCFAOrAD,OWXAiYtClhKi.cOt.h.er Homologous 25 IV. V. RGLEOFSESRAERNYCOEFSTEwRMo S ANmD AaBBRnEVIsATIONS 34 36 ii ps I. INTRODUCTION pPelarsftliucosrOoIvonedcrutsattnhroeyicp(aaFsctMiGd$)(yePhaFarssO,Aca)trhreiiseFgdleunooeurrtoaatpeosdleyrfimeresoromfMetahxnepuetferasicttmsueurnbetsrstsatnGocreaos(usapesoPsfTtwFhhEeetchSoeomrcpioestiytoef) the tehxepodseevdeltoopvmeernythiogfhsatmemppleerahtaunrdelsi.ngTtheecshenieqxupeesrtiomemnetassuirneclPudFeOd Atwroesmiaduianlselienmtehnetst:estfirst, `sumbestthaondctehaatt isnucblupdaretd pdeersibginlloiofnnleevwelesq,uainpdmesnetcoanndd, ptrhoecdeedvureelso.pmTehnitsowfotrhke wthaesrmpaelrfteosrtmed by 3M Company and Dyneon LLC onbehalf of the FMG. throughSrienpcoerttsheanbdegtiencnhinincgaolfdtihsicsuspsrioongsr.am,Thtehe fFirsMt Grephoarst iwnafsorsmuebdmiEtPteAdoftoththee progress US EPA in April 2007, and the second was submitted in September 2008. These reports covered work done from late 2005 through May 2008. eJuxlpyer2i0m0e"9nT,htiasatnitdhoinrp,drearsneedpnotsrstumiomnnfaormriemztaehtsoiodtnhdeaebrvoeeuslutoltptshmoeefnttetchchoonsveieqreusxepswerouisrmekedncttasor.rpieerSdpfoeocuritmfiftcrhaoelmlnye,Mcatehysesa2rr0eyp0o8rtto includes => (AAdSiEs)cutsosidoentoefrmtihnee pwrhoettohcoelr,bparcokcgerdouurnesd aPnFdOrAesuwlatssofpraecsceenlteirnattehde tseosltvesnutbsetxatnrcaectuisoensd in the thermal tests, and => rTehseultfsuortfhseromdeevetlesotpimnegndtonaendwiftinhalthdeesoirgignionfaleqdueisipgmneonft tthoepteerstfosrymsttehme,tahnedrmtahletreesstu,lttsheof initial testing using the redesigned equipment. suspens`iTohnegtresatdesuPbsTtFaEncseupupsleidedinbAyStEheaFnMd Gthemtehmebremarlctoemsptianngiemsetthhoatdswawsasmaanmuifxatcutruereodf TweistthoSuutbsutsainncgea, PstFaOndAaredmuPlsTiFfiEera.ndTmwooditfyipeedsoPfTFsEu.speEnxspieornimgreandtes wPeTrFeEpweerrfeorimnecdluodnedthienttehset tshuebstteastncseubasstraencceeihveadd (Test been ASuSbEstsaonlcveen1t) waansdhaesd raen-dmicxreydom(iTlleesdt.Substance 2) as well as after blank, wIhniacdhdiatliloon,wetdhefotrheirmmparlovteesmteanptpsariantutshewaansalryetidceasligmneetdhtoodoilncolguydetoarseidmuucletatnheeoulso.wer bliamsietdofonqutahnetirteadteisoing(neLdLOteQs)t.appDaartatausg.eneTrhaeterdmailn ttheisst rdeaptoartinaenadrlisehroTwanbliensTawbelreesge1n4e-r1a9tweedre using the original single reaction flask equipment configuration. types re"lTahtiisveretpoorPtFdOetAailasnda,nafloyrtiscoamlereesxupletsrifmoernetas,chaolfstohfeoraobtohveer-pmeernftliuoornoecdartbesotxysluibcstaacnicdes (PFCAS). To simplify the report, data are not always presented in chronological order. 3 p.6 `The overall goal of the work has been to develop a reliable method to assess whether PFOA would be released from the test substance, when heated to 315 C for 24 hours in a streamof humidified air. This necessitated developing the ability to quantify the amount of PFOA released. This program has required new analytical methodologies and unique concepts and equipment, and as a result, has presented significant challenges that have necessitated new approaches "Throughout this report the analytesof interest are referred to as "acids". This term is inclusiveofboth the free acid and various saltsofthe free acid, such as the ammonium salt. Tt should be noted that the actual species being quantified is the anion of the acid. In the case of PFOA, the anion is the perfluorooctanoate anion. In addition, testing was also performed for other homologuesof PFOA, namely PFHXA, PENA and PFDA. The analytical techniques used in this study are not able to identify the cation associated with the anion in its dissociated state. IL. KEY ASPECTS OF METHOD DEVELOPMENT EXPERIMENTS A. Accelerated Solvent Extraction Accelerated solvent extraction (ASE) is a fully automated technique that uses common solvents to extract solid and semisolid samples rapidly. ASE operates at temperatures above the normal boiling point of most solvents, using pressure to keep the solvents in liquid form during the extraction process. Typically, ASE methods are completed in 15-25 min, while consuming only 15-50 mLofsolvent. ASE was introduced in 1995 by Dionex Corporation and is recommended under US EPA Methods 3545 and 3545A for extractionof organophosphorus pesticides. In this method development the Test Substance was extracted using methanol as the solvent with the cells being maintained at 150 degrees C and 1500 pounds per square inchofpressure applied. B. Thermal Test Apparatus 1. Single Reaction Flask and Impinger Train "The single reaction flask and impinger train system is an instrument configuration that uilizes a single, pre-heated inlet gas source connected to a single reaction flask within the the heated zone (oven). oven connected to a This set up uses a glass setof two impingers in transfer line from the series. The impingers reaction flask within are outside the heated zone and arc maintained at zero degrees C by immersing the impingers in an ice bath. The impinge train exhaust was passed through an XAD resin trap placed in the exit air stream flow to collcet any material of interest not captured in the aqueous matrix within the dual impingers. See Figures 1 & 2 2. Dual Reaction Flask and Impinger Train has a sin`gTlhee,dpurael-rheeaactteidoninflleatsgkaasnsdouirmcpeincgoenrnetcratiendstyostaesmtriesaamnsipnlsittreurmaelnltocwoinnfgigtuwroatrieoancttihoant 4 7 ffllaasskkss wtoitbheinustehde oinvethnecoovnenne.ctTehdistostetwoupseupsaersattewosetgsloafssttwraonsifmeprinligneerssferaocmhtchoenrneeacctteidonin isenriaens. iceBobatthh.seTtsheofiimmppiinnggeerrtsraairne emxahianutsatisnetdhraotuzgehraondeXgAreDesreCsibnymaitmemreiraslitnrgaptphelaicmepdiningetrhse wexiitthianirtshterdeuaaml filmopwintogecso.llecTtwaonygamsatfelroiwalmoefteirnstearresetantottacchaepdtutoretdheinextihteaarqusetorueasmmsatarlilxowing operators to balance the flow equally through both reaction flasks and impinger sets. See. Figure 4. 3. Standard Conditions developMedanduyroifngthdeiaelxopgeureimbeenttwseewnerUeSpeErPfAoramnedd under the the FMG: following standard conditions => Temperature: melting point oTfhtehetetemsptersautbusrtaenfcoer atsesdteitngerwmaisnesdetbayt di1f0fedreegnrteieals sCcabnenlionwg tchaeloornismeetotrfy the (DSC). This temperature was determined by triplicate testing using DSC to be 315 degrees C. => Time interval: The standard time interval was set at 24 hours duration. => hPuemricdeintty.relative humidity: The percent relative humidity was set at 50% relative => aCacrornisetragnatsfalnodw flow rates: rate of 100 mTihlleilsittaernsdapredr tmeisntutcea.rrier gas was zero grade air maintained at 4. Other Conditions: necessarCyonadnidtiionncsluodtehearlltohtahnerthoepaerbaotvieonsatlancdoanrdditcioonndsitaisodnessacrreibdeedscortihbeerdthiannthtehetesxttanadsard operational conditions. C. Analytical Approach and Progress I. Instrument Minimum Detectable Limit analyte)Miossatnaalnyazleydt.icaTlhiinssstirgunmaelntiss rperfoedrurecde taosaisgntahle envoeinsewlheveenl. a Tbhlaenkin(smtarturmiexntwidtehtoeucttion tlihmeitstsantdhaerdandaelvyitaeticoonncoefnttrhaetniooinsethaletveil.reTqhuiisremdatyo pbreopdruaccetiacaslilgynamleagsreuarteedr bthyaanntahlryezeintgimes seitgahntdaorrdmdoerveiatsitoanndfarrdosm atthethmeeeasstuirmeadtecdonicnesnttrruamteinotnsdoetfectthioosne lsitmaintdaarndds.theTnhicsalicsutlhateinnugstehde to vesatraibaltiisohnsoanfitnhsetrmuemtehnotd.detAesctsiuocnh,limtihte wihnisctrhumdeonets dneottecitnicolnudleimtihte matrix or value isof tlhiemietxetdravcatliuoen for purposes of meaningful quantitation. 