Document 1QQxB739MDygJJbDabGRe0Odq

AR226-2713 AR226-2713 UDR-TR-2004-00025 FINAL REPORT Laboratory-Scale Thermal Degradation of Fluorocarbon Materials July 2004 Final Report - July 6,2004 Laboratory-Scale Thermal Degradation of Fluorocarbon Materials Takahiro Yamada, Ph.D. Philip H. Taylor, Ph.D. Environmental Engineering Group Energy and Environmental Engineering Division University of Dayton Research Institute Day3to0n0, COoHlle4g5e46P9ar-0k114 Prepared for: Robert C. Buck, Ph.D. DuPont Chemical Solutions Enterprise Barley Mill Plaza 23/1324 Lancaster Pike and Route 141 Wilmington, DE 19880-0023 TABLE OF CONTENTS ^ 3 2 2 N -----------. List ofFigures List of Tables Abbreviations Executive Summaiy 1 Introduction 2 Experimental Protocol 2.1 Introduction/Objectives 2.2 Overall Experimental Approach 2.3 Samples 2.3.1 Atomic Composition 2.3.2 Thermogravimetric Analysis (TGA) Results 2.4 DIne-tleinrme GinCat/iMonS Analysis and 99.9% Destruction Temperature 2.4.1 ExApnearilmyseinstoalf SCeotmupbuasntdioPnroBcyepdruordeuoctfsIn-line GC/MS 22..44..32 AGTCR/MSSECxpheermimiceanltCalaClibornadtiitoinons 2.4.4 GCT/hMerCmDaleDteercmoimnaptoiosintioonf MPraojfoirleIons for Construction of 2.5 aTt1re0a0te0dCand Untreated Articles: PFOA, Fluoride, and Chloride Analysis 2.6 OTrrgeaanteicd CanodmUponutrnedat(eVdOACrt)icAlensa:lOysfifs-laint e10G0C0/MC S Analysis of Volatile 2.7 Treated and Untreated Articles: CO and C02Analyses at 1000C 2.8 XPS Analysis ofPyroprobe Cartridge 2.9 Telomer B Alcohol Combustion: GC/MS Analysis 2.10 Perfluorooctanoic Acid (PFOA) Absorption Study 2.10.1 PFOA Absorption Study PAGE v ^ j 2 2 2 2 2 3 4 4 g6 10 14 15 16 17 17 18 lg 1 TABLE OF CONTENTS (continued) SECTION____________________ _______________________________ _-____ pag i 2.11 PFOA Transport Studies 22..1111..21 PPFFOOAA TTrraannssppoorrtt SSttuuddyy -- AGaqsuePohuasseSaSmamplpilnigng j9 1291 2.12 PFOA Calibration Curve and Detection Limit Study 22 2.13 Test Matrix and Quality Assurance Procedures 23 2.14 Quality Assurance Narrative Statement 23 3 Experimental Results 25 3.1 33D3In...1e11-t.l..3e12inrmeFTUlGirnunetCoaarrtte/iieMaondtnaeSAtdeArdAtniAcratlliceycrlsyeilsicaPndol9y9m.9e%r Destruction Temperature 32222855 3.2 ATrneaaltyesdesanadt 1U0n0t0reCated Articles: PFOA, Fluoride, and Chloride 37 3.3 SIF4 Analysis from Fluorinated Acrylic Polymer Combustion 38 3.4 Treated Article Gasification: XPS Analysis of Pyroprobe Cartridge 41 3.5 Telomer B Alcohol Combustion GC/MS Analysis 43 3.6 Treated & Untreated Articles: Off-line GC/MS VOC Analysis at 1000C 44 3.7 Treated & Untreated Articles: CO and C 02Analyses at 1000C 46 3.8. PFOA Absorption Study 3.8.1 PFOA in Aqueous Solution 47 47 3.9 PFOA Transport Studies 33..99..12 PPFFOOAA TTrraannssppoorrtt SSttuuddyy ---GAaqsuepohuasseSSamampplilningg 47 4497 3.10 PFOA Calibration curve and Detection Limit Studies 52 3.11 AAPFrntOaiclAylessiAsannadlytshies FfrloumoriCnoamtebduAstciroynliTcepsotslyomfethreUTsirnegatIend-l&ineUGntCre/aMteSd 56 ii TABLE OF CONTENTS (continued) SECTION_____________________________________________ 4 Discussion 5 Conclusions 6 References AppendiTExoxAtpaelrIimonenCtharloCmoantdoigtiroanm(fToermDpuePraotnutreS,aFmlopwle RIna-tlei,neanGdCP/rMesSsuAren)aalynsdis AppendiEfxoxrBpPeFriOmAen, tFa,l aCnodnCdiltiAoqnu(eToeumspSeoralututiroenaAndnaFlyloswis Rate) and Results AppendiETxxoCptaelrIimonenCtharloCmoantdoigtiroanm(fToermTpeelroamtuerre,InF-lloinweRGaCte/M, aSndAPnraelsyssuisre) and AppendEaixnxdDpeCri0m2eOnftaf-llCinoenGdiCti/oMnS(TAenmaplyesriasture and Flow Rate) for VOC, CO AppendiTExrxaEpnesrpimoretnEtaffliCcioenndcyitiTones(tTaenmdpSeyrsatteumre SatnedamFloEwxtRraactteio) nfor PFOA AppendiECxxaFpliebrriamtieonntaalnCdoDnedtietciotinon(TLeimmpiet rSattuudrey and Flow Rate) for PFOA AppendiMGxeeGntheoradlsDfeosrcTriopttailoFnluoofrAinTeR, SanSdtaQnudiakrCdhPemroceMduerteh,oWd ifcokrbFolludoTriodrecahnd Chloride in Water 60 62 63 A-l B-l C-l D-l E-l F-l G-l PA in LIST OF FIGURES FIGURE_________________________________________________ _______________PAGE 1.1 Fluorotelomer-based Polymer Description 1 2.1 TGA Result for Untreated Article 3 2.2 TGA Result for Treated Article 4 2.3 TGA Result for Fluorinated Acrylic Polymer 4 2.4 General Schematic of the Advanced Thermal Reactor System (ATRS) 5 2.5 Position of Thermocouples in Reactor Assembly 5 2.6 CF3H Calibration Curve 8 2.7 C A Calibration Curve 9 2.8 CgFig Calibration Curve 9 2.9 Total Ion Chromatogram and Peak Identification for Untreated Article at 600C H 2.10 Mass Spectra at 13.4 min for Untreated Article at 600C 11 2.11 Total Ion Chromatogram Peak Identification for Treated Article at 600C 12 2.12 Mass Spectra at 13.5 min for Treated Article at 600C 12 2.13 Total Ion Chromatogram and Peak Identification for Fluorinated Acrylic Polymer at 600C 13 2.14 Extracted Ions (69 and 77) for Fluorinated Acrylic Polymer at 600C 14 2.15 Off-Line Aqueous Sampling for Fluoride and PFOA 15 2.16 CO Calibration Curve 16 2.17 C 02Calibration Curve 17 2.18 Schematic for PFOA Absorption Test 19 2.19 Schematic for PFOA Steam Extraction of the ATRS 20 2.20 Schematic ofPFOA Transport Efficiency Test Through the ATRS System 21 2.21 Schematic ofPFOA Direct Injection to GC Injection Port 22 IV LIST OF FIGURES (continued) FIGURE 3.1 Untreated Article Destruction Profile Normalized by Sample Mass 3.2 7E0x0traacntded72Io5nC122 (benzoic acid) for Untreated Article at 600, 650, 3.3 E6x5t0ra.c7t0e0d,Iaonnd174295(tCerephthalic acid derivative) for Untreated Article at 600, 3.4 EUxnttrraecatteeddIAornti1c2le2C(boemnbzouisctiaocnida)t a1n0d0014C9 (terephthalic acid derivative) for 3.5 Treated Article Destruction Profile Normalized by Sample Mass 3.6 E70x0tr,aacntedd7I2o5nC122 (benzoic acid) for Treated Article at 600,650, 3.7 E70x0tr,aacntedd712459C(terephthalic acid derivative) for Treated Article at 600, 650, 3.8 Eanxdtr7ac2t5edCIon Count 69 (*CF3) for Treated Article at 600, 650,700, 3.9 E72x5traCcted Ion 119 (*CF2CF3) for Treated Article at 600,650,700, and 3.10 E72x5traCcted Ion 131 (*CF2CF=CF2) for Treated Article at 600,650,700, and 3.11 EfoxrtrTarcetaetdedIoAnrCticoluenCt o12m2b(ubsetinoznoiact a1c0i0d0)aCnd 149 (terephthalic acid derivative) 3.12 Fluorinated Acrylic Polymer Destruction Profile 3.13 E70x0tr,a7c5te0d, aIonnd 68900(*CCF3) for Fluorinated Acrylic Polymer at 600,650, 3.14 E90x0tr,a9c5te0d, aIonnd 61900(0*CCF3) for Fluorinated Acrylic Polymer at 850, 3.15 E60x0tr.a6c5te0d.7I0o0n,7775(0,CaFn2dC8H0=0CCH2) for Fluorinated Acrylic Polymer at 3.16 Extracted Ion 77 (CF2CH=CH2) for Fluorinated Acrylic Polymer at 850, 900,950 and 1000C 27 27 28 29 29 30 30 31 31 33 33 34 34 35 v LIST OF FIGURES (continued) FIGURE_________ ____________________________________ __________________ PAGE 3.17 E65x0tr,a7c0te0d,7I5o0n,1a1n9d(*8C0F02CCF3) for Fluorinated Acrylic Polymer at 600, 35 3.18 9E0x0tr,a9c5te0d, aIonnd 110190(0*CCF2CF3) for Fluorinated Acrylic Polymer at 800, 850, 36 3.19 E70x0tr,a7c5te0d, aIonnd 810301(*CCF2CF=CF2) for Fluorinated Acrylic Polymer at 600,650, 36 3.20 E70x0tr,a7c5te0d, aIonnd 810690(*CCF2CF2CF3) for Fluorinated Acrylic Polymer at 600, 650, 37 3.21 Eanxdtr7ac5t0edCIon 85 (SiF3) for Untreated Article at 600,650,700, 725, 3g 3.22 Eanxdtr7a5ct0edCIon 85 (SiF3) for Treated Article at 600, 650, 700,725, 39 3.23 E70x0tr,a7c5te0d, aIonnd 88500(SCiF3) for Fluorinated Acrylic Polymer at 600, 650, 39 3.24 E95x0traacntded10Io0n08C5 (SiF3) for Fluorinated Acrylic Polymer at 850, 900, 40 3.25 Temperature vs. Integrated Normalized Peak Area of Ion 85 (SiF3) 3.26 XPS Result for Blank Cartridge 41 42 3.27 XPS Result for Sample Cartridge (First Analysis) 42 3.28 XPS Result for Sample Cartridge (Second Analysis) 43 3.29 Eatx2tr0a0ctaenddI6o0n077C(*CF2CH=CH2) for Telomer Alcohol Combustion 44 3.30 VOC Analysis for Untreated Article Combustion at 1000C 45 3.31 VOC Analysis for Treated Article Combustion at 1000C 45 3.32 TThortoaulgIhonACThRrSomatograms Obtained from PFOA Transport Test 50 3.33 Total Ion Chromatograms Obtained from Direct Injection 51 vi LIST OF FIGURES (continued) FIGURE_________________________________________________________________ PAGE 3.34 PFOA Calibration Curve 52 3.35 PFOA Extracted Ion 131(*CF2CF=CF2) for 1.10,5.50,10.16,50.80, and 100.40 |ig 53 3.36 PFOA Reference Spectra Obtained from NIST129K Library 54 3.37 PFOA Full Scan Spectra for 100.40,50.80,10.16, 5.50, and 1.10 [lg Injection 55 3.38 PFOA Full Scan Spectra at 16.2 and 16.6 min for 100.40 |Jg Injection 56 3.39 Extracted Ion 131 for Treated Article from 14 to 18 min Retention Time at 600,650, 700,725, and 1000C 57 3.40 Extracted Ion 131 for Untreated Article from 14 to 18 min Retention Time at 600, 650, 700,725, and 1000C 57 3.41 Extracted Ion 131 for Fluorinated Acrylic Polymer from 14 to 18 min Retention Time at 600,650,700,750, and 800C 58 3.42 Extracted Ion 131 for Fluorinated Acrylic Polymer from 14 to 18 min Retention Time at 850, 900,950, and 1000C 58 3.43 FSipgeucrtera3f.4o1r the Peaks 16.35,17.10,17.70, and 17.95 min at 600C in 59 Vll LIST OF TABLES ______________________ 2.1 Weight Composition (%) ofDuPont Samples 2.2 Atomic Composition of DuPont Samples 2.3 Pyroprobe Gasification Temperature (C) 2.4 Linear Fit Equations for Standard Calibration Curve and Detection Limits 2.5 Linear Fit Equations for CO and C02 Calibration Curves 2.6 TelomerB Alcohol Characterization 2.7 Solution Concentration (PFOA in Methanol) and Volume Required to Produce 1,5,10,50, and 100 |ig injection into ATRS 3.1 Major Ion Counts of the Untreated Article 3.2 Major Ion Counts of the Treated Article 3.3 Major Ion Counts of Fluorinated Acrylic Polymers 3.4 Gasified Sample Masses 3.5 IFnltueogrriantaetdedPeAackrAylriecapoolfyImoner85 (SiF3) Normalized by Mass for the 3.6 Approximate Atom % Surface Compositions 3.7 (SaCmFp2CleHG=aCsHifi2e)d and Normalized Integrated Peak Area of Ion 77 3.8 Net Mass of Sample Gasified 3.9 Flow Rate Monitored for CO and C02Analysis 3.10 aCta1rb0o0n0RCecovery Rate for Untreated and Treated Article Combustion 3.11 Summary of PFOA Absorption Tests . 