5 ps 2. Minimum Detectable Limit (Method complet`eTdhedumreitnhgoadnmainnaliymsiusm. dTehteecsteaboltehelrimnietc(esMsDaLry) mies tahffoedctsetdepbsy(asnucyhaadsd:itdiiolnuatlionsst,eps Sexitnrcaectdieotnesc,tasbolleutliiomnittsraanrsefedresf,icnoendceinnttreartmisoonfsetrerpos)r,altlhiasddwilalddniattiuornaalllyopipnocrrteuansietitehse fmoeraesrurrore.d `demteetchtoadblmeilniimimtu. mThdiestedcettaebclteablliemiltim(iMtD(Lwi)th all stepsof the analysis included) is called the 3. LQoweuraLimnit tofitati(LoLOnQ) reasonab`Tlhyetlelolwtehreldiimfitfeorfenqcueanbteittawteieonn t(wLoLOdiQf)feriesntthevalliumeist. ofThcoencLeLntOrQaticoannavtarwyhich one can dmrianmiamtailcadleltyecbteatbwleeelnimdiitff(eMreDnLt)laabsn.d iOsvegreanlelr,altlhye LLOQ is approximately $ times the lowest point that is fitted on the the eixntcrlaucdtiendg stthaatndpaoridntc.urSvpeecwihfiecraelltyh,e curve in this iptrsoejlefcptrowdourckestheacLceLpOtaQblies ersetgarbelsissihoend values by the lowest s`ptoainndtairndclcuurdveed. in the regression analysisof the matrix matched, full method extracted 4. Values between LLOQ and the minimum detectable limit (MDL) distinguViashlubeestlweesesnthaannytthweoLdLifOfQerecnatnvanlotuebseraecacsuornaatbellyy (qwuiatnhtiintaatcecdepatsaobnlee vcaarniantoiton) by dreefpionritteidona.s Tchoenrceefnotrrea,tivoanluvaelsuefsa.lling between the LLOQ and MDLofthe method can not be 5. Blank Corrected Totals `concentTraatbiloenss tahbatovienctlhuedeLL"OcoQr.recTthede total concentrations" results that have the vhaalvueeoafcttuhael "mbelaasnukr"edrebalctainokn flask creosmueltctseudb"trraecstuletds.from that of the "test substance" reaction flask are considered "blank results wReerseultlesssfrtohmant0h.e5sinngg/lge (rtehaectLiLoOnQf)l.askTshyersetfeomreal,l ahlladrebslulatnsk irnunthsectoambplleestceodmpwlheetreed the ruessiunlgtitnhgecsoinncgelnetrreaatcitoinosn afslarsekpoirntsetdrusmienncte aslelt-bulpanhkaveextnroactbiloannsk pceorrrfeocrtmieodn uapspilnigetdhetostihnegle reaction flask instrument configuration had measurable blank concentrations less than the LLOQ LLOQ w`Waisthabtlhee tiompbleeamdejnutsatteidontoofa tlhoewedruavlalrueeacatnidonblfalanskkcionrsrtercutmeedntresmuoldtisfiwcearteiotnhsenthaeble to be included in selected tables as reported. 6 po 6. Analyte Description a. Perfluorcoacctida(nPFoOiAc) syntheticP,ersfalbuloeropoecrtfalnuooircinaactiedd(cPaFrOboAx)y,liaclsaocikdnaonwdn falsuoCr8osuarnfdacptearntf,luoOrnoeoctinadnuosattrei,alis a aapcpcleipctaetdiomnetishaosdsa sfuorrftahcetaqnutanitniftihceaetmiounlosifoPnFpOolAymaerreizbaatsieodnoonfhfilguhorporpeoslsyumreersli.quGidenerally icnhsrtormuamteongtartaipohnyi(s HalPsLoCk)naonwdntarisplLeCs-tMaSge/MmSa.ss Tspheecsterocmoetmrbyi.neTdhitescchonmibqiuensatairoenwoelfl aprceeircdfo)lg,unopirezoreofdclttuaoonorloosincofnoaracnimodeia(csPuaFcrOiidAng)(Cvp9aerraifcoliuudso)rfoalbnuudotraponecorhifeclmuiaoccraiolddse(cCian4ncolaicuciddia)nc,gipdbeu(rtfCln1uo0otralocihimdei)xtaeantdovitoec:raycildow(C6 VcooLnc1e0n3t,ra1t7io6n-s18(4O)lsen et. a 2007 EHP vol. 115, 1298-130 and Ehresman et. al, Env Res b. Other perfluorocarboxvii acids (PFCAS) (peCr9flaucoidrO)otbhauentrdanPpoeiCrcAflascuiodriod(edCnet4ciafaniceoidid,c),qaupcaeindrtfi(ltCua1otr0eodahcaeinxd)da,nsopiecciafciicdal(lyC6meancitdi)o,npeedrfilnutohriosnroenpaonrotiicncalcuidde: D. TestSubstance I. Test Substance I - "As Received" "Test Substance 1 ias blended polytetrafluoroethylene (PTFE) powdered matrix as grreacedievePdTaFnEdpirnoidtiuacltlsy masixseudppbliyeDdybnyetohne cLoLnCt.ribIuttiisncgoFmpMrGisemdeomfbeeqruaclompporatniyonmsoanfufsaucstpuernesriso.n 2. ZestSubstance2 "Remixed"Test Substance] laboratoTreystpeSrufbosrtmainncge t|hewaacstumailxteedstoinngaarnodtaltaiboenlaeldmaisxeTresftorSuabnsatdadnicteio2.nal 24 hours by the 3. Crvomilled Test Substance 2 reduce tChreyopamritlilceled test size. suTbhsitsanpcreocisesTsesits Substance 2 also known atshaftreweazesr cmriylolgienngi,cfarleleyzegrrogruinndditnog, and pearrytoimcillelisnigz.e bIyt uissitnheg racetpoefatceodoplhiynsgicoarlchiinltleirnagctaiomnast.erWiahleanndchtilhleendrbeydudcriyngiceit,ilnitqouiadscmaarlbloenr edlieocxtirdoestoatriclisqpuirdayniintgroagnend,otthheerrmpopolwadsetricpsrcocaenssbees.finIenlythgerocruynodmitollpiongwdperroscessusi,talbilqeuifdornitrogen chilling and oscillating magnets were used to produce a very fine powder for analysis. 7 p.10 4. ASE Solvent-Washed Test Substance 2 Test Substance 2 was subjected to ASE conditions (minimum 3 cyclesofASE. solvent-washing) and then harvested from ASE cells. Multiple cells containing ASE washed Test Substance 2 were pooled to provide adequate amountsofthis matrix for further testing. I. RESULTS OF METHOD DEVELOPMENT EXPERIMENTS A. Accelerated Solvent Extraction (ASE) During ASE extractionsofPFOA (Larsen ef al., Analyst, 2005 vol. 130, 59-62.) the test substance is heated to 150C for 24 hours prior to the initial methanol extraction. The test substance is then extracted using methanol and a Dionex ASE system. The automated system moves a stainless steel cell containing the test substance, and purified sand (Ottawa sand) in between special filter media, into an oven where the temperature is raised to 150C. Methanol is then introduced into the cell and the cell pressure is raised to 1500 psi. Afier holding at this temperature and pressure for a set number of minutes, the methanol solvent is collected in 40 mL glass reservoirs. The "Method Development Test Program Guidance Document" specifies multiple extractions to the point where less than 5%ofthe initially. recovered value remains. To date, this has required four complete cyclesofpreheating and extracting as recommended by Larsen et al I. ASE extraction of Test Substance 1 and 2 `The primary goal for ASE work was to extract PFOA from the Test Substance e1x.haOuusrtivfierlsyt.goaTlhewaosritgoindaelv"eAlospRaecperiovceedd"urTeeswthesruebsbtyanacsetwanadsarrdefceurrrvede tcooualsdTebsetcoSnusbtsrtuacntceed using blanks and Test Substance | samples extracted and quantitated via the ASE. Fiftcen ASE extraction cells were loaded with Ottawa sand and preconditioned with `methanol. 10 ng/g PFOA IS (internal standard) was then added to all cels prior to the first elution cycle. Various amountsof PFOA were added to nineofthe cells in order to create a standard curve Test Substance ranging | were from 0.5 placed in to the 17.5 ng/g center of PFOA. In the cells. the The next final five two cells, cells 2g aliquots of had no standards or samples added to them, and were the ASE blanks. All the cells were placed in an oven for 2so4lvhersntat(C1y5c0leC.OneN)e.xtTthhee fcievlelscewlelrsecosnutbajiencitnegd TtoesAtSSEubwsittahncmeet|hwaenrole aasgatihne pelxatrcaecdtiionnan moevtehnafnoorl2(4CyhrcsleatTw1o5)0.C.ThTehseesefivfeivceelclesllwsewreerethernunpltahcreodugihn AaSnEo:vaensefcoornadsteicmoendus2i4nghrs at (1C5y0clC.e ThSruebes)e.queAnttltyhe, ctohnecfliuvseiocenlolfstwheirsesreuqnuetnhcreo,ugalhl tchoellAecStEedavtohlirudmetsiomefmuesitnhganmeotlh(acnaoclh approximately cach to a 25 ml 19-22 mL) were brought 0 a final volumeof exactly volumetric flask and "topping up" with methanol. 25 ml by transferring 8 pt disposabAlne aploilqyuportoopfyl2e.n5emtiubferocmonctaacihnivnoglu5m0e0truLi.cofflrasekagweanst tghreandetrHa;nOs.ferrTehdetomeathnaenwo,lclweaasn, etvhaenpoerxattreadctferdotmhrthoeugthubSePsE.usiTnhgearLesaublCtionngccourRvaepihdaVdaap,lianneadrtrheegrreessisdiuoanleaqquuaetioouns wpihtahseanwa"sR" value equal to 0.9992. "The ASE blanks all had measured concentrations less than the LLOQof 0.5 ng/g. The CPyFeOlAe. OnIen bToetsht CSyucblsetsanTcwe o| sanadmpTlherseeh,adthreecroevceorvieersedoafmo1u1,n1t.1o,faPndFO12A, 1.0and 1.2 nglg. from eachofthe Test Scouubnsttsa"nocfet|hsearmapwledsatwaaswelreessctohlalnecttehde LanLdOiQnt(esgereatTeadbblye 1). the LInC-TaMbSl/eM1S, "iAnbsstorluumteentArsoefatware. `These data are converted using the instrument calibration curve to ng/g. AAA they areCobuenltoswththaet LarLeObQelfoowr tthhiesLinLsOtrQumleenvtelcuarrveen.otTchoenvaebrstoeldutientaorenag/igntceognrcateendtrcaotuinotnss fiofr tihnete0g.r5atnegd/gabsstoalnudtaeradreina tchoiusnetxspdeurriimnegntsuwbesreequ4e5n2t,7e7xt9raccotuinotns cycAlsesin(dCiyccalteesd in Table 2 and 3) 1, the were all cloesnscetnhattratthieonisntdeugrraitnegdecxoturnacttsiofnorctyhcele0s.52nagn/dg3straendmaaridn. leTshsitshiannditchaetLesLtOhaQt PoFfOA0.5 ng/g as established for this assay. Test SubstancePF1OA(1C5o0ncT.) Abs. Area bs. Area SSaammpplloe#1|| ASE11Cyc| l1e 50,29 AS7E5C5y9c1l5e2 | ASECycled [[S(aomSmpasmlplolee##sm2||| 11 12 | | 56/090570894 | | 192553 | 144243 | 167.416 et2rs | 10 e| seam Wem |tae] [ B "S PFOAa C#on5cem e ]ntratp i1onsl 2(ng/g)of| oreAS_E Cy6d0eLs7124& 3 were less 1t7h6an02L1LOQ o|f1054ng/9g 466| -_ Absolute Area (counts) of 0.5 ng/g Standard: 452.779 this caseA, duplicate experiment a large aliquotofthe had Test rSeucbosvtearnicese with was rnee-amrilxyetdhetosaenmseurreeseulvtesn(dsiesetrTiabbulteio2na)o.f In tfhreomdicfofenrternitbuPtTioFnEsopfrosdtuacntdsarmdaaknidngmoudpifthieedcosmupsopseintsei.onTghreadoersiogifnaPlTcFoEmpaocsqiutierewdasfrpormeptahreed bflouerndceodmpaanndimeisxsepdonatsoornienogftthehegecnoemrpaatinoyn'steslt.aboTrahteorirees-.mixTehdesTees"treS-umbisxteadncTeesstamSpulbesstawnecree samples" will be referred to as "Test Substance 2" for the remainderof this report. 9 p12 TABLE 2: ACCELERATED SOLVENT EXTRACTION Test Substance 2 (100 T and 150C) Table 2(a): AcceleratedSolventExtraction at 150 C PFO(nAglCgo)nc. | (cAobusn.tsA)rAeSaE| (cAobusn.tsA)rAeaSE | (cAobusn.tsA)rAeSaE p ASE Cycle 1 Cycl1e Cycle 2 Cycl3e [sample#1| 16 703.007 [ sample#2| 15 | _esaoe6 |7ie |s32o 6216r| [TT samplews to | seerss | ssvers| sssioz | = Absolute Area (counts) in 0.5 nig Sid. = 495,128 *_ Suspected contamination iniqud transfer _ Based on this work, the amount of PFOA extracted from the re-mixed Test Substance samples (Test Substance 2) was reduced to instrument background levels after one complete ASE extraction cycle. To ensure that the PFOA concentrations were reduced to background levels, a total of three cycles were run during each ASE experiment. 2. 100C ASE test PFOA and its salts, the ammonium salt in particular, are susceptible to thermal degradation. Becauseof this, it was speculated that the PFOA may not be completely extracted at 150C using ASE, as this temperature is known to be the onsetof thermal degradation for the ammonium salt (APFO) Larsen, et al 2005 Analyst 130, 59-62.]. To avoid this complication another ASE experiment was conducted with Test Substance 2 under the same ASE conditions as before, but at 100C insteadofat 150C. The oven temperature between cycles was held at 100C as well. Once again, after the first cycle, we recovered 1.1-1.4 ng/g PFOA. After the second and third cycles through the ASE, the PFOA concentrations remained less than the LLOQ (see Table 2b). It appeared running the ASE experiment at 100C instead of 150C had little effect on the amountof PFOA that was able to be recovered from Test Substance 2. Table 2(b): Accelerated Solvent Extraction at 100 C PFO(nAglCg)onc. | (cAobusn.tsA)rAeaSE | (cAobusn.tsA)rAeaSE | (c"oAubnst.sA)rAeaSE Sample ASE Cycle 1 clo 1 Cycle 2 "Cycle [Sample#1| 1 671.879 283.464 [sample#2] 12 714,343 [sample#3] 14 [| "7reesz | 2e3737 | 250042 | [-- Avege| 12 -- ALbLsOolQut=e0A5renag(gcounts) in 0.5 ng/g Std. = 519,091 ASE Blank Concentrations in ASE Cyd 1 all < 0.5 nglg 10 p13 3. ASE solvent-washingof Test Substance 2 the startTohfethoirsigmientancoadstdienvsesleoqpumeenncte wasorakgrceoendsipsotred;odfuttihrnegc discussions steps: with EPA prior to 1. ATeGsEt Se.xitdraaicatnicoen.ofthe samp iv quantify the "baseline" levelof PFOA in the 2. `hernal testing via exposure to high temperature with trapping of any PFOA released. 3. TAessetcSounbdstAanScEe estrictionof the afer the thera sample test to quantify the level of PFOA in the `much,if"Tahney,thPreFeOdAatawapsoirnetlsewaseerde dtuoebetoudseegdraidnaatimoansosf tbhaleanTceestapSpurbostaacnhcteo sdaemtpelremidnuerihnogwthe thermal tes. thermalIttewsatisngdetcoirdeemdotvheatPTFesOtASurbessitdaunaclem2atserhioaull.d bAeS"EASsEo:lvseonltv-ewnats-hwiansghwead"spreixoprecttoed to rPeFdOucAe ntehaerutnhceerLtLaiOnQt.y inIttwheasovaelrsaollextepset,ctseidncteowheelwpedrieffefrienndtiinagtemebaestuwreaebnlePFcoOnAcenrterleaatsieodns of pfrriommatrhyepsaurrtfiaclcee oorfptohteenTteisatl Sduebgsrtaadnacteio2nopfarTtiecslte,Suvbesrtsaunscere2ledauserifnrgotmhethteheinrtmearliotreosft tchycele. "iTnhteerrioerasoofntthheatpatrhtiisclteessot fwToeusltd dSiufbfsetreanntcieat2e ibsetthwaetetnhePAFSOEAsoonlvoerntnewaertsthtehesusrufrafcaeceorweilnlt,hebut Sdoolevsenntot(mpeentehtarnaotle) into the particle. or by any other coTemsmtoSnulbystuasnecde's2olivsernto.t soluble *. or swellable by the ASE full cyclAeSsEa-ssodlevsecrnitbwedasahpuivne"ivnasseccatriroined[1oLuAt.b1.y sAubbojeuctti3n0ggToefsTteSsutbsStuabnsctean2ceto2thwraese ASE ASE solvent.washed and set asic for nse in future thermal test experiments B. TheYerst Amppaaratle: conditio"nTshebethienfgiuasletdeisntioutraemet"ahiosodfdtehveeluovpemraelnlt mweotrhkodarbeeaisngfodletv~ewsl:opeHde.atTha esatmhpelremoalfttehset RTeTs)t, SaunbdsttaranpcePFatO3A15exiCtifnogr t2h4ehsoaumrpsleinacelsltirneaamnofizmpeirnogegrratrdaein.airThiunmsirdaiifniecdontsois5t0s%ofRtHwo(at tirmappinagneyrsPFcoOnAtatihnaitngmahyighhapvuerimtiygwraatteerd,tbharcokuegdh utphewiimtphiangieXrsA.DThreesiinmcpairntgreirdsgealosnotchoeolentdhe.to rhoetacatiironstfrleaaskm iesxiatsinmgaltlhecoonviecnalinflwahskicwhhotsheesianmteprlieorriesacctoiaotnedflwaiskthisahseilld.oxaTnheecosaatmipnlgeto Fmiignuirmeiz1 efoardasorvpiteiwoonfofthPe FsOamAploentroeatchteiwonalfllsaoskf,thaendflFaisgkuraend2 the for atuvbiinegwoefxittihengitmhpeinflgaesrk. See train. n p14 Figure 1. - AT -- A SE 1 E . Figure2. rl Wd = pa a iN hd a ~ -. ES A 1. Single Reaction Flask Testing a. Steps fo Optimize Test Apparatus methodOdveevreltohepmceonutrsweoorfkthteo tphaestpoyienatr,thtahtetchoenrdeitisiocnosnfhiadveencbeeetnhaoptthiemirezseudltfsorartehermal test consistently showing how much PFOA (perfluorooctanoic acid) is being transferred from the 12 p15 swhaamtplbeacceklglrtooutnhde liemvpeilsngoefrPtFraOinA. Twheerefiprsrtessetnetp iinn othpetismyisztienmg itthsieslfs.ysTtheemsewaPsFOtoAdebtaecrkmgirnoeund lisevleolcsatmeadysihnacveelboew-elnevienltrqoudauncteidtaitnitvoetahnealtyhseirsmafolrtePsFt OsyAstisemcofmrmoomnailryipnetrhfeorromoedm iinn twhheiscahmie daeb.terOmvienre the the csoyusrtseemo'sfebiagchktgrmoounnthdsP,FnOiAn.e seTphaersaetebl"abnlkanrkunrsunwse"rweenroercmoanldlyucctoenddutocted bteefmopreeraotruarfetecrycolteheurseedxpweirtihmetnhtestwhehremrael atcetsutaslytsetsetminwgaosfaPlFwOayAst3r1an5sfCerfoocrcu2r4rehdo.urs.TheInall nthieneoLfLtOhQes0ef b0l.a5nnkgr/ugns(,seneoTasibnlgele3)i.mpTihnegreefroorre,XaAllDblraenskinrcuonnscceontmrpalteitoendofwePrFe OcAonseixdceereeddedto be< 0.5 ng/g. Based on the nine blank runs, our routine background PFOA levels should be less than 0.5 ng/g. ee | Shem it a ar TBlAaBnLkER3u:nsTHUEndReMrASLtaTnEdSaTrdACPoPnAdiRtAiTonUsSfo(rS2I4NGhLoEurRsEACTION FLASK) p in Impingo#r1| in Imping#e2r | in XADResin | in Rxn Flask| (gig [[BBlaannkkRRuunn##2|| "<05 <05 |" <0s | <05 | <o05 | <o05 | |""<0s | <05 | <05 [| <05 | [BlanBklaRnkuRnun##43|| <05 |<0s | <05 | <05 |<05 | <05|<05 | <05 | <05 | <05 | [BlanBlkanRkRuunn#5#|| <05 | <05 <05 | <0s | <05 | <05 | <o05 | | <05 | <05 | <o05 | [B[ a[n0Ek0B mR-su0kna 5m#msngln g||l <<k w00os5sR| I |u<<n o00ss5#| T | <os =<o0ss T | |< <<0oss50 | | 1<<<5 o0o0555 || | b. Evaluation of PFOA Standard Curve Recovery. impingeWretrawienrwehaebrlee ittowianstrcoodlulceectaedPFanOdAqusatnatnidfairedd.inTtohethsetsaandmaprldesfwleasrkeapnldacmedovien tihteo the shoaumrps.le Tfhlaeskimlpociantgeedritnratihnewoavsenl.ocTahteedoivneannwiacse btahtehn ahnedatheaddtoan31X5ADC arnesdinhecladrttrhiedrgeefpolra2c4ed oinmptihnegeerndtrtoaintrsaeptuapndwacsollveecrtyaenfyfiPciFenOtAatthcaotllmecatyinhgaPveFOmiAgrtahtatedwatshrionutgrhodtuheceidmpinitnogtehse. This s1a0mnpgl/eg.flTasokt.alFrievceocvoenrcyeonfttrhaetsioenssotafndPaFrdOsAinwetrhee iimnptirnodguecredt,raiinncsleutduipngwa1s.0,be2t5w,ee5.n0,607.