3.12 PFOA Recovery as Fluorine (Wickbold Torch Analysis) 3.13 Summary of PFOA Transport Studies 3.14 Wichbold Torch Determination ofTotal Fluorine viii PAGE 2 2 7 10 17 jg 22 25 28 32 3g 40 41 44 45 46 46 47 47 48 48 TABLE LIST OF TABLES (continued) 3.15 PFOA Recovered from Steam Extraction 3.16 PFOA Recovered from Pyroprobe Rinsing 3.17 PFOA Peak Area 3.18 PFOA Mass vs. Corresponding Peak Area PAGE 49 49 50 52 IX LIST OF ABBREVIATIONS Abbreviation ATRS d EPA Eqn ft GC/MS He HPLC i.d. LOD LOQ min NIST o.d. PFOA QA QAPP S/N sec SOP TCD TGA UDRI VOC XPS Explanation Advanced Thermal Reactor System Diameter Environmental Protection Agency Equation foot, feet Gas Chromatography / Mass Spectrometry Helium High Performance Liquid Chromatography Internal Diameter Limit ofDetection Limit of Quantitation minute(s) National Institute of Standards and Technology Outer Diameter Perfluorooctanoic acid Quality Assurance Quality Assurance Program Plans Signal to Noise second(s) Standard Operating Protocol Thermal Conductivity Detector Thermogravimetric Analysis University of Dayton Research Institute Volatile Organic Carbon X-ray Photoelectron Spectroscopy Executive Summary fTahbirsicstsuudbystrreapteor(t"satrhtieclfeir"s)ttkrenaotwednwstiutdhieasfltuooirnovteelsotimgaetre-bthaseetdhearcmryallicdepgorlaydmaetirounnodfear lpaobloyreasttoerry/cceollnudloitsioens cleovnesle.rTvhateivsetulydireesperemsuenlattiendgttyyppiiccaallmmuunniicciippaallwinacsitneeirnactiionnercaotonrdictoiomnbsuosftitoimn ec,otnedmitpioenrastuwriet,haanndaevxecreasgseair iiatdtnnhenecmetdtiehnppcpeeoetaarrlepayabnettelveuresidrttraeeroamernor/acemofteeue1eldnxln0utpwt0l.oeo0icftshtCePeFsfdouaOtrbcoAhrgibrcaeiestafrdltfeueeoarosrttromerodvoteeeywdrleouidatmnphadpenarerdo-rfbxlntuayiomospteriaobdctteaeealllacymorsmy2uilgeniscnrie-cicpbfiioparcealsayselnimdidtneeascnocrinrcudyeerilcsritpaecimtoioposeofen.pldyceTmoorhffneleuidrnoiritesmrisooduunoelnscts.stitacrdTniopeohyamieelcrdoweanfacasonistrddrteea,(ntPaetoenFtxdhOtaiAlte)s cccFteooolxutmttttoooiplrnneor.s,itsewaelnododmomlpe)aarai-pnnbeldayrstseooydfnicamtehclperlytauilrclitoc(osipii.celo.alfypinbmodelerwy,r-sapetrs(eitBnreacrr,enippk-aaesml,lllyeeidtnweac,oly.-o,ptdo1ro9pt9phu4yelp;mle.Kn. ieSTs)osefamxi,bet2ielp0res0afp1aae)nbrdarmirctehsaaeyapirrapebllsmiloeednacddtooesn.ftthraPoieanmpsfueinrbrafeiatsrucsreasoluf(cih.ea.s aiTnnhtdeerpeeansptve(irHroaenrkmesteoenfrtt,eaenltfiaanltc.e,in2oe0fr0pa3ete;rdfSluwcohhrueilnntzat,theeedtyacahl.re,em2d0iic0sa3pl;os,Dsesidum.cihtNraoosv,ifnleuftooarrlmo.,tae2tl0ioo0mn4er;reS-gbtaoarcsdekid,negstueabmls.t,ias2ns0ico0en4ss)i.sfTrooefmxgtirloews. ing wrtTt(irhne"hehpaceaeerirrftnteneeiiescrdfierslotaentarit"ktresii)ton,niicntontgrhlwceeoteiaynnfitppseetsreirdrticaxeunawttadceilsliiidmeopet.hssanulaoatnobfrifolcpliycuinapuovepsarxeelosoprittefneitgrctlcehoatieanimtsedteeewrttdraho-otewbibroatkeihnsthweepcrdrfoamelsanusacdeotlornirytdotidloetiieecngntlrseopmarmoodmulfaeynittrnmiii-comebienpaetrhs,aoueeltfnedweamdpnapervpsrooietllredryaoaubaentcsosumttrrsdeaeeirit,ns/soccatraaeanylvlrdldafcuaeeiolltdxoanecsbdtoeeeliestxffi.staotihTbanleeihrsriitoccslreroessvapnutetuasbelepds.dretyTvrraaa.rhrtetteeiipvcoleerltys DacTcTonehhulmdeePlucmostleeunooslbstltnuesflstolyrfuoraibsmbutiseescutrerwslfada.itabtefisFeoowracrnsbhatwr(rosecishcaoaesottnfitswnaoetbgnoicrt,thiboewcemxaoctnrpiooedlomedpwssrppietaiursitinohlespdnnoe)tduphautaatosipasvefefbdearle.uboienolfTnerpbhongaoetdpeethnfeloolreusf.mryopaFnerololrtllyh-uytbeeoedaltsroeisotcmseetcdraeernl(iarobedcbmterhandyeysa.lrelti-(ecudbUnrpapaeSsoolegl4lfydyli7ybmm4acec2eorer1srlry,4ttulrthi0esecaeraatpedtnmpaodwrhleeytUanhmustSaseawlemi5cpde3rraai4oencr4peitt9dereims0)ext3atetoai)ndslred.tys The test protocols used were similar to those developed for recent testing of fluorinated materials efg(rYxaopsamiemfrii6cama0dt0eainotatnons.dc1o0TTn0had0yeitlCisootrunf,dos2i.r0ea0sT3meh;meeGraumrnlaaa,htlgeaeadmxst-p,ype2phr0iiacm0sa2eel)nrm.etssuTinwdhieeecnrrimpeceatohltgiewrmnaavescitoomenfied2ntur.c0icicntseaeednrcaaa.tltoy8nrs5oic%sno-wmfelabxasucmeusetssiseordeanaitcrcoowtodnaredstfietiuinmoseenptdsehrwfeaotirutharelalsn average temperature of 1000C or greater over approximately 2 sec residence time (Giraud, 2004). wCoermebcuosmtipolnetteedst.s Tfohrethfoelltorewaitnedg oarbtjieccleti,vtehsewunetrreeaadteddreasrsteicdl:e, 1a)nddettheermfliunoartoiotenloomf tehre-btaesmepdearcartuyrliecfpoorlymer ut9rn9et.ar9te%eadtecadonndavruteinrcstlireoe,na4t,)e2dd)eadtreetirtcemlremin, ia3nt)iaodtineotonerfomthfiemnacatojioonrncpeonrfotrcdaautricbotosnnoofmfiPanFscsOombAaplialnenttcehecesoeamftfb1luu0es0nt0itofCnroafmtor1a0tlh0le0tetrsCetsaf,toeardntdhane5d) xi darettiecrlemsi.nation of the concentration of fluoride ion in the 1000C tests for the treated and untreated The temperature for 99.9% destruction of the treated and untreated articles was 725C. This temperature regime (700-750C) for 99.9% conversion is consistent with the results of prior tests of hydrocarbonbased materials using UDRI thermal instrumentation systems (Dellinger, et al. 1984; Dellinger, 1989; ptThoaalynylmothre,aret wtmaaels.as11u90r90e00d).Cfo.rTTohtheheeterTm9f9lpu.9eovrraaitnluuareteefdfoomrrta9ht9ee.r9fila%ulosdruoestseitnlrougmcttheioer-nsba(aTms9ee9d.9ea)xcoprefyrtlihimce epfnloutlayolmroaepterplwaormaasteurss-lbi(gaGhsrteladyhaahcmirgy,hl2eic0r 02). The difference may be related to the levels of excess air present in the respective combustion tests. wCoitmh bouthsetirofnluteosrtisnawteitdhmthaetefrliuaolsroetmelpolmoyere-dbacsoendsiadcerryalbiclyphoilgyhmeerreuxsceedss8a5i%r leevxecless.s air, while previous tests wedoEamerbxattsiscepceecllorotleveblyseedsend(e.d1trAv0vctiod1eaaddr.d9bGiuetoaiCtnnoend/nrdMmmearl1aSiltn0syhsi3e,ne.bots6htaef%hfleae-c,lpnoicrrncneoeeedsmsspieGtebwnioCcucentse/irMstveioeowSoflnyabhws)tteeaaaacsivstnatsire1eebodm0ro,f0fnpltr0ehlomosemCsyot.evrntdehooTaelxthatoiecetdidodleomeea.ntnfeblFlydruulmpusoutriorninoiortneirdnnaeuttaathceettedtesetddopbsrfyaooeirprsnftgreictocanholndecemiuescuc.ponbtlsIetfy.nrtvpee-NoralcoiltnoaeodetdmupilcGeaebtansCufkdlsw/sutMtiorewoerSrneiaenrtwtneeahdaotaesttd bdeytpercoteddu.cts in the gas exhaust from the 1000C tests of the treated and untreated articles. No peaks were buwablfuitCinhlylnebpuecoceplirorooodimaretnnhrweorrobeoyecndttruhaoltu1eaoistinilcf0tesnrtooidti0dadmsromru0beinaccfcaselrroteCauntrtoeen-itlu.pdmcibstdna,Meltaioeslgatttshnhikameoctoeenshdotfna.hyemfctssaTlehio.sucorbehmTrosfouAyerpfetrsblolnheiltieuugoticaecxeoosimlstplpntrnyreoioeaoesowmrcrtllrineeiysoiamBeslnmmoosourte-mAflefiepbntnrttsrolaehtphd.csiusrereeno-eencAebdfhdrtodldeaaiotunscatsalfoi1faceccorri0rtdrotroaneoyo0mmuwd.atlr0eilceActdeltmrdhCohfsypnefmaet,lloaohituf9cteletaoreey9rrebtprln-im.someaosb9tuemlela%failyltsrdrtteeomo,eiewcdrodmantteenforetauslryiudiaotcfnwmrldtirifdcuoeoydeitacdtbnliridetiotevesuiciednooastcwdpanennrionleoireuaineomsgltrlmtdyytfeyrcieum.tnobothicoPhyeetmeethfoereerfecpbtdidowserrooueafunttmeslmochontytrioieperdmaefoimaoleNgnnfecurvoiborIitnntolrSeutywidlstostTspasahtattftsiiutesimacoetldohatenpoaiilfetebnosceesmtdstlsomxheeye.mupesrrmpppnevberereeiruieccrdamtist.ataprtueinBataoirnldloeantnssseodf AtOrenfaaatldeyddsiiatsirotfioncarlelPiFtnoOtedAreetsientrwmcoainmsetboiufdsietnitcoeinrnmeterisnattesiowonfhotehftehtreterraePtaeFtdeOdaAratniwcdlaeussnfmtoreramayteebddeaaasrtsiaocurleerscauetlot1of0P0f 0cFoOCmAbuusinisnttighoebnoeotnhfvtihreonment. HtofhlfuPePorLeFrCofOot/erMAeloSbwm/eMoecurSo-lbdnaacbnsleeudddfioenard-cmlritynheleadictGfuprConomd/lMyemtrShteeywrp.ineicrceainlcemornaudtniuoiccnitpeoadfl.awNtaeosxttdeileietneoccirtnapebarlpaeteilroenvsuecblosontrfdaPittFeioOtnrAesantweodassiwgdinetihtfeiarcmaninteqdu.anIttictyan In addition, transport efficiency tests for PFOA using aqueous sampling (followed by HPLC/MS/MS) and HlgianPseL-ptCehm/aMspeSers/aMatmuSrpealsinnoaglfy(1sf7ios0llpoCrwo.deudAcbletyedrintnra-atlniivnsepeloyGr,tCien/fM-fliicSnieeannGcaCiley/sMsiosSf) ltweesesstrsethucasoninnd2gu0Ac%tTeuRds.SinArgeqaAuceTtooRurSsansrdeaamtcrpatolnirsnfagenrwdliittnrhaensfer AAteTmpRlpaSeursPaitFbulOreeAsPForeOfs2Ap3o5lnossCes pbmryoetdchhueacnreeidssmptroandnusserpioonrbgttteahfinefiecadiqebunyecoideuissreoscaftmgirnpejlaeintcegtriottrhnaanonsfp7Po0Fr%Ot tAe(dstiesntetmormathyienhegadavsbeycinhdvrioovmlivdaeintdoggtrhaeph). absorption onto the unheated silicone transfer line tubing between the ATRS vent and the bubblers (see Y11 Ff5oicgra.Pp2Fi.lO1la5Ar)y.ccoTonhldueembnanssasitsuiopfnoprointrhtti(hspehhayebnpsyoolt-rhmpetseiiotshnwyalanssdilttohrxeaansnsterpo)ondrgtutrieinsnttgesr.tahcCetriioynno-gloienbnesiecGrvtCeem/dMpbSeertaawntueareleynssPiwsFeaOrneAdntaohntedreetvqhiuedieDrneBdcetaosttrraopngPFinOteAra. cPtiFonObAetwwaeseenfftheceticvaepliyllatrraypcpoeldumusninsgupthpiosrctoalnudmtnheatanaatleymtepeorfaitnutreereosft.40C, thus indicating Based upon the combustion product analyses, it was clear that carbon-fluorine bonds were severed at aumw1nn0oadt0turr0eilioadxCnt.be.cdeAhTeanrxrhoatpimilscyelaswceittsooeagduftorlt1adro0pfr0hfleuo0ysorumiCrnlitddhbieinyycidatothtrrneoaedpg(fpeiofnlnirundmofiglcaruatithodtiioerevindeg[Feaoo`sf][feHfbHolueFuFlo]sorbfweionyfrfeamlruneaaeaatotnlciymottitnioisnc)na[aiFlwnq]dui.ceteohtFoemhlucuybtsoiduobrrsniuotnibgloeibemnalnettioretassmsv.tfassoiSlolaaulrfobbetwlsheheeeiqidgntuhrbeetlhynyaettsercaedomaacmpntibldviunesgatinodn i(ifhd(fsenSnlHlaioxuuctgmwaFeoFrohemr)r4prn-pao)iwtlsidrseetnwteeeemiradttleawahotgipasitdmeomiietootnhnrnhebnaeeoorotrsi-wutsfanebfirtitrcaadlenehvirssidcdeeerfeaoifeaddfmcebasrgaaroaictirentsacdmteongoirpaunyttrocthpeblsedoiiedseymncimcdpp(tfptpS,rbrroiooeoeohuiflrms0dnosyateuts2hwtmin,uiceoonecSrtenv-rfeeirile.Oe,tnioaahnrcXHctt,efeohttfiP)oneeenGlSuxrmssod.Cieopifsapcre/tTttnMieaeehrnharitnsemeeaSlittysstrosuwe.estiionnriasgiseTtttcntavashohhtilleobfeefiraiirneotycpsshtcsaniuwpurlegnirearcnekftpfarhaeaeaaeyscrnllctitroyeuncero6m.eshg.dp0sipuRarynpS0otreigoeotobearmntgvlooenodsrindofaecdstgtvmaheh1foaredeoe0stflvrrr0cHrifaeiS0derldnauFogaedcFeCmcenats4tvsi.ctootiaseuhshrnShssiiecsobigetouloowldcihfrencofewheotfaemroidynchxrtdmbeceaaatr,uoemmtinotmsnnhrepgittgaaniaoaeeofparritnsln-nhpatutliftieoionotsulnnhurnofreieeoetdtaodahretribfeetdlsoteyhttehe hGarirgiashhinlaygmffl,ruo2om0r0in2caa).trebdomn-afltueorirailnseubsoinngdhbirgeha-ktienmgp. eSraFtu4rheafsubseedensiolibcsaerrevaecdtoinrsp(rYevaimouasdacoamndbuTsatyiolonrt,e2s0ts03o,f bTaosesudmacmryalriiczep,otlhyemseerreissudletsstdreomyeodnsatnrdatneothdaetttehcetapbolelyaemstoeru/ncteloluf lPoFsOe fAabisricfotrrmeaetdedunwditehr tayfpliucoarlomteulonmiceipr-al psiniogclniynimfeirceaartnidotinsspocouosrnecdeditooioffnPinsF.mOTuAhneiinrceitpfhoaerlewe,natvesixtretoilnaenmsdeaninntd.cipnaepreartetdreaarteedexwpiethctesudctho abefludoesrotrtoeyloemd earn-dbansoetdbaecarylic xin 1. Introduction Fluorotelomer-based acrylic polymers (Banks, et al., 1994; Kissa, 2001) are applied to the surface of cctceoooxtmttttooiplnner.,siswaendodomlp)aaaipnneldyr stooyfnicmthelpeltauirclto(osiii.cel.afpinbodelrwy,-apetrseitnrecrr,iepp-aaemllllyeidnwec,oy-optdoroptphuyelpmle.n. SeT)oefmxibetielpresafpaaenbrdrmitchsaeyairraeblsmloenacddoesn.ftarPoianmpfeinbraeitsrusrasluc(ih.ea.s Tiannhtdeerpeeansptve(iHrroaenrkmestoeenfrtt,eaenltfiaanltc.e,in2oe0fr0pa3ete;rdfSluwcohhrueilnntzat,theeedtyacahl.re,em2d0iic0sa3pl;osD,sesidum.cihtNroaosv,ifnleuftooarrlmo.,tae2tl0ioo0mn4er;reS-gbtaoarscdekid,negstueabmls.t,ias2ns0ico0en4s)fi.rsoTomefxgtirloews ing wrtTt(irhen"hehpaecaeerritfrnteneieisercdfiesrloteatnari"tktresii)tno,niictonntgrhlwceeoetiaynnfitppseetsreirdritcaxenuawttacdeilsliiidmepoet.hsasnulaoatnobfrifolcpliycuinapuovepasrxeeloosprittenfeitgrctclehoatieanimtsedteeewrttdraho-otewbibroatkiehnsthweepcdrrfaomelsanusacedotlornirytdotidloetiieencgntlrseopmarmoodmulfaeynittrnmiii-cmoebienpaetrhsa,oueeltfnedweamdnpapevprsrooietlrledryaoauabentcsosumttrrdseaeeirit,ns/soccatraaeanylvlrdldafcuaeeiolltxdonaecsbdtoeeeliestxffis.tota-ihTbanleeirhsriitoccslrreoessvpanutetuasbelpeds.dretyTvrraa.arhrtetteeiipvcoleerltys DcTacTonehhulmdeePlucmotsleeunooslbtsltnuesflsotlyfruoriabmbsutiseescutrerwslfdaa.itabtfeisFeoowracrnsbhatwr(rosecishcaoaesottnfitswnoaetbgnoitrc,thiboewcemxacontropioedlomdepwssrppietaiuristniohlespdnnoe)dtuphautaatosipasvefedfbearle.uboienolTfnerpbhongaoetdepethfnleoloerusfm.ryopaneFrololrtllyh-utybeeoedlatsroeisotcmseetcdraeernl(iarobedcbmterhandyeysa.lrelit-(ecudbUnrpapaeSsoolegl4lfydyli7ybmma4cec2eoerrsr1rly,4ttulrthi0seecaeraatpedtnmapowdrhleeytaUnhmustSasaewleir5cpdes3rraia4oencr4peitt9dereims0)ext3atetoai)ndslred.tys if "Fluorotelom er" i Functionality A. U o r C H 3) Polymerize with other acrylic monomers Fluorotelom er Acrylic M onom er Fluorotelom er-based A crylate P olym er Figure 1.1 Fluorotelomer-based Polymer Description. 1 2. Experimental Protocol 2.1 Introdaction/Objectives The incineration study was conducted for three samples provided by DuPont: a fluorinated acrylic dwe(catcpdAexilhooeissmpdlmtTlcooeyeepuRrrbmsrlesimyiauSdsmremsaee)iurntetd,swipiuenoeouliritndentnentahdhltbtfwoerhosyuvefteeirpsaahs9trirrtiueen9ensioproeg.dcdam9,uciluta%ntstsawiceroeoltstsoricsnasstcaotm.aiplCtanneimrbopOsdvoinp,leecl,iilapnresteCsnytegddiuOdnuopadidrn2narnie,eoerdasCantsf,itqitacFala5umnle3nne0eaHdsoaeollty,Ctfuhyhrt0esaetioiaci4sandsccat%ocsbahelrlledatuesmeenamtawcnindemoheidtdndtnnhpheeCitoalsqstetdngc.euhsrrdFfeemiQr,ubsodpauiemewaonnadttldeeanyteadrshtammli.sesutqapTeeissuntrweehai.eacvdemhOdlieifefa.tpinoraydeleePnredvaaet(masglhslrnesyeafeauvclsesjurseeiioasAtfodlruinrwocptgdochafpyoaeoteces.iacr(oonltmQaTnandolnAvashitfxoeolee)tmirrhGpcAsseeepita)aToar.ewcctfnRrteioT.aoodmSrtrrhmuF(kehesPrlneyeauwFddtssoteOatworfebtsioaAmeidatilreolel)etnbwhdaeenads 2.2 Overall Experimental Approach Sample gasification behavior was investigated using thermogravimetric analysis (TGA) and results are seadissnyfnahef-smdoclltuiowepvnemmloennelsptgiam.nofatPrissalSoiFettcmeeiOhoocrirtrAntaiogholp,maesnrfnaoelw2iutxfco.eoi4hlgrcre.aeiarduaorTfesbpeftG,ohdelanyAiatnn/co(mdehrVteachaOsshsneausCldmlAots)surppTidswldeReieecnetSatgersrneroatomdommufifisipend-neltlaecdiretnnyisintetooiw(enfGGrydeawCCertmeete//eMtractrhehjmoeoSeplrril)mmenecsrceoafyatolmtesnhrtdcdmebeomiuansnensaddwtaamuiqiloacnypunstzlieseveubeoiyspguttehpyaasderrsdsoaiitorfetdoeiltcucuegoeacctexmttitsionopo.bnerenurrQ(aasitTntmetueiCmdoaetDnndnphtetee)ibsttrayeatabhnrtptyimeudrvrorceimeGdno.CuaeCllcldTOe/tMchbs,t.eyCiSnAOgn2, HPLC/MS/MS and ion chromatagraphy using Exygen, Inc., an analytical laboratory selected by DuPont. 2.3 Samples 2.3.1 Atomic Composition Tables 2.1 and 2.2 show the weight and atomic compositions of the samples as provided by DuPont. Table 2.1 Weight Composition (%) of DuPont Samples. Sample FUTlrnuetoarreteiandtaeatdertdaicratlicecrlyelic polymer C 4499..17 40.5 H 5.1 44..90 F 350..52 0 44556...825 Cl 13.1 N 0.3 Table 2.2 Atomic Composition of DuPont Samples. Sample UTrnetareteadteadrtaicrtliecle Fluorinated acrylic * Number polymer is neglected fo000r...C333th354e400sto0i00c...h44H4i012o102metr0i0c.0.Fr10e81a5c*tion000s...hO022o433w098n Cl be0l.o0w3.7 N 0.002* mThme)upnutrrecahtaesdedansdpetrceifaitceadllayrtfiocrletshiws eprreojpercetp. aTrehdeufsluinogrianaotnede-ahcorlyelpicupnoclhywmietrhwaadsiapmreeptaerreodfu6simngmo(udr= 6 2 huannifdo-rmmaddiemmenetsaiol ntesmapnldatme awsshiwchergeivoebsta"ihnoedckuesyin-pgutchke"seshaappperdoapcohleysmfeorrseaamchplseasm(pdle. 1.6 mm). Relatively Based on the atomic composition, the stoichiometric oxidation reaction can be written as follows. * Untreated article C0.34H0.42O0.24 0.3902 O.34CO2+ O.2IH2O * Treated article C0.35H0.41O0.24+ 0.39O2 - 0.35CO2+ O.2IH2O ---------- (Equation 1) ---------- (Equation 2) * Fluorinated acrylic polymer C0j 3H0.40O0.04F0.19Cl0.04+ 0.35O2 - 0.33CO2+ 0.19HF + 0.04HC1 + 0.085H20 ---------(Equation 3) wThheicahmisouenxtploafinoexdyginenSnecetcieosnsa2r.y4.2fo.r complete oxidation was used for the gasification time calculation,' 2.3.2 Thermogravimetric Analysis (TGA) Results wfAtCeraoSmTsmIpGgMeraAroosaoidtsfmueituerleddt1eyfw0mo5wirpt0ahcesToraamGcitroupAnarlened(tduSteocttogthtehnaedseewi-pfpPireocriioeaignmtrhitottcwon%ohdoAeerfrevneemeaaltlaochyihpetnirmtcieenaesgilnstIwtmnnoosaatfstrfeturuhremriecatheolt.enersTdrtstewG)pdperAoairgsotwohgfcaturosalnomlpcsitesmnir.ofoenoAdrrdopmaefptretraetdoomhxieniepmasefttrlaaioantbtewgulliyrisrneah4.gtetmhaoeigrfu2os5finsCagm/ampilne o2abF5cb.e5i5grsh0y%eualrrCvivecfiesoofpdror2oru.wul1yunnamnttasritnelerodaer6b.ta02est0.deTe2rdhavCsenaeh,nddgowdatwfrhsoteirerTfaeribtGaeceotadnAetthdeiaoarrasenrtarlsitycmouilclfep1tlstse0lh,es0fesr,o%.erprseoGpugslepnayacetssmrticiiefftveiaiiccrevtaealesytdttlii.ayooar.nnFtneWdiwsdgttauaearsrreittegaoeahtd2breto.sda3rueetransmv3rhdte8oaid10ciw.n0leas0isnnT,gdCrGe3.asAf5Cpt0eoerrnceCgtstiiuavnasleuntislfodyiufc.eoasnrtSwidtoihemendeigiwflahaltaurt6solg0or7ais0nssaiaanfwtnidecdadastion 3 Figure 2.3 TGA Result for Fluorinated Acrylic Polymer. 