-592a%n,d wstiatnhdaarndso,vewrhalilchavheardagaen recoveryofapproximately 79%. R? valueof0.9929 (see Table 4 A & Fciugruvree was 3). Bplaostetdedoonftthhiesse: regression analysis we moved forward testing Test Substance samples. 3 p16 TABLE 4: THERMAL TEST APPARATUS (SINGLE REACTION FLASK) Standard Conditions with PFOAtEovaluate Standard Curve Reco Bi SPtrde.dCiocnteed.| Cone. (nglg) | Conc.(nglg) | Conc. (ngig)| Conc. (nglg)| Total Conc. (nglg) | in imping#e1r| inimpinge#2r | inXAD resin | inRn vessel| (nglg 06 <0605 | <<005 <<0055 | 0168 6702 ---- 3 06 <0s 5 0 ~1L0a=05ngig 63 | 1s 0065 <<0055 7[9X] 9792 Figure 3. ReAccotuvaelrevd.fPrroemdiTchteerdmCaolncT.estOfApPpFaOrAaSttau@nsda3r1d5s Je ound ase. orsy ~ of g i3 i Priced Con 09) Results after Manipulationof Test Substance 2 (1) Thermal Test Experiments of Test Substance 2 and ASE Solvent-Washed Test Substance 2 flask to "The the firs thermal test impinger train as edxepsecrriibmeedntasboavfeerweefrfeiciceonntdturcatnesdfewriotfh PFOA from the Test Substance reaction 2 under `tThheesatvaenrdaagred caomnoduintitonosfoPfF3O1A5tCh,atacnodll2e4ctheodurfsroofm tchoenssetasnatmp5l0e%s wRaHs 19.060 mngU/mgi(nseaeiTrfalbolwe.5). I" Since the blank runs were consistently at or under the LLOQ, they were not subtracted from the average total concentration. erm CELE SEE S| Standard Conditions for 24 hours with Test Substance 2 [ sample#s| 85 | 17 | ~1L0G=05 ng/g 85 [ree gel e6| single step using SPE. The next seriesof thermal test experiments were conducted using ASE-solvent washed Test Substance 2 in the reaction flask, again under standard conditions. The average amount of PFOA that was recovered in these runs was 1.4 ng/g (see Table 6). This was a decrease in PFOA concentration compared to the amount (9.6 ng/g) that was transferred from the non-ASE solvent-washed Test Substance 2 (Table 5). TABLE 6: THERMAL TEST APPARATUS (SINGLE REACTION FLASK) Standard Conditions for 24 hours after first subjecting Test Substance 2 to Accelerated Solvent Extraction [sample 07s]| <05 | 0s [ <05 [7 16 | [_sample0#92|| `Addedto#1 | 07 | <05 | 16 | [samples| ["Addedto#t| 08 | <05 | var | [Sample #4 <08 09 Average 14 1 (2) Washing with methanol, acetonitrile and 1.0N Formic Acid ASE extractionofTest Substance 2 resulted in the recoveryof roughly 1 ng/g of PFOA, but seemed to reduce the amount subsequently recoverable by thermal test treatment by nearly 80% (1.4 ng/g versus 9.6 ng/g, see Tables 5 and 6). Since the resultof these two sets of experiments was markedly different, more tests were conducted on Test Substance 2, in an attempt to account for more of the PFOA not recovered by ASE. The first experiment was to extract Test Substance 2 in methanol at room temperature for 24 hours; the amount of PFOA that was extractedin this fashion was less than the LLOQ. . p18 "The second test consistedofextracting Test Substance 2 ina 10:1 combination of acetonitrile and IN formic acid. After shaking the contents for 24 hours, the amount of PFOA that was extracted was also below the LLOQ. (3) Cryogenicmilling Since the extraction solvent wets but does not dissolve Test Substance 2, there was a possibility that PFOA was physically trapped within the Test Substance 2 particles, where the solvent could not access it. Cryogrinding Test Substance 2 was thought to make the PFOA. more accessible by increasing the surface areaof the particles. A large aliquotofTest Substance 2 was finely ground using a liquid nitrogen mill. This cryomilled Test Substance 2 was shaken in methanol for 24 hours at room temperature; the results were promising, as 0.9 ng/gof PFOA was extracted, compared to less than the LLOQ for the non-cryomilled Test Substance 2 extracted by the same method, shaking in methanol. This showed that someofthe PFOA was protected from solvent extraction by physical trapping within the polymer particles. Several thermal tests were then conducted on this cryomilled Test Substance 2 under the standard thermal test conditions. Based on three runs, the average amount of PFOA collected from cryomilled Test Substance 2 was 9.0 ng/g (see Table 7). These PFOA concentrations were similar (0 the test results from the non-cryomilled Test Substance 2 samples, 9.0 ng/g vs. 9.6 ng/g (see Table 5). r | E aa]a Standard Conditions for24 hours with Cryomilled Test Substance 2 inImpingers | in XAD Resin_| in Ran Vessel gig [sampled] 65 12 <os | 77 | [sample#o|"78<2 os | 1 es | [Sample#to[er Tia] <05 [Tes eee Average |oo| + sTtheepcuosnitnegntSsPEo.f Impinger #2 were added1 Impinger #1, which was then extracted In a single - LLOQ =05 gig (4) Vacuum Oven Results For Crvomilled Test Substance 2 ASE extractionof the cryomilled Test Substance 2 was ruled out du to concerns that the finely ground material would cause excessive ASE system back pressure. Therefore, the cryomilled Test Substance 2 was placed in a vacuum oven in an attempt to remove PFOA. ASfutbesrtahnecaeti2ngwatos aspupbrjoexcitmeadtteolyth2e4t0heCrmianl ttheestvcaycculeumunodveernsftoarnd2a4rdhocuornsd,itciroynos.milTlheidsTfeisrstt e1x0p5e.r0inmge/ngtorfesPulFtOedAi(nsaeenToatibcleeab8la)e. deHcorweaesveeri,n rveaccouvuermedtrPeaFtOmeAntfruonmdearptphreosxeimcaotnediltyi9o.n0s dnigd/g not remove allof the PFOA contained in Test Substance 2. Ina second experiment, the cryomilled Test Substance 2 was heated to 240C in the vacuum oven for 72 hours, and then 16 pts rreucnotvherroeudghfrtohme tthheerimmaplintegsetrutnrdaeinr(ssteaendTaarbdleco8n6d)i.tioinns.a thIinrdtheixspcearsiem,e1n.t7,nngo/ng-corfyPoFmiOlAledwaTsest tShuebrsmtaalncteest2 uwnadserhesattaenddatrod2c4o0ndiCtiionnas,vaancduuthmisovseanmpfloer r7e2cohvouerrse,d a1n.d6 ntgh/egnorfunPtFhOrAoug(hsetehe dTiafbfleereSnc)c.e When compared was noted. to the cryomilled Test Substance 2 at 1.7 ng/g, no significant TStAaBnLdEar8d: CToHnEdiRtMiAonLs TfoErS2T4AhPoPurAsRaAfTteUrSfi(rsStIsNuGbLjEecRtEinAgCTTeIstONSuFbLsAtSaKn)ce 2 to Vacuum Oven Extraction (240 T) Table 8(a): Cryomilled Test Substance 2 After Vacuum Oven Extraction for 24 hours p InImpingers*| in XAD Resin | inRxn Vessel | Cone. (nglg p [a2 1 08 | <05 | "50 | WESTIE [_T_abslea8m(cp):leTe#stiSzu|bsitnaInm1cpei7nZgo(rNso*n| |-criynom<XilA0iDed5R)osAifnt| e|r V_ainc<Ruxun0mVO5evsseenlE|[x|tractCioonnea.f7or_7(ng2l_g | hours | see [tant[SSE[SRN| niin| p inImpingers*|in XAD Rosin | in Ran Vessel | Conc. (nglg [ sample#is| 16 | <05 | <05| 16 | - LusLiOngQS=PE0.5 nglg no signiCfriycaonmtilelffiencgtToenstinScurbesatsainngceth2etroecroevdeurcyeotfhePpFaOrtAilfersoimzethaendpairtniccrleeasseussiunrgfaacesiamrpelaehad rmeedtuhcaenotlheexatmroacutniotn.ofCPrFyOomAilrleicnogvearneddhbeyatsiunbgseuqnudeenrtvtahceurmuamlftoerst7i2nghobuyrsapaptr2ox4i0maCtedlidy 80% 2T,homeuagshurtahibsleclaemanoiunngtsmeotfhPodFOwAaswdeerseigsinleldrteocorveedruecde bthyetahemosuunbtseoqfuePnFtOtAheirnmaTlesttestS.ubstance 4. Results for Thermal Test Periods Exceeding 24 hours PFOA wDeuree tr0eltehaeserdesuflrtosmofhetahtetvraeactuinugmToevsetnSuebxsptearnicmeen2tsafitnerwhviacchuummeatsrueraatbmlenetafmooruunptstoof72 rhoeuarcsh,edthwehtehreermnaolmteesatsuwraasbleextaemnoduendtfoorfaPlFoOnAgerrpeemraiiondedofintiTmeesttoSusebestiafnacepo2i.ntTceosutld be 5Su6bhsotuarnsc.e D2uwraisngththeinsseuxbtjeencdteedd ttohearmtahlertmeastl,ttehset iinmpwihnigcehrsthaendtiXmeAwDasreesxintewnedreed rferpolmac2e4d to twhiethPaFnOeAwwsaest arfetceorvteirmeedianftelrev4ralshooufr4s,(85,.432nga/gn)d.5H6ohwoeuvres.r,Tthheerreeswuelrtseisntidlilcqautaendtitfhiatabmloest of levelsof PFOA recovered at up to 56 hours (1.7 ng/g) (see Table 9). 