2.4 In-line GC/MS Analysis and 99.9% Destruction Temperature Determination 2.4.1 Experimental Setup and Procedure for In-line GC/MS Analysis of Combustion Byproducts Figure 2.4 shows the ATRS, which consists of a sample inlet, reactor, cold trap, and in-line GC/MS system. The sample was placed into a sample cartridge (2 x 2.5 mm (i.d.xo.d.), 12.5 mm length quartz I2cna0cp0.i0)l)laa.tryT85htu%ebpeey,xrCcoeDpsrsSoabAiernwtaolaycstoipcnlasalecrIenvdca.ti,invOtoexlyIfnorlreedpt,r1ePsAaen)ndtagmnadustnihfiieceidcpaawrltirwtihdagssyteenwtchoaesmtiibcnusaseitrrito(e2nd1ci%notno0dai2tipaonyndrso7p(9Gro%ibraeNu(d2C,,ADiSrg- as 2004). All experiments were performed using synthetic air. The reactor dimensions are 4 x 6 mm 4 rim(nei.caadici.nnXtoetoarr.iadants.ie)osdewnmaittetbhsaltpya.p.nroTefxhfieemcttaeitmveelpylee3rna0gt0uthrCeoaffto1trh5aeclslmee.xlopTceahrtieimogneasnstwsre.assiFdmiegnoucnreeito2tir.m5edeshawonawdssr2et.ch0oesrrdemce.odcbAoeulflpotlrreeanlaosncfdaetraiolfitnnesersitnhwetehree Figure 2.4 General Schematic of the Advanced Thermal Reactor System (ATRS). Figure 2.5 Position of Thermocouples in Reactor Assembly. 5 GC/MSAnalysis Method mcTohaletdegrtiraaaslpisfmiwedaeirsneatarmeinpleelaedsweadta-sw1i2hn5ecninCtehrueasticenodgldilnitqrtauhpiedwrneaaitscrtohogerea, ntae.nddAtotfht2eer8c0coomCmbb(uwussitttihioonrnabwmyappsrinocgdoumocftpsalepwtpeerdroe,xtcihmoenacdtoeelnnydseendsiendthe 45C/min) and introduced to the GC/MS system for analysis. An HP5890A/5970B series GC-MS with DFcooBnls-do5emnGs,CeCdcAma)pawitlelaarsirayulssceowdleufrmoernrien(l3-el0ainsmeedcleofrnmogmbthu,tsh0tie.o2cn5obmldymptrraoip.dd,u.t,ch0te.a2mn5aal|tyiesfriiislam.lsTtwhhieecrksenpcelristysro,agAteiogniiwlceaanlstlyT1tetrocahp2np4oe.ldoWgaithetsihl,eeItnhce. head of the GC column at -60C. Following the cryogenic focusing, the oven temperature was held at ma6c0atusCsalsfscoaarmn1prmaleningc,eotmwheabnsusi1nt2icor-ne4ap5sr0eodcmetdo/zu2rt8oe0walCalos(wpweairtnfhoarlryammseispdioninfgasoewqfiu2de0enrCcae/nmagsienfo)oflalncoodwmhs:pelodufnodrs1in0cmluidninatg2w8a0teCr.. TThhee 1. IiSnnetltreoatdi2ru.fcleodwtoraItnelteot o1bwtahienreretshiedepnycreoptirmobeeoifs2insseecrtaetdthaendreoancetotrh.irTdwoof tthheirdflsowofitshienftlroowduicsed to 2. Record ATRS inlet flow rates. 453... IRSneestceocrotrdpldytertromapppreoterbametupirneetroaattIuntrhleeett7o1.p-1o2in5tsCshuosiwnng ilniqFuiigdunrietr2o.g4e.n. 786... RSStteaambrtiolpivyzeeroptpyhrreoosbpyersottbeeemm.pfeorra2tumreinp.rogramming. 911.10.. RRSweecceooerrpddetAneTmtirRpeSesryaintsulteeretmfalwot w7ithproahtieenlsti.sumsho(Hwen)ifnoFr i3gumrien.2.5. 1132.. SSteatrGt GCCc/oMluSmanntaelymspise.rature to -60C using liquid nitrogen. 14. HGCea/tMcSo.ld trap to 280C to release condensed materials from the trap and transfer them to 2.4.2 ATRS Experimental Conditions Flow Rate sTfihhxoeewdrnefalbocewtloorrwavt:oeluomf 0e.9o4f m1.8L8/scemc 3at(02.52Ccm. Ti.dh.i,s 1f5locwmraetfefewctaisvecolerrnegctthe)dawnidthretshiederenaccetotirmteemopfe2r.a0tuserec agsives a 0.94 mL/sec x 298 / (T + 273) (T: Reactor Temperature in C) ---------- (Equation 4) Gasification Temperature and Duration fTinaballete2m.3psehraotwurseinoiftitahleaunndtrfeinataeldteamndpetrraetauteredsaortfitchleespwyreorpersoebtea.t B35a0seadndon6t5h0eCT,GrAespreescutilvtse,ltyh.eAinlitthioaluganhd stthhaaemnTetGhleeAvterrleefasouterldtcsoainrntsdiicislcteea,ntetchdyetahpnyadtrotthpoeroffabicneialfiltiangtaaeslicgfoiacmsaiftpiiaocranitsitooenmn otpeefmrraeptseuurrlaettsuf.oreTrsthhfeoetreubmnotprtehearmatetaudtreaerrsitaifcloslrewbiseort5eh0smeCtatahetirgtihahleesr 6 were identical for consistency. The initial and final temperatures for the fhiorinated acrylic polymer were set at 250 and 650C, respectively. The temperature ramping rates between the in itial and final temperatures were varied to adjust gasification time and obtain appropriate stoichiometric conditions as described in more detail below. The temperature of Inlet 1 was set at 300C for the untreated and treated articles and 250C for the fluorinated acrylic polymer. The inlet temperature for the fhiorinated acrylic panodlybmeeforrweagsarseifdiucacteidonto. prevent significant weight loss during system stabilization after sample insertion SamplTe able 23 UTrnetareteadteadrtaicrtliecle Fluorinated acrylic polymer Pyroprobe Gasification Initial 233555000 Temperature F6i5n0al 665500 (C). Inlet 1 Temperature 300 235000 pBseaetrcatahmueeseetextrchseetsorseoaabicrttaloeirnvve8ol.5lu%Tmheeexracenefdsosrreea,isrti.hdeeSngicnaecsietfiimictaeistiaonrnoettfipimxraeedcatpincadarlaamwmieotthuenrestx,oitshftiesnafgmloepwqleuriaaptrmee cethanent nttowotpobreaedpcjauhrseatnathgbeeled to vfdlaeursoiierriedndtaoatemodboatucanrinyt lotihcfespadomelyspimlreeesdrwrwaiattihso.d1e0Ttephrgemcpianreleccdui.slaiotino,nthbeelgoawsifsihcoawtiosnhotiwmethies tghaesiofinclaytipoanratimmeetefrotrhtahtecan be mSuoplepcouselatrhweewigehigthotfothfethheyfploutohreintiactaeldpaoclryymliecrpsohloywmnerinusEeqdnfo3risco9m.8b8u. sTtiohne mato6l0a0r aCmiosu2n.t2o5fmpogl.ymTheer in this sample is 2.25/1000(g)/9.88(g/mol) = 2.28 x 1O'4moles. Fcarolcmulathteedstaosi:chiometric reaction for the polymer (Eqn 3 in Section 2.3.1), the oxygen required can be 2.28 x 1O'4mol x 0.35 T17h.e85v%oluemxceeossf aoixry(g2e1n%) aotx1ygaetmn aanndd 7299%8Cnitcraongebne)cianlcuunliatsteodfams:L with 85% excess air (85% x 0.21 = [2.28 x llOl.O^mmoLl) x 0.35 x 1.1785 x 0.082l(atin Vmol-K) x 298(K) / l(atm)] /0.21 x 1000(mL/l) = The flow rate at 600C is 0.94(mL/sec) x 298 (K) / (600 + 273) (K) = 0.32 mL/sec. The gasification time can then be calculated as follows: 11.0 mL/0.32(mL/sec) = 34.4 sec ' Since the initial and final gasification temperatures for the polymer are 250 and 650C, respectively, raasmdpisicnugsrsaetde aobf:ove, the pyroprobe temperature was linearly increased from 250 to 650C with a " (650-250)C/34.4 sec x 60 sec/min = 698C/min 7 ptTiomhleey.mkeeyr asstasrutms (p2ti5o0nsCa)raentdhaetngdassaifticthaetiofinnasltatretms wpehreantutrhee(p6y50ropCr)o,baendtemsapmepraletuwreeipgrhotglroasmsmisinlignefaorrwthieth 2.4.3 GC/MS Calibration Calibration curves 22912MI, Aldrich, wMeirlewcaruekaeteed, WfoIr)t,hGefFcogm(9p8o%unmdsinoimf iunmte,reLsot tb#a:se8dBo-n11p0r,ioSrywnQoruke:sCt LF3aHbs.(,9I8n+c%., ,ALlaocth#u:a, FL), and CgFis (98%, Batch #: 17024MA, Aldrich, Milwaukee, WI). The results are shown in Figures 2.6 through 2.8. The detection limit was determined based on EPA's detection limit criteria for identifying an unknown (EPA Method 8260B, pages 23 - 24). In this analysis, we chose the most abundant ion (target ion) and major ions whose intensities were greater than ca. 20% of the target ion. The detection limit was the lowest concentration that had the target ions and all of major ions whose relative intensify also agreed cwc1ao9iln9tihbs6ir,ts;ahttTeeinoirrtneewfyce,uirterehvntepca.reli.,ospr1e9thc9et0rr;amWwaliethdhreimncocemaie.pr,oes2it0tai%ol.n,. s1Ct9ua9dl8iib)e.sraTctiohonendfuaoncltldeoddweiitnnegcthtpiiorsonlcalebidmouriratetdowertyaesr(mTuaisnyealdotitroo,nectwoanels.r,ter1u9c9t5e,ach tAlhinekenns toarwanndnstfahemerroreeudancttotootrfhweeaaGcshChs/eMtaantSeddsayradstte3wm0a0sfoCinr.taronSdataluyncsdeiadsr. dinTsthoweMeprereoctco1endidnuertnehsewedraesaatectxthoaerctaclsoysletdhmterbaslpaym.aptA,-a1lls2ti5rnaCnths,efaenr d CcogmFibg,uasntidon13te1stfsoor Cf s4aFmg)palensd. pTlohtetemd aajsotrhieonfufnrcotmioneaocfhthsteanindjaercdtewdams oexlatrraqcutaendti(t6y9. for CF3H and wmfFarnioiogtdmhluedricteenhustceelra2ceDr.ta6isBosi-enz-d5e2l..im8GmToCsihhtleicofscoawuirpsslieaplcarlraacsoilhiyibzbsaecrt.baaoltnlyiudomdanurncdeu(atr3orv0eeamssnufimolnercmnCrgeaFtarh3is,zHee0d,d.2MGi5niSFmTgr,ameabsnlpie.dod2n.C,.s4gAe.Fgf1aT8i,lchertneoestrdpTaeenetcecdtchibvtnieeootlnltyoe.lrgimpiTeehista,ekiImlnisncph.eraoaFprvoeefloisstobwemtaqi,itunhCaetAdio)n 8 9 Table 2.4 Linear Fit Equations for Standard Calibration Curves and Detection T.imits. Sample Name CCF4F3H8 (x: moLl,inye:apreFaikt area) xx -= ((yy+- 12..6596EE65))//21..0378EE1145 x = (y - 3.94E5V6.32E15 R 0.997 00..999999 Detec(tmioonl)Limit 1.01E-8 21.3.041EE--190 2.4.4 GC/MS Determination of Major Ions for Construction of Thermal Decomposition Profile uaPdnsereedtedli6rmmw9iei(nnrCaeeFrmy13)2tae2ajson(trdbs iew7on7nezsro(eCtichc3aFoatcn2Hciddou3)u)clatfdenoddbr ett1hou4eis9dfele(dutneoftroriefirnpycahtothtehnedascltairhccuercamytciliioicdcnapdlooesfrlpyitvehmcaeiteeitrvhs.eea)rsmfsooarcl itdaheteecduonmwtrpietohasttiehtdieoanmnpdarjotorfreilpaete.eadkTashreatincidolen,s Treated and UntreatedArticles bpTerheneszruommicaalabtcleyisdtfiwrnogamswtsahisme ilpnaliretgiagetasetsdipfaeictaak6t0ifo0onrCpur.notTdreuhacettestdowtaainlthdiotmnreicnahtiemrodamal raottixociglderasatmiaotno6.b0tP0arienCle.idmFaiintgatuhrryiest2tee.s9mtsspihenordawitcusarateetdwottaahslaiton wchhreorme athtoeglraarmgeostfsthigenuanl tirselaotceadteadrt.icCleoamtp6a0r0isoCn, aonfdthFeigsaumrep2le.1a0nsdhloibwrsartyhespmeacstrsasipnedcitcrautmesabte1n3z.o4icmaicnijd mwiitnhh9a1s%strmoantgchioqnuoalfit1y4.9Tanhde fisirmstolasrtgleikpeelyakaatetr8epmhitnhaislicduaecitdo dtheerivfoartimvea.tion of water. The peak at 16 rpmtsFarhrietaogoiasoduwtseurosredcaftm2nasthn.gao1edsef1ssbuepssenohtpttwloweryewcoeeatsserpttaeneaedaar3tktao(5Osrt1taa3wihlcn.t5leidaeornmsen4i.5,iccn0Beah,tlremcwoanulm/hz.lz,aoeaRttritoeceoadgedat.hlrcliaeeTmimidnhliaan,eornaegrfdtteeetsahstutelteh.lrp,teetesr1pape9shkaeh9ttaho1eiksa)wd.llaieaocsTdrcstahaiotcctheceilaidedaatr.tcateehoraSdeemsiwembobxeiufitpnlhsaaeztlricwloortpieeancedstaeauatkrtclhtsi6fsedr0wrowpm0meeearCaretlekhdiaeoncenbotcadetnonagFsmairinilasgypettuseosdidrssoefi,wotfi2aro3i.nt31nbhd2oiatntnhhdea p3e6a%k ocofntositsatlspoeaf k13a%reaoffothreuntotrteaaltpeedaaknadretraeafoterdboarthticslaems,prleessp.eTcthiveetloyt,aal nindtethgeratteerdphptehaakliacraecaiodfdtehreivseative aenxdtraucntterdeaitoendsa(r1t2ic2leasn. dT1h4e9r)ewsualstsuasreedsfuomr cmoanrsitzreudctiinngSethcetiothne3rm.1a.1l daencdo3m.1p.o2s.ition profiles for the treated in A fc > u n < d a n o e pd8(GeeMar1ikav7.ta0ct1hcivBTIqeDAhu42351bias#ValiscteeoyrdmsfirooponnomumBnN0adTn3I1Secu.-0orTaPe0ul1hp,lmC2edAh9naotngKhysBmoisallte-seTlBsp1stninpacopo,ezte2nelnuoTcaud-ctzicnpeaeircefciarrdniddnohlcaeNnepaacsdbnolpaieladaleynromliceyvbgtdsaerieeiatisisoiv.ld)ine.ebenrbatiTrfyioe,ldou,bebntaueitnQiisesudlmoabcloyai97999sttd181tey64adlit(kao%enalny)taoaalpytseoirfsetpshohefthtlwaarlagirceeawcaidter Figure 2.9 Total Ion Chromatogram and Peak Identification for Untreated Article at 600C. Abundance 11 Abundance ID # 1 45623 Compound Name 1-PhenByle-TBn1Woez,2lnoau-zitpeceernrnaoe"ecp0iadnedione Terephthalic acid derivative*1 Quality i%)a 99869111146 bttVehaMreecerklapsagtihrcortghnoheuaqBlwnui0cdaa3ltai.ieo0ctryn0idps,ferdAioanekgmrt.iihlvNeedanItTstSipvhTTeeece1btcc2rahou9snmmKeopd.lsoootTguaninhnemdedsa)mac.rnodabuujsaolTpdlrhemniceootanlrtosassswlpcsilebmpecreaaiacrfrtlitycycr,haaiilolnnlabydgntiabacqileaunytaeisedldiiwset.bnyayttiiefsdiread.dtuac,eTbatnuooatlnuliyusesnmmiesbosiessortflolotiwfkcaseamtlreyedaa(lGol n17to0p1BoAf Figure 2.11 Total Ion Chromatogram and Peak Identification for Treated Article at 600C. Figure 2.12 Mass Spectra at 13.5 min for Treated Article at 600C. 17 Fluorinated Acrylic Polymer FTihgeubreas2e.l1i3nesheolewvsattihoentaotta8lmioinn cishrdoumeattoogforarmmaotifotnheofflwuaotreinr.aTtehdeabcaryselilcinpeoalylsmoeinr dciocmatbeusstthioenpraets6e0n0ceCo.f ioeoxxntied8na5ttiowofnhfioocfrhmthisaetiipnoodnliycomaftSievrieFaionwdf tashsuebmfsooerqnmuitaeotnrietodrneiaoncftesiaoilcnihcoornfuhnteyttdorradofelguteeonrrmifdliuenoe(rSiiidtFse,*pw)o.itteThnhttieisaslptirsmoydsputaeccmtt iomsnaatsthesoericafillaust.oerdTinwheeith recoveries. Several peaks were identified as fluorinated and chlorinated hydrocarbons. Figure 2.14 shows extracted ifseoouxnrgtrsgtahe6ces9ttepeadodnliybdomyn7s7eth(r,6.ew9NThahiIncSehdTca7olr7imeb)rbtwahureasystmiaounansjdeobdaryraipeosrnporsledafufueocsrrteisbtnhloceeefcmiinooatmnejsorberfusopstrtewiacokeonrsnebsiydqtrpeuunracotntidiftnuiiefgcidetts.hd.eTaTtthhheeeearscmtthoruatracleltdaupecrecteoaoskrmotaepfrmtoehsapeietsoireofanttihoupenrersso.ewfiTleehree results are summarized in Section 3.1.3. Abundance ID #___________ Compound Name______ Quality (%) 21 3,3,4,4,-tNetoratfildueonrtoi-fli,a5b-lheexadiene 45 4356 lP,l,e3r-ftlruNNiocoorhottl-oiinddree-opnn-tet2iinff-iitPaaabbrnolleoepiacnaocnidec 4970 7 Not identifiable V"shMeorwastiecodhniqsButa0hle3it.by0ef0sr,toAmmgaNticIleShnTtot1T2the9ecKhlinsbtoraalnrodyga,irbedusst)p.neobcttNrreaoltliaiibbdrleaenrybti,efoicaabbutlaseiendoeudfetbhtoyeldlooawwtammanaaattclcyhhsqiqsuusaaolliiftttyyw..acreT(hGe 1co7m01pBouAnd Figure 2.13 Total Ion Chromatogram and Peak Identification for Fluorinated Acrylic polymer at 600C. 13 Abundance 4000000 3000000 21000000000000 Ion 69.00 (68.70 to 69.70): PM 8-29-1.0 iA..|/|ai ,. Ion 69 Ion 77 Ion 77.00 (76.70 to 77.70): P M 8-29-1.D 4000000 3000000 2000000 *1O O O O O O 1 ,1 J ill J . 2.00 4 . 0 0 6.00 8 o o 1 o.0 0 1 2 I0 OI 4 I0 0 Ielool 8 l 0 0 2 0 l 0 0 2 2l0024l0Q26.00 FigTuimree--2>.14 Extracted Ions (69 and 77) for Fluorinated Acrylic Polymer at 600C. 2.5 Treated and Untreated Articles: PFOA, Fluoride, and Chloride Determination at 1000C tsTfhlhuheooewprrirnedoaecicn,etadoFnuridrgeeufcfdrhleuelose2rcn.i1rdti5bef,rewotdhmeeirnteehsfdeefelccuttoeeiormnmntbwi2un.ase4tsd.i1.ot.anTkToehhnfeetfhsreaeonmmttripertleahetsseeywdesxteaehrnmeadu,gusiantnsvtcirfeleiuneadtdtieanadngndadcrptoiianlcdsclseitensrdaewprta,ahtswreodsauasigmnhhpeaalaesntidemadaqitnluoader3oPm0uF0saOnCAn.e, rAtos bvtAlas(fhe1iounelene2llbndsueg0betedtttxlhirahmeo,whne,rnWLadCsitut.ebfohaasmuilAmrtr6ebdspl0nbbtiPeHnelbrmaaeeraiudrrltLgmbaldus,lnbiryaeHMteldissreoPstmtrAIenh.Ljnmaao)esCTrlntaf,rtthisioguhItreor-mssecaCthrsrodeembaoHldnemuwloEetbwacencCMnbotatiodluuttn,e.hebpr,NrrFeeliVwenc(eiagHogewawnurr,sPadnraCalrLeeosypiadnCnt2ppse.s.rtlH1eGlaooFed5cixr,fol.eailwDilmdsdnlT,ioEetdateIhwhtLoUre)eeiw)5llnwssytwntigrmli.a2sitaeptcLhTsriaouenhc1HunraheeisexmPnebWetLd3luxuoeCbapambnftsiebtggenmhralrtrgieeh,amtri,d(Srb.e0sadweutny.n.o0bwatsscx,6bstpkaet3luoohtem#e.rseird2rtnesc.s2ld(,aiioiA9.nl4stndi3oelcs.sif4,oinhbac,s0nooetAlL.eetewn1wodenn2tnstugee5oa#betcifrhniLent)ntwtq1Ftathhohu0inoega.eaNddtubtre.w3ttcr,uzxhe9obo1he,sn2b2atAn.leu1ieemnls5rcftsats teoxtEraxcytgseanddweidthtochthaienfoirfstcbuustbobdlyerf.orTmhefosramthpelaenwalaysseses.alTedhewaitchtuanl asalummpilninugmwfoasilpseerafloerrm, leadbealsedfo, lalnodwss:ent 1. Sinettroadiruflcoewd troatIenlteoto1bwtahinerreesthideepnycreotpimroebeofis2insesceratet dthaenrdeaocnteort.hiTrdwooftthhierdfsloowf twheasflionwtrowdausced to 23.. 4. RRISneeeltccecotoor2rddl.dtAetrmTaRppSetreaimntulperetersfaltaoutwrtehrteaot8e3sp0.o0inCts(snhoocwonndinenFsiagtuioren 2st.e4pa)n. d 2.15. 5. Connect bubblers to exhaust line. 768911....10.. 1132.. ISSnttasaerbtritlpipyzyerortophpreorosbybesetteeinmmtopfeoIrnralt1eutmre1i.np.rogramming. . RSweceoerpdetnemtirpeesryastuteremdwoiwthnshtereliaummofof rse3cmonidn.bubbler. DRReeiscccooorrnddnAteecTmtRpbSeurbainbtulleerrtessflaotwthreat8esp.oints shown in Figure 2.4 and 2.15. 14 The results are summarized in Section 3.2. Exhaust Line From ATRS Exhaust Line Figure 2.15 Off-Line Aqueous Sampling for Fluoride and PFOA. (2V.6OCT)rAeantaedlyasinsdatU1n0t0r0eaCted Articles: Off-line GC/MS Analysis of Volatile Organic Compound toTarhkgeeannreifcarcoctmoomrtehpfeofuleunxedhnsatuafstrto1lmi0n0te0hseChcoouwmsninbigunsatFigoiganusorsefat2mh.4epltuirnsegiantbgeadaga0an.n5ddLuonTftfre-eldailntaeerdGaCrbta/iMcgle(SsSaKwnCaaslyIansncisa.,.lyETziehgdehtfsyoarmFvopoullera, wtPilAaes). Silicone tubing (0.063 in i.d., 0.125 in o.d., 30 cm length, Cole Parmer Instrument Co., Vernon Hills, GIaLnCa)/lwMysaSessau(nssaeeldeySfsoiesrc.tthiToehnter2ae.n7ns)t.ifreeTr shliyensest.eammT,phileneccwloualdlseicngtgaesdcifosilaeddmtrapanlped,wiwnacasisnuhesereaadtteefddorianbtoa3t0mh0VanCOnCfeorrastnihmdisifliaaxnreatdolygtshaisse.(iCnT-Ohlie,nCe 02) Bdeetlaleilfeodnpter,oPceAd)uwreaissussheodwfnorbaenloawly.siAs aSnudptehlecoinQjecPtLioOnTvocloulmume nw(a3s00m.5 xm0L..53TmhemGICD,oSveUnPtEeLmCpOeraItnucr.e, TwThhaees shmaeamlsdspalsitnc-ag6n0prraoCncgefoedruwr1eamsisi1ns2,h-toh4we5nn0ibnmecl/rozewatos:eadlltoow28an0alCyswisitohfraamwpidinegraonfg2e0oCf c/mominpaonudndhselidnc5lumdiinngatw2a8te0r.C. 1. IiSnnetltreoatdi2ru.fcleodwtoraItneletot o1bwtahienreretshiedepnycreoptirmobeeoifs2insse'ecrtaetdthaendreoancteo-rth. irTdwoof tthhierdflsoowf itsheinftlroowduicsed to 2. Record inlet flow rate. 4563.... RISSnteesatcebcoritolridplzdyeterttormhapeppreostryebamsettuepirnmeetrsoaftaoIuntrrl7e1epttmoo1ii.3nn0.ts0sCho(wnon cinonFdigeunrseat2io.4n. step). 78.. CStoanrtnpeyctroTperdolbaertebmapgertoateuxrehapurostglrianmemanindgo.pen valve. 15 9. Sweep entire line with He for 3 min. 111201... RRCeeloccsooerrddTtieendmlieaptrfelroabwtuagrreavsteaa.ltv7e and disconnect a bag. points shown in Figure.2.4. The results are summarized in Section 3.6. 