17 p20 STtAaBnLdEar9d: CToHnEdiRtMiAonLsfToErS5T6AhPoPurAsRwAiTtUhSTe(sStISNuGbLsEtaRnEcAeC2TION FLASK) Thioumres) | in Impinger #1 | inColnmpci.nge(rngl#g)2|| iCnoXnAc.D (Rnegslgi)n||inCoRnxcn. V(engslsge)l|| Tota_l(ngClognc. [84 1<os 1 [<" os nA ce5s4 | [3256 o17r] [<o<0ssTwa <05 To | ar 7 | T1l0a=05--ng Total Recovery | __ 7.8 - Impinger rainwas replaced after each time interval wih a freshly slanized set Due to the differences observed i the recovery of PFOA between ASE and thermal testing, it was decided to run a series of ASE extractions on various samples that had been treated in different fashions to see ifmore PFOA could be recovered by ASE. Each ASE experiment that had been run on non-manipulated Test Substance 2 samples resulted in between 1.0-1.9 ng/g PFOA being recovered after the first cycle. Thereafter, no quantifiable levels above the LLOQ of PFOA were recovered during the second and third ASE cycles (inSeaeppTraobxliemsat| ealnyd72.)8. The extended ng/gof PFOA btehienrgmarlectoevsetr(edde.scrTihbeedseirnietsheofprAeSvEiouesxtsreaccttiioonn)s rpersouplotseedd. were: 1 ASEofTest Substance 2, to serve as a control 2 Thermal test of ASE solvent-washed Test Substance 2, then ASE again 3. Thermal test ofTest Substance 2, then ASE extracted a. ASE-solvent washed Test Substance 2, then ASE extracted again temperatSuerrei,esw2a,srde-ornuenntionsgceASifEanoynPAFSOEAsoinlvtehnetp-awratsihcleed iTnetsetrioSrubdsiftfaunsceed2ovsetrorteidmaet trootohme surface and could be recovered. The results showed that the amount ofPFOA recovered by bAeSloEw)e.xtrTahcetioAnSrEemsaoilnveedntb-ewlaoswhetdheTeLstLOSuQbsitnaenvceery2 experiment in had about 0.9 this series (see Table 10 ng/g. which was in line `with earlier results (see Tables 2a & 2b above). 18 p21 TABLE 10: ACCELERATED SOLVENT EXTRACTION ~~ _ Series 1-4 te SS v CoPnFe.O(Anglg) A(bcso.unAtrse)a A(bcso.unAtrse)a `(Abcso.unAtrse)a TABLSaEmp10l(ea)_:_Se|riinesA1:STEestCySclu1eb|stainncAeSE2 subCjycel1cet_e|dionncAeSEto AcCcycelle2e|ratiendASSoElvCeyntcl3e Extraction _ [S|a"mpSalmpele##12]] 10 08 292.692 Lo fame, 08 415.115 [Averagplod e | 10 | as0s0z| 2s2647 | 251890 | [X] TT TExAtBraLcEti1o0n(,b)o:ncSeerbieefso2r:eTaensdt Sounbcsetaafntceer T2hseurbmjaelctTeedstt(wSiicnegtloeARcecaeclteiroantFeidaSsoklwvietnht Standard Conditionsfor24 hours) Lemme Lpmeel plo#2 l n <0L 5| one men 37.504 38.445 Loma Lael TExatbrlaec1t0i(ocn)plo#a|:afSteerriTehs_e3r<:mTa0els5tTeSsutb| (sStiannglceesR2erasecuetbijoenctFe| ldaoskncweiatfhroaSAtzcac6nedlaerr|adtCeodnSdoi5lt0vie8onn1ts0for | [ s2a4mhSopuarlsm)pel#e#6S]T [_ --<05hTl2753 [ <o5 l[|ei# o51745| | isooss| is3sto | fosze0 200249 | | [TExatbrl_ aec1t0i_ (odn):S Ser_. ia e--s 4<m : T0esp 5t Subs|tancS e2025su4Y b5j6ectY e|d twiY ce1t9o_ 4A3c0c8eY ler|at1-- ed9SoS 0lve0nt23| [s --a --m --p <Yol 5Yo | k#e2 ase]| 70686 G [Double Blank #2| --<05 |" 78144 | i292 | e430 | ~- LTcohLre0reQasb=poovn0edi5rne1gsugtlotsthare LfLrOoQm einxpeearcihmeenxtpserruinmeatnddiiffeerr.ent times, so the absolue area counts solvent-IwnaashcoendtibnyuaAtSioEnowfapsrreuvniofuirsstetxhpreoruimgehntthse,rmTaelstteSsutbisngt,anacned 2thtehnatrhunadthnortoubgehenthree AthSeELcLyOclQeswe(sreeedTeatbelcete5dabnydATSabEle(as10schfoowrnreifneTreanbclee).10N).o mTehaessuerasbalmeplleevselwseroef PthFeOnA above hcoanrdvietsitoends ffroorm2t4hehoAurSs.E cPelFlsOAancdonrcuennatrsaetcioonnds trainmgeitnhgrofurgohm t0h.8e-r1m.a1l testing ng/gof uPnFdOerA standard were raevceorvaegreerdecforvoemretdhecsoenscaemntprlaetsiodnuroifngPFthOeAsewcaosnd0.t9henrg/mga.l test cycle (sce Table 11). The 19 p22 TTeAsBtLSEub1s1t:ar nTcHeEa 2RsMuc AbLjt eTcEtSi etTodTAo hPerPmn AaRlATTesUtSing(,StIhNeGnLAEcRceEilAerCtaTtiIedOoNSonFlLvsAeSnKt). ExtthenasecondThermal Test (Standard Cond for 24 hours) -~ Sample _| iCnoInmcp.in(gneglrgs)*|| iCnoXncA.D(Rnegslgi)n || iCnoRnacn. V(negslsge)l (nglg [sa[mspalme#p5]lo0#098s|| <<055 <<005 o0s8 Sample#7| 11 | <05 <05 " + The contents of Impinger #2 were added to Impinger #1, which wAavsertahgeen]e0 xtracted in9 a | - sLiLngOlQe=st0ep5unsgilngg SPE. Results shown are afte the second 24 hours of Thermal Testing under Standard Conditions. e RPeesruflltusorfoocrarPbFoOxAv,licWiAtchidOsther Homologous "These results led to two questions 315? 1) Why were low levels of PFOA continuing to be recovered even after 56 hours at perfluor2o)caIrfbPoxFyOlAicwaacsidbsei(nPgFCrAelSe)asbeedinbgy rheelaetaisnegdTfersotmSTuebssttaSnucbest2aantce3125aCs,wewlelr?e other `might The help irdeeanstiofnyintghebseohuirncdeoqufestthieoPn F2OwAasrethcaotvetrheedrefcroovmerTyesotf SPuFbCstAaSncoeth2.er than One pPotFeOntAial PsoFuOrcAeoifs utsheedPaFt OmAanuinfatchteuTreisntg SpulbansttsantchaetwmaaskceonthteamTiensattiSounbsdtuarnicnegcmoannstuiftaucetnutrsi,nagn.dSince pmoasnsuibflaec.tuIrficnrgoesqsuciopnmteanmtinmaatiyonbebysheamrueldsibfyiedrifgfrearednetPpFroOdAuctosc,cucrrroesds,cootnhtearmiPnEaCtAioSnwiesre not ceoxnpceecntterdattioobnes porfehseonmtoalsogcoonutsapmeirnfalnutosroscianrcbeocxyolmimceracciidas.l PFOA ARer does not contain this testing began significant it was flelauronreodpotlhaytmearsmeacnounfdacptotuernetrisalaclsoontmaamniunfaatcitounresofulrucoeroistelluoomreorteprloodmuecrtschienmtihcealssa,mseinpcleantsso.me (ppreersfelnucoeTrhooefrheeffxooaurnreo,oitcahaetcrhiedp)re,mrafPllEutoNersAotcwa(rapbesorxfryluluniocurnoadnceiodrnsa:sntoaiPncdFaaBrcAdidc)(opanednridftliPuooFnrsDobAaunt(dapnteoerisfctleuadocrifoodrd)etPchaFenHoiXcA raceicdo)veurseidn,gsLimCi-laMrSt/oMoSuripnsrtervuimoeunstaftiinodni.ngs.TheInraedsdulittsiosnh,oqwueandti7f.i0abnlge/gaomfouPnFtsOAofwPaFsHXA (2. 1 ng/g). PENA (3.8 ng/g) and PFDA (3.2 ng/g) were recovered from the impinger train. The amount of PEBA present was less than the LLOQ (sce Table 12). experim`eAnstas rweosuulltdocfotnhtiisntuheertomatlesttesftoretxhpeerpirmeesnetn,ceitowfatshedseeciPdFeCdAthSat(efxucteuprte thermal PFBA) test to see if any trends existed between the concentrationsofcachofthese acids. 20 p23 TABLE 12; THERMAL TEST APPARATUS(SINGLEREACTION FLASK) Startdard Conditions for 24 hours withTest Substatic 2 PFCA Imp(ingnlggers| XAD(ngRlegsin Rxn(nVgelgssel | Tota(lngClaonc. LePFBA| | <0| E<0E s |SE 05 [a 0s | [rma --a ee 1 cos 1 2t [PPOATM60 TT 10 <os | 70 [ Tha e cP loo --nofr 2te mp6iengeno r#|t2wesrA a a0addee6dl to ImpL|ingoer #w1,<woehisch La was then exiracted in a single step using SPE. `Testing under wet or dry conditions and in the absenceof oxygen was initiated. In all testing up to now, both oxygen and water were present during the thermal test, due to the use of humidified zero air as the carrier gas (as suggested by the EPA). We first created a "dry" oxygen-free system with approximately 1% RH by exchanging our zero air cylinder for a nitrogen cylinder, and bypassing the humidification chamber. A blank run experiment under 1% RH 100 ml/min dry nitrogen flow for 24 hours at 315C resulted in the recoveryof no quantifiable amounts above the LLOQ (0.5) for PFHxA, PFOA, PFNA and PFDA from the impinger train. An extended thermal test experiment was conducted, this time under 1% RH 100 ml/min dry nitrogen for 120 hours at 315C. During this thermal test run, the impingers and XAD resin were replaced with a new set after 24, 48, 72, 96 and 120 hours. PFOA, PFHxA, PENA, and PFDA were recovered from Test Substance 2; mostofit in the first 24 hours (see Table 13a). We then switched the carrier gas for the thermal test system back to 50% RH zero air and re-tested the same sample used in the dry nitrogen experiment. This was done to see if the 50% RH zero air would cause the release of more PFOA, PFHxA, PFNA and PFDA. `This second test was run under standard conditions (50% RH 100 ml/min zero air at 315C) for 96 hours. During this run, the impingers and XAD resin were again replaced new sets after 24, 48, 72 and 96 hours. The compounds with the highest recoveries were PFOA and PFHXA (see Table 13b). Low levels of PFOA and PFHXA were recoverable from Test Substance 2 even after heating for another 96 hours under zero air at 315C. 21 p2e Ceram cos |cos | cos |<os | TDrAyBNLiEtr1o3g:eTnHCEoRndMiAtLioTnsESwiTtAhTPePsAtRSAubTsUtSan(cSeIN2GfLoErR1E20AChTouIrOsNfFolLlAoSweKd). by Standard Conditions (zero air)withsame Test Substance 2 Sample for 96 hours } Table 13(a):[ Dry Ngii terorge#nm Czo|n p 3di 3foi tr| 1i20ohn on2ur5s4s g | 2e 8 |d1] s | [[ impin CC woReewsn|<ee00osr 7[|1#a0coeis ||| |c<2_ o0s85<|||<0 <t0osss5||| -- mgog | 050s || <c0o5s ||<<uo05s|| CC Tah] mpmowgl <eosr|| # <o<0oss|| |[_ <<<o0os5s<||0<<u0s5 5|| [ m%pon0gReers#n2|| _<<0055[|c<o0s5 ||<<o0s5 || <<00s5|| mpnTgeor#w1| <<o0s5 ||<<0o5s |[<<o055| |<<o005s || [ [ oR t mongere #2] _i <c<0oo5sso n |[|<<<o0| 0ss5 |[|<w o<cos0s 5||| <<<oo0ss5|_ [Tom]i _impmgem rsi] cosm |<a0f5T|o o<nois | <Teonst TouRXeac0vovRoeesrwiyn| 005s || <<o0s || <cooss ||<<0oss || ncarrted" In ater 120 us) cos | < s | <os - LrimLHOQp,ro=vP0i.oE5uNsnABg/iagrndfkorrPaslRl Acuhodwmeeprroeyundo0s .g5a3 contin, background eveosf FOR, (Table 13 continued on extpage) 2 p25 |CToanbdliet1i3o(nbs)(:zSeraomaeirT)efsotrS9u6bshtoaunrcsethen subjei ctteod S-tandard Time| Sample Namo | P(nFgOlgA gg PnEglNgA re 24hr[ mp|i12n| g1e 3|r<o# 0s | <05_ pena] or | cis Ths] <05 |XwOResn| |<o |<s 0s | <os5 Tom 1s | 13 |<0s|<us| "sm co| cs os | <05 [10 [<05 |<o05 | [impinge#2r| <05"<05 |xaoResn|<0s |<0s ||_<<o0s5| |<<0055| | [ Tow[<os [ 10|<os|<os| 72hr |imping <0e5 r|#114]| <05 <05 | mpinger#2| "06 |<05|<0s |<05| XaDResn| 05 |<0s |<os | <o5| Tol] 06 | 14|<05|<05| 96hr Impinger #1] imping#e2r| _0<075 |<0256 | <<00s | <0055 XADResn| <05 |<0 | <5 05 | <05 Total RecovTeoryl| | 07 | 26|<05| i<0s uncorrected) <0s .(aiers6rs) | <05 ~ 11=0050nglg oralcompounds 2 <0 5 , Approximately 4.0 ng/g PFOA was recovered in the first 24 hoursofdry nitrogen thermal testing (See Table 13a). Subsequent testingofthis same sample `sing 7ero air and 50% RH released approximately ar: additional 1.9 ng/g ofPFOA in the first 24 hours, and a totalofappioximately 3.1 ng/g after 96 hours. Measurable amountsof PFOA and PFHXA continued t6 be recovered even after undergoing extensive heating with dry nitrogen for 120 hours and humidified zero air for 96 hours (see Table 13b:above). Note un Table 13b that lesser amotints of PFOA, PENA & PFDA were recovered (in total) when we completed thermal testing afte fist subjecting the Test Substance 2 sample to dry nitrogen insteadofjust humidified zero ar (standard thermal test conditions) during the first 24 hours (compare to Table 12). The total amountofPFHxA recovered actually increased after subjecting the sample to dry nitrogen conditions before running the sample under standard conditions (2.1 ng/g to 6.3 ng/g). 2. Dual Reaction Flask Testing a mal Test Apparatus "Re-design" Al thermal tests are lengthy; many run for several days at a time. Becauseofthis some variability in the values of the system blanks was experienced. An improved blank 23 .2s Mae added theme Tne 10 crest an dependent blank Syste qteusatnitnigtamteitonho(dLLwOaQs),neeeldiemdintaotaecthhieeveeffemcotroefcsoynssitsetmenctonrteasumlitnsa,tainoni,mapnrdovperdovliodweer"rleiamlittiomfe" System blanks. These goals were achieved by providing airflow to both a sample test system splitting the and a blank heated system. trAanssfeecrolnidneiimnpithnegeorvetrnain 200 ml/mTihne, amount so that bofotahirsfylsotwemtshrwoouguhldthheavheeaatneedqturaanlsfaeirrfllionwe ionfto10t0hemolv/meinn.wasEarcahmpteesdt to coaSyvyose.tnmemmTB,ooobtnlhamonwvpkeeinran.engdreBesrosattmahepndldiewm,aipntiwhnaXgtsoAhreeDqrsuarainmepeepaepwdcreoawrcrieetrshKiseeiptf.tsoro1cwTlnhheeeasenasimsanpylesaetneedhmsoslsdabweanrtie,hsrat(trdSainoeesnnf,eFiriaagnllidunreibmo9ovt)uhetorsfyhatrheed Figur4e. = CY N . p |- [& [LS 8 py IR- + igs P RT. ER IELhe | AA] 1 E |i i: a1LI \ . y . 3: Before cach experiment was conducted, the airflow trough cach system was equilibrated by gas flow meters placed on the exits. This allowed adjustment to maintain the rLPesFotOsbA ysandswitthahendobtahtcehkrgrPsoCupAntslPfFtoOusnAdycmoentanemibnlAaaltnlikoownteedsitntshthyesdtteehmneircemoaaultdiesob.ne sofQuabutnrayacntptedoafrlroelmevhealts of found nthe sample ts yam. A double bark un measured Iss than 0.3 ng of PFOA 2 par for each sideofthe redesigned test system under the standard conditions for 24 hours. Both sides of the airflow stream measured had comparable concentrationsof PFOA. The amounts of PFHxXA, PFNA and PFDA measured were less than the LLOQ. b. Results for PFOA, With Other Homologous Perfluorocarboxylic Acids Once the redesigned test system was constructed, thermal test experiments. `commenced to develop and optimize the dual system. All method development work from this point forward was performed using the dual system. The first experiment was conducted using 2gofTest Substance 2 sample. This was placed in the sample holder and heated at standard conditions, a repeatofearlier tests. The amount of PFOA that was found in the `experimental sample test system was 5.3 ng/g and the blank test system had a PFOA level below the LLOQ. The concentrations for the other PFCAs were as follows: PFHxA (3.6 ng/g), PNA (5.0 ng/g) and PFDA (3.3 ng/g) (see Table 14). The blank test system contained less than LLOQ amounts of PFHXA, PFNA and PFDA. TABLE 14: THERMAL TEST APPARATUS (BUAL REACTION FLASK) StandardConditions with Test Substance 2 . [[-- mongiersmt|| p 80s9i| |<ns0esg| |e4o3rr| |#a0r62|| [Re[ act-- ionVX essel|e200D 55 ||R<<00e 5s ||s<00i s5 ||n<<0o| 5s || Tow ss |se[so|33] [Bl|an_ k Fla_ sk [_mmep |n <<00n 55g||g <<e 0055o r ||<<r # 0055 # ||2<<001 ] 5s || [Re[ act0 ionVResesseln|| <<00s5 || <00s5 ||<<005s ||<<00s5 || [Co[ rrectedToa ameo an |<u53s[|<3os6w |<5o0s ||<3o3s || In the next experiment, 2gof Test Substance 2 was held at 315C for 48 hours under 1% RH (dry) nitrogen. Then the same 2g sample, in the same reaction flask, was held at 315C for 48 hours under 50% RH zero air. PFOA continued to be recovered in measurable amounts in 50% RH air evenafter 48 hours in dry nitrogen. The second 24 hours in zero air failed to recover further PFOA (see Table 15). 25 p28 TABLE 15: THERMAL TEST APPARATUS (DUAL REACTION FLASK) Dry Nitrogen Conditjonsfor48hours withTestSubstance 2followed by Standard Conditions (zero air) with same Test Substance 2 Sample for 48 hours TABLE 15(a): Test Substance 2 subjected toDryNitrogen Conditionsfor48 hours Prox Pr POR `Sample Flask Impinger#1 40 |3|9 a1 | 26 I3m4p0inRegse#irn2|| <_<0055 |<05 |<05 |<05 | Total | 40 | 39 | a1 | 26 | BlankFlask |_ impinger #1] _<05 |<05 |<05 | <05 [ [ iXmapDirnRgeoers#in2||<<<00o5s5[||o<<00s55 |<05 [|c<o0s5 |<05 | |<<o0s5 | || [Gomctoa tommero | 40139 | a1 | 20] AfterAdditi2o4Hnouarls Dry Nitrog LH Toll 08 10s as SamploFlask| __ [ iImmppiinnggeerr##2|| <0085 | 09 |<05 | 06| 05 | |<05 |<05 | <05 |<05| <05| [ impinger#1]<05 |<05 |<05 [<05 | beseew|e<0s5 [|<o20s8 |<os|<ooss | Commatommesa 0s 0s 0s 0s] (Fable 15comimed on net page) 26 p28 TABLE 155): Test Substance 2 subjected to Standard Conditions (zero al) for 48 hours subsequent to 48 hours under dry nitrogen(Table 75(s)) | ris | somponame | ge | iy | roy | mm | After 24 Hours Standard Conditions Lo ) [ mpinger#i 1.1 TT"22 [ 06 | 04 | | mpinger#2| 03 |"<025| <025|<025 | XapResn| 1326 | 08 | 07 | Blank Flask Ipinge#r1 [ <025 | <025 |<025|<025_| Impinger#2LIELomLa he -- [ XADResiTontal|| <<002255 |<025|<025|<025 | [com(eumc mmt | 2e 7|a48T | 1o5|t1m 1 | After Additional 24 Hours Standard Conditions 2 ] [ru| sumponane | ogi | roy | iy | PoFaOA <025 XADResin| 03 |"05 |<025|<025| Tol] 08| 08 [<025|<025| Blank Flask|__ impinger #1] 03 |<025 |<025|<025 | [impi "04n|g "<02e 5 |"r <02# 5|2 <02| 5_| XADResn| <025|<025|<025 | <025 | [ To| 07[<o025 |<025|<025 | [__comoctedTotal (samp sung[01[08[<0z5 |<ozs| - LLLOQLffoorraO allllccomoG pmoupndosunds== 00..52nng5gi/mmLLfofrorssampalems iinpnTTaalbblleee1155sab. Regarding the PFHXA recoveries, a total of 10.4 ng/g were recovered; this is more than the total amount ofPFOA recovered (7.6 ng/g). Mostof the PFCAs were trapped. during the first 24 hoursofheating, regardlessofwhich carrier gas was used (see Table 15). "The conditionsofthe next experiment were modified slightly. 2gofTest Substance 2 was held for 24 hours at 315C in 1% RH dry nitrogen. After the fist 24 hours under dry nitrogen, the sample was kept in the sample holder at room temperature for 24 hours. This sample was then run under 1% RH dry nitrogen for a second 24 hour period at 315C. The sample was then held at room temperature for a second 24 hour period. Finally, the sample was held at standard conditions (315C for 24 hours, 50% RH zro air). Impinger trains were replaced after each 24 hour heating cycle. We were looking foranyeffects that would occur by resting the sample at room temperature in the middle of an extended heating process. The resultsofthis experiment were not significantly different from previous extended thermal test experiments (see Table 16). Mostofthe PFCAS were recovered from the sample holder during the first 24 hoursofheating using cither the nitrogen or the zero air 7 p30 It appears that the second and third sets of impingers used in this experiment may have been contaminated with small amounts of PFOA. much isMsothatmhafseorrtehd f2r4sth2i4nahouurns.orWdhreyniathgiesns,amtpleeewsaosweerxepdossedantothuamfiSdLsiFeEthCeA urencdoevrerniietrsoogfen.allTPhFeClAevselionfcrreeacsoevdesriegdniPfiEcHanxtAly wcaosmphairgehedrttohtahnetsheecaomnodutnwtenoftyPfFoOurAhours recovered under these conditions (see Table 16). TABLE 16: THERMAL TEST APPARATUS (DUAL REACTION FLASK) Dry Nitrogen Conditionsfor48 hours with Test Substance 2followed by Standard Conditions (zero air)for24 hours with same Test Substance 2 Samp 2T4AhBoLuErs16((aw)i:thTaes2t4Shuobusrthaonlcdein2gspuebrjieocdtiend tswaimceetcoaDprpyeNdiftlraosgkeantrCooondmitions for perature inbeteaw che 24he ourn int I) TFlaM sk A p _inglg)| (nglg on oo Sample Flask -- XaDRe9sn| 034 2 | coz os Sion[ k Flask|m_ ommonggeTroe sw||_m ra00s24#|||2 <01021| %|||o a<<00e%z5s||| <<50o3%m5 | L Corero TomTeoul|| 307s |<coo7sns[|cc4ao3mz{|c3om3s]| After Additiona24l Hours Dry Nitrog Flask " go) | (nga) | (PogEgR) | (ngs [[ toixmw apnogReers#n2|]] 0t02s3 || <0022s5 [os ||<[c00o%sm5I|[uo<s0m%5] comorTottal|| o1v3zm| <m00245[m|o<0rs25|mu"<0oms2m5 ] (Table 16 continued on next page) 28 p31 | |ee|fn| fom TABLE 16(b): Test SubstancZesubjecntesefdo Standard Conditions (zero |i) for24hoursafter48hoursunder dry Yitdgen (Tab 16(a) Flask Sample Flask SampliemNpaimp ngee#ri 1|~n 5g/0g|e8r g7ig # |"2 ao'0g || 3(n4glg | [[ TTixmaDResn|"1210 |"0088 | | 03 03 | | <026 03 | [imTp otili|nn a0g i5ge ||e#<r0r 32#5|# |i<1 2 0426] 5||| 37 <025 | [ [ixmADpResn| 19 08 |"<025 |<025| |<025|<025 | <025 <025 | | "LfLoCroPOrFreOcQAt=ed0T.o1tanlga/mmoireLa.lmasnyamp|les 49 | 113 |_a6 | a7 || -LLOQ for PFHxA, PENA& PFDA = 0.25 ng/mL.fo alsamples regardleSsismoiflraerstaimnoguntthseotfesatllmaotfertihaelPbFeCtAwesenwehreeatriencgocvyecrleedsuusnidnegr5d0r%y nRiHtroagnedn zceornodiatiirons. "fTohre2s4imhioluarrsaamto3u1n5tsC,forreasltlinPgFfCoArS24rehcoouvresraetd rwoeorme otebmspeerrvaetdurafetearn:d1)hehaetaitnigngagwaiitnhfnoirtr2o4gen hleonugrtshwyintahtunrietroofgetnh,esoer e2x)puenriinmteenrtrsu,ptiet dwahseadteincgidfeodr 4no8thtoourrespeuastintghdersyentietsrtsogaens.ecoDnudetitmoe.the second "aTnhde tnheixrtd s2e4tohfouerxppeerriimodenwtisthinhvuomlivdeidfiuseidnngidtrroygneint(rSoegeenTafobrle2417h).ourCsomfoplalroiwnegd bthyesae wdieffenrietnrcoegewnarsesnuolttesd.to WthheernesutlhtessdaimspcluessweadsabeoxvpeosaenddtdoethauimlieddifiineTdabzlereo1a6i,raafstiegrniefxipcoasnture to dthraynnwiterroegernec(oNv)e,remdowrehePnFuOsAinagnhdumtihdeioftiheedrnPiFtrCogAeSn.weBraesreedcoovnetrheedsefreoxmpetrhiemteensttaslyrsetseumlts it w(oCuolmdpaarpepeTaarbltehat16motoreTaPbEleCA1S7)are recovered when oxygen (Oz) is present in the air stream. 29 p32 TABLE 17: THERMAL TEST APPARATUS (DUAL REACTION FLASK) Test Substance 2 subjected to Dry Nitrogen Conditionsfor24 hours followed by WetNitrogen Conditionsfor48 hours with sameTest Substance 2 Sample Sn [SmpiNnagaemre#m2| PpFOAl0(9nges) | PPHXtAs (ngis) |[ PENaAe(gio s) | PFoOtr Aesrg] | [Blank Flask |_mTpenwger0a#101|[|coisr | si cor as <o1 | mpnger#2|__ 0o1z | coi | <or |<oi | [_ECSomeetedTomo w| an | 36 | 19 31 | a3 TABLE 17(b): Test Substance Then SubjecttedoWet Nitrogen Conditionsfor48 Hours EE 95 -- ree Sample Flask | __ gImipnigngeerr ##12| oorz |_<0014 || c0o5r | |<0oi5 || XADResin 0i2 <o21) os <oo1s Blank Flask| _~imIpmipinnggeerr##21 of <o1 [ [XaDResint | o01w [|o_<ro1 |e e<oonr |ocorr | [ComeceaToten | __07 0%] 05 65] "Flask |[SagmpaloNramse | PFO0 A(ngi6 g| P0 FA (ng) | PFNA(nga) |PFDA (ig) | er [ora <or ] [=o BkFimsk|_mppnegRerrEl#1 e N8a |e cor[ca oiecs or] [ComcedOTVEoRAmLeLTOmTAwL| _ 0453 | 2052 | o#a0 | o37s --| | - mLrpLiOnQen =rs0.18p nXgA/agDfroarosaB lilncs woemre poouco hnadnsgedso kbrowdecnrs20anr24aavskrvepaaris I HEE 30 p33 Experiments were designed to find the optimal temperature for PFCA recovery from or 28 hour. Tn this experiment, oly one sample holes and one lank sample holder were "Test 100 Substance 2 m/min 50% rdeulraitnivgethheumtihdeirtmyalaitrefstl.owAftor10204hCr,s.2gTohfeTessatmeSu2bgstsaanmcpele2 was was run run under sequentially at 150C for 24 hrs, at 200C for 24 hrs, at 250C for 24 hrs and finally at 300C used. Impingers and XAD resins were changed between each temperature level. Between temperature levels, the oven was ballistically rampedto the next temperature. It was noted that an increase in concentrationsofeachof the compounds were recovered when temperatures exceeded 250C with the maximum occurring at 300C (see Table 18). TSeAqBuLeEnc18e:oTfHVEarRiMabAlLe TTeEmSpTerAaPtPuAreRACoTnUdSit(ioDnUsA(LuRnEdeArCzTeIrOoNairF)LfAoSrK2)4- hourintervals on same Test Substanc2e Samp EE arse | 3h | i| a Li 1 300 Resin [07 oO 0 wLR o0rm s0 [e cct0 oortm m L |<o b oon 1im [0 c<| oo| ] ii] [ Comcat o oo0s [|<o1||<<o1[[<o1 || ro[ mmo| n 01 |[g G<o0i 1e | cr arL||=is o15| [ ES o0R7en|B 01 |<01|X <01 |<01 | [[ om| raah|--m--mpi nmXe aanCggRt eersan||a_rcc<0o0om 1r1ts[|||ct z<ccoooow rt|rrm||[|c<rco<oooi1rr[o [[cc<oaomiri||] [ omo 0s[cor[oi 02] (Table 18 continuoend next page) 5 pat Fie AE Table 18(c): SameSample After Addi2t 4Hi ourosant2a0l 0T Sample Flask impinge#r1]06| Coe or iXmpAiDngReers#in2|] <<00.11 |<o01|<01|<"ooi1| |-- Blank Flask | Total| Iimmppinignegre##1r2] ] 06| 03 <_<00..1 _1[eo | Te0er8T|ee07r] XADResin| <01 |<01 |<01|<01 | Tow|<o1 |<o1[<ot[<o1| Corrected Total (T-eBlsantk) | 0.6 03 08 0.7 Table 18(d): S[ ame Sampm le Aftea r Addn it12i44o Hog |nurasal0t82a 50|T 2s 0| 1] s| mXpAiDRnegsie#nr|2]0.012 || <<00t1 || <0o1t iBam rkFplaskn|[ ger#Toim|[ 16| 08 | at| ts| [To <cooi1|l |<<oor1 [| <] 01[<o1| Table 18(e): SaCmorerecStaempdleTotAalft(erresAwadngd| i21t46Hio|urosant03a800l|T 21| 18| [rSuampnloFlas|k[|miCCmasopnmpnogrgsemoarr|s#ge021y12||||| g13y||1 ogo)||8 ttogo)|| 04 | 01[<01| [ Total eoRre[sn8| 025|| 1530 ||2o6r[|2o6r|| [ mpinger#i]<01 |<or[<oi [<or | <0 cor [c|o<ot 1 | C CumCorru ecteds Total t (resv ts |e<63o412r |||<o 43o011w [| |<o25| r66[||<2os6ra || T~ TiBmeLpt0iwGne=geens0t1e&mnpXeAgrDatTruoerrseailnlsocvwolemsr,peoousvnwedanpswpaesd boaultsbtceatlwyeenraemapcehdtteompnexrtattuermepelroavteure temperatEuxrpeerlievmeel.ntsSewpearreatreunthaetrm2a2l5tCe,st 2e5x0peCr,im2e7n5tsCwearnde 315C to refine the optimal conducted at cach temperature, where 2gof Test 24 hrs. Table 19 Spruebssetnatnsctehe2 rweasusltrsu.nwuhnidcehr s1e0e0mmt/omiindnic5a0te%thraetlaatsivtehehutmeimdpietryatauirrefolfotw hfeor 2 p35 sample is increased, moreofeachof the PFCAs are recovered from the impinger train up to at least 315C (see Table 19). TABLE 19: THERMAL TEST APPARATUS (DUAL REACTION FLASK) Variable Temperature Conditions (underzero air)for 24 hour intervals with different Test Substance 2 Samples [Cmp1o 7 | ge0sr|stta|| CC Tewl 26 |[ 0s c | oao tr uor i_|| Blank Flack [inXpAi0nRgesoinr|_00#20222 ||_c_<o<0or11 | c<oor1 [cor| | oi |<o1 | [CometsTomemaTo]w[20s 0|0c5 oi [|i<o71 |1<1ot]| Table 19(b): After 24 Hoaut2r50s T [ [CmpXoAgooR= rasstn|| 2055]|= os |o 2= 2 |z o1t2 || [[mimppnignogorre##wi2]] 034s | | coi 02 |_<o1 [a |1r 5 | | | <<oo1i ||<cooir || [XeAoRwes|n| 0e5s || <o0r1 [|c<o0ri [|c<o0ri || [ComectedTotal(ewww | _26 | 08 | 27 | 15 | Table 19(c):After24Hoursat 275 CT [| i[mCpmipnXogAgoooRrre##s2in|]| 2170 | | <ioi1 | otro || 0to4 || 05 | oi | os | oz | impiengew#r1 a[0z6 [a2 [2<9o1 | ts | [[XtmpiAonge0wr#2R]es010231n||| c<o0r |<<cooor1r |<<o0r]| Come Touma [51 12 29 7s] (Table 19 continued on next page) 33 5.36 Table19(d):After24Hoursat 315 C (Dat from Table 14) s [CT rroa(ya | Pri (ngs) |Pra|gPFOAaIg))| Corrected Total(rest lank 53 |36| so |33| ~ ALdLiOfQer=en0t.1sanmgp/glefofrlaalslkcaonmdpboluanndksfltaessktewdasexucseepdt faotretahceh3t1e5mpCersaatmuprleelewvheelre LLOG = 0.5 ~+TIhmepinegxepresri&meXnAtDwarsesirnusnwuenrdeerscwoanptpienudoubset5w0e%enReHaczher2o4aihrr period _ IV. GLOSSARY OF TERMS AND ABBREVIATIONS Accelerated Solvent Extraction (ASE) ~ An automated instrument that uses a combination of high temperature and high pressure solvent in an extraction process. This instrument was designed to increase recoveryofselected compounds from semi-solid and/or solid materials Ammonium perfluorooctanoate (APFO) ~ Ammonium perfluorooctanoate i the ammonia saltofperfluorooctanoic acid (PFOA), having the chemical formula C-F1<CO>NHs, APFO is identified by CAS# 3825-26-1. See also PFOA. Differential Scanning Calorimetry (DSC) - a thermo-analytical technique in which the difference in the amount of heat required to increase the temperature ofa sample and a reference mass are measured as functionof temperature. The main application of DSC is in studying phase transitions, such as melting, glass transitions, or exothermic decompositions. These transitions involve energy changes or heatcapacity changes that can be detected by DSC with great sensitivity Framework Test Program Guidance -- a document entitled "Framework for Test Method for Measurementof Perfluorooctanoic Acid Generated from Thermal Degradation of Fluoropolymers." Lower Limit of Quantitation (LLOQ) the lowest amount ofan analyte in a sample that can be quantitatively determined with suitable precision and accuracy. The LLOQofthe analytical methods used for PFOA analysis in the PSE and TGT methods is equal to the lowest calibration standard actually used in establish in the actual calibration curve. Method Development Test Program Guidance --a document entitled "Method Development for Testing Generation of Perfluorooctanoic Acid from Thermal Degradation of Fluoropolymers." Modified PTFE --refers (for the purposes of this study) to those grades of polytetrafluoroethylene that are made: 1)by a suspension polymerization process (Drobny, Technology of Fluoropolymers), 2) typically without using PFOA, and 3) contain a second comonomer. The comonomers are typically perfluorinated vinyl ethers, and are present in low amounts (~0.1% or less) in the final polymer. Modified PTFE is identified by CAS# 3825-261, or by CAS 26635-00-5 34 p.37 iPnarstcipeenrcemainlldieonngi(npepemr)inag,ndtopdaerntostpeerrelbaitlilvieonpr(opppobr)t:ionPsaritns-mpeearsnuorteadtiqounanitsiutsieeds,; peasrpteicciuallalryly in low-value (high-ratio) proportions at the parts-per-million (ppm) 10 and parts-per-billion b(iplplbi)on1e0q"uallevepla.rtsOins ea ppaarrtt pineronbiellmioinl.lio|nneaqnuoalgrpaarmts/ gisraampa(rptppbe)romfilPlFioOn,Aownoeulpadrtbein one. 0.000000001 grams of PFOA in 1.0 gramsofmaterial (such as the test substance). aPceirdf,lhuaovrionogcttahneociheeamciicdal(fPoFrOmAul)a--CP;erFfilsuCoOr;oHo.ctaPnFoiOcAacisididiesnatiffiuleldybfyluCoAriSn#ate3d35c-a6r7b-o1xylic sWpheceinfictahlelyt,ertmhePpFerOfAluiosrouoscetdaninoattheisaPnriootnocioslt,heit cihseimnicclaulsisvepoecfiebsotdhetPecFtOedA bayndthAe PaFnaOl.ytiMcaolre methods used in this study. pPoollyytteettrraafflluuoororeotehtyhlyelneenema(dPeTFbEy)a-sursefpeernss,ifoonrptohleypmuerrpiozsaetsioofnt(hDirsobsntyud,y,Tetcohtnhoolsoeggyroadfes of aFllsuoorkonpoowlynmaesrs")grparnoucleasrsePsTFanEd"tbyypitchaellfylnuootroupsoilnygmePrFOpAr.ocesPsTiFngE imnadudsetryb.y tPhiTsFpEroicsess is identifiedby CASH 3825-26-1 `ScoloimdpoPuhnadssethEaxttraraectdiiosnso(lSvePdE)or--sAustpeecnhdneidquienathaltiqiusida mseipxatruarteioanreprsoecpaersastbeyd wfhriomchother `lacboomrpaotournidess iunsethseolmiidxtpuhraeseacecxotrradcitnigontotothceoirncpehnytsriactael aannddpcuhreimfiycsaalmpprloepserftoiresa.naAlnyasliys.tiScoallid `ipnhcalsuediexntgruarcitnieo,n bclaonodb,ewuasteerd,tobeivseorlaatgeesa,nasloyilt,esanodf ainntiemraeslttfirssoume.a SwiPdEeuvsaersietthyeoafffmiantirtiycoefs, wsohliucthestdhiesssaolmvpeldeoirs psaussspeednd(ekdnoinwna laisqutihde (stkantoiwonnarayspthhaesmeo)btiolesepphaarastee) afomriaxtsuorleiditnhtoroduegshired uannddeusnidreesdiirmepdurciotmipeosneinnttsh.e sTahmeplreesaulrte risettahiatneeditohnerthtehestdaetsiiorneadryanpahlaystee.s Tohfeinptoerretsitonorthat cpoanstsaeisntshtrhoeugdhestihreedstaantailoyntaersy oprhausnedeissicroeldleicmtpeudriotireds.iscIafrtdheed,podretpieonndrientagionendwohnetthheerstitationary cpohlalseectiinocnluidneasntahdedidteisoinraeld satneapl,ytiens,whtihcehy ctahenstthaetniobnearryepmhoavseedisfrroinmsethdewsittahtiaonnaarpyprpohparsieatfeor eluent TLeLsCt;SapnodnsE.oI.rsd--ucoPlolnetctdieveNley,moAuGrsCaCnhdemCiocmaplasnyA.mericas, Inc.; Daikin America, Inc.; Dyneon Test Substance ~the industry PTFE composite sample specified in Section If ofthis Protocol Trifluoroacetic acid (TFA) ~ a strong carboxylic acid with the formula CFsCO:H. b`TyhtehremTaelsTteSspton--stohres.thTehrimsaltetsetstsuisbjaectetsst acosnadmupclteoedftushiengTeastspSeucbisatla-npucreptoosea dsepveicicfeidedeveloped temperature under passes through the specified device in caocnodnittrioolnlsedfoarnad srpeepcriofdiuedcitbilmeemianntnerevra.l. TChleeaonu,tlemtoiasitrusrtirzeeadmaiirs sampled to collect PFOA potentially released from the polymer. 35 p.38 XAD - a highly absorbent ion-exchange resin used in continuous samplingof organic materials, especially for monitoring ofpollutants in gas streams. It is used for collecting specific compounds in air because it traps and retains compoundsof interest even in the presenceofother compounds, doesn't alter the compound of interest, and allows the collected compounds to be readily extracted for analysis. Zero Grade Air (or Zero Air) ~ Commercially purchased compressed air that has met standards for hydrocarbon content at less than 0.1 part per million (ppm). Every cylinder of zero grade air is supplied with an individual certificate ofanalysis to insure the quality required was provided. Zero Grade Air as certified is required to have oxygen content between 20 and 21 percent, less that ppm residual water and less that | ppmofthe following contaminates: carbon monoxide. carbon dioxide, and sulfur dioxide. V. REFERENCES Framework for Test Method for Measurement of Perfluorooctanoic Acid Generated from `Thermal DegradationofFluoropolymers (April 24, 2006). Method Development for Testing Generation of Perfluorooctanoic Acid from Thermal DegradationofFluoropolymers. (April 24, 2006). Drobny, J. George. Technology offluoropolymers; CRC Press LLC: Boca Raton, FL. 2001 Ehresman, D.J.; Froehlich, J.W.; Olsen, G.W.: Chang, S.; Butenhoff, JL. "Comparison of human whole blood plasma and serum matrices for the determination of perfluorooctanesulfonate (PFOS), perfluorooctanoate (PFOA), and other fluorochemicals." Environmental Research, 2007, Vol. 103, pp 176-184. Larsen, B.S; Kaiser, M.A.; Botelho, M.; Bachmura, S.F.; Buxton, LW. "Comparison of pressurized solvent and reflux extraction methods for the determinationofperfluorooctanoic acid in polytetrafluoroethylenc polymers using LC-MS/MS". Analyst, 2005, 130, 59-62. eLxatrrsaecnt,ioBn.oS.f;peKarifsleuro,roMo.cAta;noBaotteelfhroo,mMp.o:lyBtaecthrmafulruao,roSe.tFh.y;lBenuextfolnu,orLo.pWo.lym"eErff.i"cAineantly`stto,talV'ol. 131, pp 1105-1108, 2006. Olsen, Zobel, G.W.; Burris, JM; Ehresman, D.1.; Froehlich, J.W.; Seacat, A.M.; LR. "Half-lifeof serum climination ofperfluorooctanesulfonate, Butenhof, J.L.; perfluorohexanesulfonate, workers." EHP, 2007, Vol. and perfluorooctanoate 115, pp 1298-1305. in retired fluorochemical production 36 Fe | 1