2.7 Treated & Untreated Articles: CO and C 02Analyses at 1000C wraTenhesaperleeyscszateemipvdpaeulrleyassit,necwdgohfallriecoGchmCtew/odTetfrhCoeeDrrpVrc(eo8Oim6nC1spt0oaaClnulaneglddayssbsiuycsshtwirhnoeegmrmeaaata6olnsgfuotrfamaupcsohteul,derScefuRrolr(IaSCrIRnsOsiIetIravnunesmdtpreCauncm0tkse2,endTatnsoca)ro.lrlyauAsnmecssen.t,aaCTnndhAdae)sr.CdilCiOccaOaalignbaednrladCctiCoo0ln2u0mww2 nears,e ceoqnudatuioctnedofpCriOoratondthCe0a2naclaylisbersa;trieosnu.ltCs aarrbeosnhomwanssinbaFlaignucreesw2a.s1c6aalcnudla2t.e1d7.baTsaebdleon2.t5heshsoamwspltehegalisnifeiaerdfit and the amounts of VOC, CO, and C 02measured. The results are summarized in Section 3.7 Cone, (ppm ) Figure 2.16 CO Calibration Curve. 16 lauie .3 Linear ru L JLiguauuus iui auu v-auui a Sample Name (x: moLli,nye:apreFaikt area) cCoO2 jc= (y + 3.04E2)/8.13E-l jc- (y + 8.57E1)/1.37E0 R 00..999929 2.8 XPS Analysis of Pyroprobe Cartridge pThhoetosuerlefacctreoonfstpheecstraomscpolepyca(rXtrPidSg)etousiendvefsotrigtraeteatfelduoarritdiceledegpaosisfiitcioantioonnwthaescaanratrliydzgeedsbuyrfxa-crea.yThe results are summarized in Section 3.4 2.9 Telomer B Alcohol Combustion: GC/MS Analysis Iinnv-leinsteigGatCe/Mif tShean7a7lyisoins owbassercvoendduincttehdefcoormTbeulostmioenr BtesAtslcoofhtohlecfolumobriunsattieodn aactr2y0li0capnodly6m00erCis tfoormed. Iacoconcmo7pr7doininsegnthttoemtmihxeotusptrreaeblwiumhnoidnsaaenrtyfoicormonmuolbfauthastenidoflncuotoenrsictnesan(ttesredaetaiSocnreycrltaiiconngpeo2la.y4rm.e4se).hrocTwohmnebiTnuesTltoiaombnleebry2Bp.6rA.oldTcuohchetogelfeifnslueareinmctufoltrim ula is estimated based on the average concentration of each constituent and can be expressed as: C0.30P0.52H0.15O0.03 DcounevteortaesxccaerscsitfyluoofrihnyedtroogHeFn.inMthetehtaenset swuabsstsaunpcpel,iemdeathtatwneicweathsealsstooiscuhpiopmlieedtraics aamhoyudnrotgtoenensosuurrece to fSlcuioernintieficc,oHnvoelrlissitoonn,toMHAF). wAas1u0smedLtogassutpipglhyt msyertihnagnee(.SGThEe, Astouisctihni,omTXet)riacnodxsiydraitniogne pcaunmbpe(eKxdpressed as follows: 17 C0.30F0.52H0.15O0.03 + 0.185CH4 + 0.5625O2 -> 0.485CO2 + 0.52HF + 0.185H2O (Equation 5) Tath1e5s0amanpdle2i0n0leCt a, nredstpreacntsivfeerlyli,naensdwthereefkineaplttaetm1p5e0raCtu.rePwyraosphroeblde finoirti1almainndtofinenalsuteremcpoemraptuleretes were set gasification. Two tests were conducted at reactor temperatures of200C and 600C. The results are summarized in Section 3.5. Table 2.6 Telomer B Alcohol Characterization. Name Formula R aCn goene(.% ) 1,1,2,2-Tetrahydroperfluoro- CH2OHCH2(CF2)3CF3 1-2 11,-1H,2e,x2a-nToeltrahydroperfluoro- CH2OHCH2(CF2)5CF3 27-34 11-,1O,2c,t2an-Toel trahydroperfluoro- CH2OHCH2(CF2)7CF3 29-34 1111,,--11DD,,22eo,,cd22ae--ncTToaeelnttroraalhhyyddrrooppeerrfflluuoorroo-- CH2OHCH2(CF2)9CF3 CH2OHCH2(CF2)11CF3 17-21 6-9 11,-1te,2tr,a2d-Teceatrnaohlydroperfluoro- CH2OHCH2(CF2)i3CF3 2-5 11,-1H,2e,x2a-dTeectaranhoyldroperfluoro- CH2OHCH2(CF2)isCF3 1-2 1-Octadecanol CAovneer. a(g%e ) 1.5 30.5 31.5 19 7.5 3.5 1.5 2.10 Perfluorooctanoic Acid (PFOA) Absorption Study tAeshtxunepdpeiynrridohmepopeewnentnsmsidteueyxnciahtnmsPwyiFsnhtOeiecdmAhthwPceaFanaOsbbbAseuoimtrlrptaattniyooscfnseoteurnrfddefyidecnPifesrFeonOmcinyAttohhaefebPsgtFoearsOsptpAtsihyoaisnnst.eetomTtoa.hqteuhpeeuoaruqpsuosesooeluuostfisotohnleuaatnibodsnos.orpuTtghiohisnt tstoeestetoxwafmasintoe 2.10.1 PFOA Absorption Study Figure 2.18 shows a schematic ofthe PFOA absorption study apparatus. PFOA was weighed and placed iOnxtofoards,amPApl)e, wcohnictahinwears(2axls2o.5wmemigh(ei.dd.pXroio.dr.)to, 2s5ammpmlelelonagdtihngq.uaTrthzecsaapmilplalreyctounbtea,inCeDr SwaAsnpallaycteicdailnItnoc.a, hmeLatginlagstsujbaers(,4exa6chmcmon(tLacinLixnog.d6.)0, 2m0LcHmPlLenCgtghr)a.dTe wheaateqru(eHouPsLCabGsorrapdteioUnlstyraspteumrecWonasteisrt,eSdtoocfktw#o22192304, Lot #L10N39, Alfa Aeser, W ard Hill, MA). Silcosteel tubing (1/8 in) (RESTEC Co., Bellefonte, PA) hmawhfeeaLtlaesd/trmeuahdsitenef2adrt0foila0nmosgwC.arortfTaoroathmerne5satmefnmemdorilpnlbaie.unrrbeaaTbmtbhuleeeorteduwvnttaeohtperoono1rf7utiP0hgzFeehCdOhthPweAeaFitatOaihnvqAgauaietlwtouaebubamslseepssaefownroladeurtptuabitborueusnbos.rbiarnlpTmegtrhip.oceinanTsrgawhrmiereaarpshtelfecelaaootclwifconaung(plstaptayutirennbodteexhrfiearmwtoniacmadtsaettriwlhray)ene2iasdg5ftiehf1rCfe9edl/.irm2neaengincaweiananisnd wcaelciguhlattbeetfhoereabasnodrpaftitoenr heefafitciniegn.cyT.his amount was compared to PFOA determined in aqueous solutions to 18 The heating tube and Silcosteel (RESTEC Co., Bellefonte, PA) transfer line were rinsed with 60 mL HcoPnLdCengseraddoenwhaetaetrin(Ag ltfuabAe easnedr)traanndsfceorllliencetewdailnlsto. jar 3. This was to facilitate capture of PFOA PEFacOhAaqdueeteorumsisnaamtiopnli.ngTjhaer rwesauslltasboeflethde, sseecsutureddie,sanardesseunmt tmoaErixzyegdeinnwSietchtiaocnh3a.i8n. of custody form for Exhaust Line Figure 2.18 Schematic for PFOA Absorption Test. 2.11 PFOA Transport Studies Icnonodrducetretdo. eFviarlsuta, tPeFtOheAtrianntshpeoArtToRfPSFeOffAluethnrtowuagshstahme AplTedRiSn, atwnoaqinudeeopuesnsdoelunttioexnpbeuribmbelenrtssywseterme for HGPCL/MCS/MaSn/aMlySsisa.nalysis. Second, PFOA in the ATRS effluent was sampled and analyzed using in-line 2.11.1 PFOA TransportStudy - Aqueous Sampling tfTaeonwmrdotphaetneeraassltteysucsrwoeensetdordeetpescrscoetrnviwbdeeanudstcts3iean0dm0SupesClcien.tigcoAontnhll2de.te5rsna.ansmaTstfehieoeArntlTeianRmneSdsp,edsrreeeatcatuoucpmrtoeuprfs,ooeasrdinttfdihooecnrof.PilrFdTsOtthrteAaepsi,ntfwjwleuecaortseriiomd1n7eap,0ioanCnrttad,siancwneheddlortaerhtikedtehetpeesmtasamaptmep1rel7aint0ugrCe for both 170 and 300C transport tests. The sample was placed into a sample cartridge (2 x 2.5 mm Asfi(nrhio.TsodmeRw.rxStnoe1.d0eidn0fi.f)nFl,Ctuio1get2nuIon.tr5el1wem72ta0.ms11pC5ul.aseasinnTstgegththdehtehttqherruaarpotaneyurstrfgozoehfprc7tralwoi0pnbioelCelaa/a(qmr1nyu2identuoignabuanesssd,iisflCoiihcelDeodulnStdaieotA1nt17un7b0ba0uilCnybCgtbif.clo(ea0rTrl.s40hI6cnemo3cpni.,niynnOregoicxi.pdtvfero.io,dnrb0dgie.n,1aPt2setAe5omrt)iiapenalesnrootad.ofdtut5.ch,romeeCllciwoenalca.ertstrTPPiidanhFrgceOmreeAearsaesd Co., Vernon Hills, IL)), was rinsed with 5 mL HPLC grade water (HPLC Grade Ultrapure Water, Stock #22934, Lot #L10N39, Alfa Aeser, Ward Hill, MA), and added to Jar 1. pAcoefrltlfeeorcrPtmeFdeOdfrAtoomweaxthstrecaocAtlTlaeRncytSepdeoxisnhsaitbhulesetaPlqinFueOeoaAunsdcsoconoldnuedtineosnnasstee,dareilnmotwoaitpnwrineosgsgiulnarsetshsevteiAaalmTsR(e4Sx0tsrmaycsLtteioVmni.aplTr,ohAceemdsbtueerarem, wWwahsaesaton, Mfolillolvwililneg, NprJo)cwedhuicrhe wwaesreucsoednnfeocrtsetdeainmseexriterascatinodni.mmersed in an ice bath as shown in Figure 2.19. The 19 ssgTytehernaeienmerganeettexiprdtuerbamAcyptTiionR(MnjSe.cost5dyioesmnlteL1tmo0o1i(f,niHnKlelPedttL1,SCrhceieageacrnttaetodidfrei,cttworIana3ntc0es.0,rpHo(CAro.tlllfliTianshetAoe,enass,nyeMdrri)ncAwgo)eladaspntuirdnmajpaep)c5twwemdaassLinuhstseyoeardtiienntdlgoeettio.n13jSue0tcse0itanwmCgaawpterarisoart to a icnonthsetaincterabtaet.h.The steam was collected as condensate using two 40 mL vials which were placed The steam injection flow rate was limited to 200 mL/min at 300C. Five mL of HPLC grade water (Alfa taAscehtnoxeeendtasrrneaamaercdw)cteditwaoxsesntdatrhnsapteoocritnoAvivjcoieiTesnacdiRltbpueS1lrdre.oeeaccVxwetohidanaaausdlruraep1estnetewtsrloaofianotmfsiero4msenaeamneaisdndLluerft/tdhehhiveirwtse,hfigvetitirehimsaantmlaee.vlrsuoiaFamuctolionnilwntnlgosouaewm1sfc7wiurn4fitanogimvtsieleee,Lradllycc/amw.hobneiisVntdltheeiesada5ntl,mesma1aemdneLw.xdatfHVsrlsaoePiwcnwaLttleiCtot2ihognrgwh,Eoretaauxhdsdgyeebhgnseeowtiflhntoiaecwwrtoeeseinrytiaehgs(nAthtdaeuelmbfcadahfi.nbtaAeTegirnechtsaheoeuerfs)e HcuPsLtoCdywfaotremr infojercPtFedOtAhrdoeutgehrmthineastyiorinn.geAwHePreLaClsgorapdroevwidaetedrf(oArlbfaacAkegsreoru)nbdlaPnFkOaAnddeatesermcoinnadtbiolann. k of lsTgatrhubaededliepeeydswr,aoaarptenerdrosu(bsAmeenlmuftastaeoArdiEzetesoxedyrhg)ion.elndSTewthhciiesttihowsnaaam3tce.ph9rla.es1iancmaorpftrlceiudwsgteaosdfopyrlafgocaresmdifiifncoaratPigoFlnaOswsAajasdrea,tlesseromarliienndsaewtidoitnuh.sianTlughme1i0rne0usummltLsfoHoilfP, tLhCese 4 0 mL Vials Figure 2.19 Schematic for PFOA Steam Extraction of the ATRS. 20 2.11.2 PFOA Transport Study - Gas Phase Sampling Solid PFOA samples were obtained from Oakwood Products, Inc. (West Columbia, SC, Lot No.: 210002) bPPGeFFClOOo/MwAA.Stirnaajnneacsltpyioosrnits.ienfOtfoicptieherenactGiyoCwn/aMalscSdowentdietirhtmioPinnFseOfdoAbryitnhcterosomedptuwacrtoiionsngtuitdnhiteeostoIwntaleelrtPe1FidOoefAntthiiecoanAl pTaenRadSkafaroereldlaoeowsbcetrdaibibneyeddiinnb-yldiendteiarielct For the ATRS tests, the temperature (inlets, transport lines, reactor and the cold trap) were set at 235C. pmiwtS1nyy1yaicprnnsrmeo.etsphaoLtAresaf/oetrmfsibtdtcaeeeimdtnarot.iegptro2maTlwe8sihpi0nacfeesliorecCGnautattsCt2auaie)otirdnietntnheoa,wiresttmiahuarcseasalaetiitrsennderytimcofsaerotfirpeenr2agemt0strahhaesweetd.Cuapsr/fTsmrearheomswivemwnpiatoelaos1eupnt0ssartd0eelwsthsfttioaileudtotldhed3w4yn0H0fcr0(oeaseCretCfte5eioamwarSmnte3eaditcsnhimhtnseiaeoiettlnrhntda2eaat28fetnor.013edora30Cft1c.h21m.tmeo0)Lr0iGwn/amC.aCtsi2T/tnmuehsms(eiee2ncpd2taeeatmrnmtoad2tLplu3ohe/r5maereadlidCptnuPr.aroFtetogOT3wrihaA0naem0l.sesmtCaTm1ihnfaeoegnrd2 rut2Fwea3somate5ersdptuaChefsloer.seaorddtTtui3hfhrro3eeeercnmpwttyhtLGahreso/eCmAptGhriiTneonCRnj.beeStciTentsmthicaeoermspnetesasptar.selameestdtupgsrt,laeoeHspiw2fer3iaocw5sgaatriCinasomtunraos,mtedwadiunhrcaagiesltewdethtoiahnesfetoacsiptantarphjrrerteioeceGtdxriiofCumlnsoaiiwpnnteojgealrytcnthtdw2ieo0tasnhsaCepmk/ofemelrpottitwenuamsratiannp4tgde0erhttaChheteur.lodrseTuafgphomherropti1lghnermejaecimicanntrmijtaoerticindntogpgerort pTSeehacektiPoaFnrOe3aA.s9w.t2oa.tsaluisoend cahsrtohme aPtFogOrAamtrpaenaskpoarrteeafsfifcoirenthcey ttwhroomugehthtohdesAwTeRreS.inTtehgerarteesdu,ltasnadrethseurmatmioaorifzethdein AIES Figure 2.20 Schematic of PFOA Transport Efficiency Test Through the ATRS System. 21 Cartridge in Figure 2.21 Schematic of PFOA Direct Injection to GC Injection Port 2.12 PFOA Calibration Curve and Detection Limit Study wTchhirtiohsmsstaaumtdoeygrewaxmapse, rcqioumnaednnutitcfaytlepPdrFtooOceiAddeuinrfetiitfuyissethfdoerfmaocrettudha,elasrneadmtednpetltieeorcnmotmiinmbeeutshotefioPPnFFtOOesAAts.idnTetthehecetsiGaomCn /plMilmeSictotuonsttaianlignioetnrhe ATRS (2 x 2.5 mm (i.d.xo.d.), 12.5 mm length quartz tubing, CDS Analytical Inc., Oxford, MA) was loaded with 1,5,10,50, and 100 xg PFOA. To load these minute amounts of PFOA, three PFOA solutions with dsuifmfemreanrtizceodnicnenTtarabtlieon2s.7w. eTreheprreepsualrtesdaares sshuomwmnairnizTedabilneS2e.7c.tiTonhe3p.1r0e.paration conditions are also Table 2.7 Solution Concentration (PFOA in Methanol) and Dried Sample Mass (pg) L1UUUSVoVlu-Mtion Used (Concentration) (mg PFOA/mL ------r-Sao-l-u--ti-o--n-----Loaded (|il) Dryi(nhgr)Time 1510 15000 MeOH1) 11 1110000 511 51 135 1335 MeOH: Methanol t2tTafhhot0heer20er39ceACo.ma4lT/cdmimRtnotiTrSnra.T,/pamahitnntei2odlnegs2ht(aes18es,c90litdfa.ri6aCteand3mt.s03TTPp00hFo./0merOCtGiC.AlniTnCftwehoocsear,ois2pnancylnmdeorditontiin1rpdoereatnaoonnscbsdtgweeoa9drtese.rti8ameeftymmtpthPhepLeeFre/aOsrmctaaouAtimurlnde.reteAtwoasrafsaiwtpnsethleriaerengntecaad2rssc)ereitaeftutoislacaeelamtadtc3siafoeo0irdmn0no,tfmbaCotuihrn.1seiTt0anis0oh-yslneatsionmttteoee3mpstG0atlsel0wCgiran/CeaMsssSiasSdfetwlecoabntewiyrpcoaethnwtweet2aiaimo.stt4ihfsen.1eHgi.tne In order to determine if PFOA was lost during solvent evaporation (drying), similarly prepared 500[ig rseammapilneesdwdeurreinwgedigrhyeindgb.eTfohries acna.d 1a0ft%erddirfyfeinregn. cRe eissuwltisthsihnotwheedunthcaetrtmaionrteytohfatnh9e0a%naolyfttihcaelPbFaOlaAnce used for the weight measurements. 22 2.13 Test Matrix and Quality Assurance Procedures A thermal decomposition profile for each sample was generated from 600C to T99.9. A blank analysis wtceamarsrpypeoervrafetourrrwmeawesdiotbhbesafeoirrrve(efdeo,arctrhheeaccroetmoarcbtauossrsteaiomsnsbetlmeysbatlntyod, ectrxoaalpdm)tiarnanepd,aHannyedc(fGaorCrryGcoCovleucrmoflrnuommwnap)sraecnvlediaoanuessdetecasottnsed.lebIvlfaaatnenkdyanalysis wpearsfopremrfeodrmuseidn.gTthhee csalemaneipnrgocperodcuerses, bwuatswciothnotiuntuseadmupnlteilinnosecratirorny.ovUepr ownascoombspelrevtieodn. oBfltahnekrmruanls were dwsaeemcroepmldipnetogesraimtnidoinnaenpdarofloyfisllleeosswwfionergreeaapcdehirsfscoaurmmsspieolden,inbteetmtrwippeeliercnaatUtuerDeastRttIhoeapnsedprfeDocruimfPieoCdnOtt.e,mCCpOOe2,ra,CtfuOlur2eo,.rfildTueho,eraidtneeds,tPamFndaOtPrAiFcaeOnsAaalryeses shown below. (1) IAnl-llitnhereGeCsa/MmpSleAsn, aulnytsriesa:ted and treated articles, and fluorinated acrylic polymer were analyzed using the in-line GC/MS system at temperatures from 600C to T99.9 at 50C increments. (2) VUOntCre,aCteOd aanndd tCre0a2teAdnaarltyicsleess: were analyzed using off-line GC/MS for VOC and GC/TCD for CO (3) PUanFndOtrCAea0,tFe2dlautaotnhrdiedtesrpeaaentcdeidfCieahdrltoitcerlmiedspeewAraentrauelryeassni.sa:lyzed using ion chromatography and HPLC/MS/MS for PFOA, fluoride, and chloride at specified temperatures. (4) Aiii))ddXTiteiPolSonmaAlenSratBluydsAyislc: oShaomlpAlenaclayrstirsid: gTeeluosmederfoBrAtrelcaotehdolarctoicmlebucsotmiobnuastti2o0n0. and 600C. vviivii)i))) PPPPFFFFOOOOAAAAATCSrabtaelsniaobsmrrppaottEiirooxtnntTraTeCcseuttsiraotvtnaet1aa71tn073d0a0Dn0Cde.Ct3e0ct0ioCn.Limit Study at 300C 2.14 Quality Assurance Narrative Statement This program involved conducting thermal decomposition tests on a fluorinated acrylic polymer, an htiasenpracctenihoccdnrlileapiiqnlotiurgzreaeeoastdetf,weddndeiaonrwtneatoi-ptfshputealrrtlnifhyooderrcampEordonPelfdaAyonmw-raamelipytrehp,tdiractohtnaovedleAtaadepnNcQphuSrnuonIia/ptqAlrriuetiSeayaQsttAeeuCdAsssaeESurd4tTriafcMrrnleieclqleoypurPridorUreevomvSijed-eeElecnodtPtpPsAbel(dyaAsnSDtSasOunQ(PdPU,aosS1rnwd9-tE.9hm4PiAce)A.htlh,Alho2alad0nlvs0aae.l0nyb)aAs.leiynsesynaisnd 1. Study Design: The overall study design is described in Section 2 of this report. 2. ESaPmApQleuHalaitnydAlinssguarnandcCeuPsrtoogdrya:mCPhlaainnso(fQcAuPstPosd)ywperorecefodlulroewsepdredvuiroiunsglythdisevperloogpreadmu. nAdellrsUaSm-ples wsaemreplceosm, ipnocslueddiongf paunrychhaaszeadrdcohuesmcihceamlsiocaflksn, owwernepruecrietiyvoedr,salambpelleeds parnodvliodgegdebdy, wDiutPhohnatz.aArdlolus mremateorviaeldsfprloamcesdtoinratogeaepxrcee-epxtiasstilnagbeHleadzaprrdeopuasreMdastaemriapllsesHfaonrdilminmgeFdaicaitleitsyt.udSya.mples were not 3. Sample Analysis: Only samples ofknown purity were purchased. All analysis techniques were performed in compliance with appropriate standard methods. Any specialized, non-standard 23 analytical techniques have fully developed SOPs that were followed and which have been incorporated into prior EPA-approved QAPPs. 4. mCaelaisburaretimonenatnadnPdearnfoarlmytaicnacleeAquniaplmyseinstoufsSeadminpltihnigs parnodgAranmalayrteiccaol mMmetehrocdiasl:lyAalvlaoilfatbhlee and csaamlibprlaetsewd aasndpemrfaoirnmtaeindeudsiinngacecstoarbdlainshceedwGitCh/tMheSmmaentuhfoadcstuinrecrl'usdSinOgPtsh.eQuusaenotiftacteirvteifiaendaliynsteisrnoafl standards as needed. 5. ATRS Operation: Known amounts of the samples were gasified with 85% excess air. The mean gas-phase residence time in the reactor was maintained at 2 sec. The reactor and transport line temperature and carrier flow rate were monitored and logged before and after the experiments. The reactor temperature was kept within 1C of the set temperature for most cases and 2C for few cases. The flow rate was kept within 0.2 mL/min ofthe set flow for all cases. 6. rDqeuadatualictReydewddeuarcteati.coanSltcaaunnlddataRerdedpfdoreorvtmiinagltii:noenTasar,broleergsnroeosnfslciionalneiabcrroareetifgofrinceisdesanitotasn,waaennradelyofsuthersenriossfhtdeadtai,tsata.ilcoaAnllgml wdeaaittsahuargerresaposuhfbsdjoaetfcat to internal review by the project leader 7. tIoahnirretgeoatnenfdminecopdpelUrrooawsdteuuerocretftshrtehtaoqneuaD8inr5ae%etdaq:.tuoTiTvhdhaeelesedtdnraotatatylaeavtghleseelonwpeparirratoehtvenaidtdmmiendeattaghenuirsiieadxslatpuwnodcisyetuharweasenttrioeemftufehisecoeiidfed2nteocnsyepticorfoifacv>naitd9di9oea.ng9leuo%vifdeoaalnrnogdcafeaneliaxlcscetoss products and the temperature required to destroy them. 8. E>ab9vi9alil.9tuy%attiooandnedoteafrltlmhoeirnSgeautnchicecestpesrmoodpfuethcratestuPtorreoajrenecqetu:qiurTievhdaetloesundcteclseetvsroselyowfthtihtehepaparrmeonejeatcnmtewaxtieplrloibasluewrienittdihimcaaenteoedfff2bicysieeocnucaryndofa level of excess air of no lower than 85%. 9. bRcoyemvthimeewopnsroopjrfeatcchtteilceSeatdufeodrryaePnxldtaenhr:insaTlrehrseeevasiterucwdhybteypaltmahnewasniptdhointnhseothrp'esroEtpencovhsienrodicnaamnl aerelnypttarilecEsaelnnmgtaienttiehveoerdionsrgwdGeesrreiogupnprae.tpeItadrised alternate. 1 24 3. Experimental Results 3.1 In-line GC/MS Analysis and 99.9% Destruction Temperature Determination Thermal decomposition profiles for the untreated and treated articles and fluorinated acrylic polymer wexetrreacgteendeiroantecdhurosimngatothgeraAmTsRaSt ewaicthh tienm-lipneeraGtuCre/MfoSraenaaclhyssiasm. pTlheeatrheeprrmesaelndteecdoimnpthoissitsieocntiporno.fiRleaawnddata for all experiments are presented in Appendix A. 3.1.1 Untreated Article Ions 122 (benzoic acid) and 149 (terephthalic acid derivative), which are the major ions of the untreated article at the temperature of complete gasification, were used to determine the thermal decomposition profile. Table 3.1 shows total ion counts and summation of ions 122 and 149. Both ions disappear at 725 and 700C, respectively. The analysis was repeated at 750C to ensure complete sample destruction. The rtFccoeoaistglmapculuepricleooatsuitnven3dced.2ol.syuTa.w9nn9teId.s9orewn3ws.ne3aor1sest2ohr2aobelasfwtaoonirdennmxeo1tedrr4dma9acatawtt7leihed2zri5eigeodhCanbels.syro1tFge2eiamg2xsuptiarfrenaierecdad3tte.1us1d4rae9sfm.ohfporoFlwcreiogtsmhmuterhabeseuus3nsd.atte4rinoegsdanrhatteaodhdtwaet1asir0roett0lnhiac0eptlierrCvoeeasfttiuodl6leete0gson.0rsfa,uOtd6hra5neet0lityuo,h7nnaa0ttwrb0etaha,acsetakesnedgdrao7rut2in5cdleC. , signal was observed, and there is no indication ofreformation of these compounds. Temp (C) 776620055000 775500 Table 3.1 Ion 122 421...538312EEE+++000887 000...000000EEE+++000000 Major Ion Ion 149 4001....40030081EEEE++++O000Q760 0O..0O0OEE++O0O0 Counts of the Untreated Article. Total Mass (mg) NBorymMalaiszsed 241...758633EEE+++000887 O00...00O00OEEE+++O00O00 111...100112 011...900704 21..4881EE++0088 4000....40004000EEEE++++00000070 Relative % 100 71207...908560 00..0000 25 Untreated Article Temperature (C ) Figure 3.1 Untreated Article Thermal Destruction Profile Normalized by Sample Mass. A bundance *1sooooooooooo 600000 -4-00000 200000o I o n *12 2 . 0 0 (1 21 . 7 0 t o 1 2 2 . 7 0 ) : U T 6 0 - 2 . D 600C A bundance *1oooooo 800000 600000 400000 200000 T im e --> A bundance I o n *122.00 (1 2 1 .TO t o 1 2 2 . 7 0 ) ; U T 6 5 --2 . D ! -,..............,, ..... ...,-....................,-..-.,-...,-..-.,.-..-....i-AK -LV'* 5 ,0 0 1 0 .0 0 -| 5 . 0 0 2 0 .0 0 2 5 .0 0 V| I . I I 3 0 .0 0 3 5 .0 0 650C 700C *1OOOOOO 800000 600000 O-240-000000000 l o o *122.00 <12*1 .TO t o 1 2 2 . 7 0 ) : U T 7 0 - 3 . D TOpDWKti 725C 1 OOOOOO 800000 600000 O-240000000000 Io n *122.00 ( 1 2 1 . 7 0 t o 1 2 2 . 7 0 ) : |_|T"7'3.0 Figure 3.2 Extracted Ion 122 (benzoic acid) for Untreated Article at 600,650,700, and 725C. 26 Abundance 400000 320000000000 1OOOOO O Ion 143.00 (148.70 to 149.70): UT60-2.D 5.00 *10.00 15.00 20.00 25.00 30.00 35.00 400000 230000000000 -I OOOOO O- Ion 149.00 <148.70 to 149.70): UT65.D 5.00 10.00 15.00 20.00 25.00 30.00 35.00 400000 300000 200000 o1OOOOO lor-1149.00 <1*43.70 to 1*49.70): UT70-3.D 400000 300000 200000 O1OOOOO loo 1-49.00 (148.70 to 1-49.70): UT73.D 600C 650C 700C 725C Figure 3.3 Extracted Ion 1496(0t0er,6p5h0th,7a0li0c,acainddd7e2ri5vaCti.ve) for Untreated Article at Ion 122 Tim e-- Ion 149 900 800 700 600 500 -400 O23 00 00 lOO Figure 3.4 Extracted IUonnt1re2a2t(ebdeAnzrotiiccleacCido)mabnuds1ti4o9n(atet r1e0p0h0thCa.lic acid derivative) for 27 3.1.2 Treated Article Ions 122 and 149 were also used to determine the thermal decomposition profile of the treated article. Table 3.2 shows total ion counts and a summation of ions 122 and 149. Ions 122 and 149 disappear at . 7Ta9n09d0.93aw.n7adss7ho2ob5wtaCitnh,eerdeesxaptter7ca2tci5tveedClyi.o. nFTsigh1ue2r2aena3an.l5ydss1ihs4o9wwfasostrhrteehpedeeatrgteeradatdeaadtt7iao5rnt0icpClreotfaoitle6en0os0fu,tr6hee5c0tor,em7a0pt0eled,taeanrstdaicm7le2p.5leFCdig,eustrreusc3ti.o6n. rooeCbtshsFpeee2rrcCvftleiFuvdoCeerlFiyvn2.ea)ntIewoadntessr7ep2feo5acrlsiCfeols,uebfoxruratitrgnatmahctteeeednadtmsawpnoeaducsniaeotrsebwfssarehasrogvvwmeedrneynfiotnssrmFt(ah6igle9lu.tfrroeIeorsant*3esC.d81F,a133r9,.t19iac1,nl9eadnfco1do3rm31.b1Cwu0Fes,2trrCieeoFsnd3pe,teseactsnrttiod.vye1Ielo3dyn1.asftIo1o7r2n2256a9Cnwd. aN1s4o9 were extracted for the combustion at 1000C to ensure these compounds were not reformed at higher temperature. Figure 3.11 shows the results. Only a background signal was observed. Temp ( C ) 766005000 777255500 Table 3.2 Major Ion Ion 122 Ion 149 2.80E+08 2001....03040809EEEE++++00008006 0.00E+00 056O....041O035OEEEE++++OQ00O760 OO..OOOOEE++OOOO Counts Total ofMthaesTs (rmeagt)edNAboryrtmicMalela.iszsed 321...344449EEE+++000886 000...000000EEE+++000000 11111.....2222253224 1.23 2O11....O792452OEEEE++++O000O886 00..0000EE++0000 Relative % 711.2070 0000....40005000 Treated Article Temperature (C ) Figure 3.5 Treated Article Thermal Destruction Profile Normalized by Sample Mass. 28 Abundance 600C 650C A bundance 1200000] 1OOOOOO 800000 600000 420000000000 Tim e--> A bundance 11200000000000 800000 600000 400000 200000 loo 122.00 (121 .T'O to 122.70): TR70.D ' 5.OO 10.00 -15.00 20.00 2 5 .0 0 30.00 Ion 122.00 <121 .*70 to 122.70): TR73.D 35.00 5.00 10.00 15.00 20.00 2 5 . OO 30.00 35.00 700C 725C Figure 3.6 Extracted Ion 122 (benzoic acid) for Treated Article at 600,650,700, and 725C. -OOOOO 300000 O200000 1OOOOO T i m a --> A bundance 400000 1OOOOO-300000 200000 Time--> Abundance 400000 300000 200000 O1OOOOO Son 149.00 (148.70 to 149.70): TR60-2.D -A 5,00 Ion 149.00 (148.70 to 149.70): TR6S.D 10.00 IS.OO 20.00 25. OO ^ 30.00 35.00 Ion 149.00 (148.70 to 149.70): TR70.D 400000 300000 200000 O1OOOOO Ion 149.00 (148.70 to 149.70): TR73.D 600C 650C 700C 725C Figure 3.7 Extracted 149 6(t0e0rp,6h5th0a,7li0c0a, cainddd7e2ri5vaCti.ve) for Treated Article at 29 A bundance aoooo 60000 40000 20000 80000 60000 40000 20000 Io n 6 0 .0 0 (6 8 .7 0 to 6 0 . TO): T R 6 0 - 2 .D .OO LjIMidlUi. Voloo 1 s !oO 2 0 loo 2 5 .0 0 3 0 .0 0 Ion 6 0 .0 0 < 6 8 .7 0 to 6 9 .7 0 ) : T R 6 5 .D 3 6 .0 0 600C 650C 5 .0 0 1 0 .0 0 1 8 .0 0 2 0 .0 0 2 8 .0 0 3 0 .0 0 Ion 6 0 .0 0 < 6 6 .7 0 to 6 9 .7 0 ) : T R 7 0 .D 3 8 .0 0 700C 80000 60000 40000 O2 0 0 0 0 i c< 80000 5 .0 0 , 1 0 .0 0 1 8 .0 0 2 0 .0 0 28-0 0 3 0 .0 0 Jon 6 0 . 0 0 < 6 8 .7 0 to 6 8 . 7 0 ) : T R 7 3 . D 3 8 .0 0 725C 60000 40000 20000 T im e --=> l | I""I- I".'!-- T".T.-,".-rA'M"t'l ! I l V 1'|"..T -p-- ,--l l l | ' 1 0 .0 0 1 8 .0 0 2 0 .0 0 2 8 .0 0 3 0 .0 0 3 8 .0 0 Figure 3.8 Extracted Ion Count 69 ("CFs) for Treated Article at 600,650,700, and 725C. AO u n d a n c e 1800002 8 0 0 0 0 200000 8 0 0 0 01 OOOOO Io n 1 1 9 .0 0 < 1 1 8 .7 0 to 1 1 9 .7 0 ) : T R 8 0 -2 .D 8 .0 0 1 0 .0 0 1 8 .0 0 2 0 .0 0 2 8 .0 0 3 0 .0 0 3 8 .0 0 18000022 06 00 00 00 00 1 OOOOO 80000 Ion 1 1 8 .0 0 < 1 1 8 .7 0 to 1 1 8 .7 0 ) : T R 8 6 .D 5.00 1 0 .0 0 1 8 .0 0 2 0 .0 0 2 5 .0 0 3 0 .0 0 3 5 .0 0 22 50 00 00 00 00 150000 1 OOOOO 50000 A b u n d a n cs 250000 200000 150000 O1 OOOOO 50000 Io n 1 1 8 . OO < 1 1 8 .7 0 to 1 1 8 . 7 0 ) : T R 7 0 .D 5 .0 0 1 0 .0 0 1 8 .0 0 2 0 .0 0 2 5 .0 0 3 0 .0 0 3 8 .0 0 Io n 1 1 8 .0 0 < 1 1 8 .7 0 to 1 1 8 .7 0 ) : T R 7 3 .D 5.OO ' 1 o l o o I S Too 2 0 .0 0 2 5 .0 0 3 0 .0 0 3 5 .0 0 600C 650C 700C 725C Figure 3.9 Extracted Ion 119 (CFaCFj) for Treated Article at 600,650,700, and 725C. 30 A fc>u n d a n e e 600C 650C 300000 22 06 00 00 00 00 11 SoOoOoOoOo 50000 lor* 1 3 *1 .0 0 <1 3 0 . TO to 1 3 1 . 7 0 ) : T R 7 0 . D _r_ 5 .0 0 1 0 .0 0 _r_ 1 5 .0 0 2 0 .0 0 --r* 2 5 .0 0 _T_ 3 0 .0 0 3 5 .0 0 700C 300000 250000 200000 150000 1 OOOOO 50000 Time--= Io n 13 1 .OO < 1 3 0 .TO to 131 . 7 0 ) : T R 7 3 . D 725C 1 0 .0 0 1 5 .0 0 2 0 .0 0 2 5 .0 0 3 0 .0 0 3 5 .0 0 Figure 3.10 Extracted Ion 131 (CFaCFK Ty for Treated Article at 600,650,700, and 725C. i^a.7-o>: *rm oo-i .o Ion 149 Figure 3 .ll Extracted IoTnre1a2t2ed(bAenrtziocliec Cacoidm)baunsdtio1n49at(t1e0re0p0hCth.alic acid derivative) for 31 3.1.3 Fluorinated Acrylic Polymer Ions 69 (*CF3) and 77 (CF2CH=CH2), which are the major ions from the gasification of the fluorinated acrylic polymer, were used to determine the thermal decomposition profile. Table 3.3 shows total ion counts and a summation of ions 69 and 77. Ions 69 and 77 still exist at 1000C, but the relative amount iroemn caoinuinntgs iws e<r0e.1a%lso. nTohremaanliazleydsibsywgaassriefipeedatseadmaptle10m0a0ssCatnoderneslautrieve99d.e9g%rasdaamtiopnlerdateestwruacsticoanlc. uTlahteedt.otal pT9o9l.y9mwears, oanbdtaFiniegduraets130.0103aCn.dF3ig.1u4resh3o.1w2 tshheowexstrthaceteddegIroanda6t9ioant plorwofi(l6e0o0f~th8e0f0luCor)inaantdedhiagchry(8li5c0 ~ 1000C) temperatures, respectively. Figures 3.15 and 3.16 show the extracted ion 77 (*CF2CH=CH2) at low and high temperatures, respectively. Figures 3.17 and 3.18 show extracted ion 119 (*CF2CF3) at low aanndd h1i6g9h(teCmF2pCerFa2tuCrFe3s),,rreessppeeccttiivveellyy.. FAiglluiroenss3c.1o9rraenspdo3n.d20toshthoewfltuhoereinxatrtaecdtceodmiopnosun13d1, w(iCthFt2hCeF=CF2) exception that ion 69 (*CF3) is relatively small compared to ion 77(*CF2CH=CH2), and these ions are negligible at combustion temperatures over 800C. Temp ( C ) 776688055050000000 1990500,000 11000000 Table 3.3 M ajor Ion Counts of Fluorinated Acrylic Polymers. Ion 69 Ion 77 Total Mass (mg) NboyrmMalaiszsed 46381111........7822140190931424EEEEEEEE++++++++0000000078898989 421...411323EEE+++000566 2.08E+09 427351111.........624611455245135404EEEEEEEEE+++++++++000000000866977666 1.08E+06 231...352615EEE+++000999 24863531........0629322168756519EEEEEEEE++++++++0000000068887686 1.60 1111....66669382 111111......666556113882 2.20E+09 47521.....2410463070EEEEE+++++0000088889 731...336206EEE+++000776 22..5023EE++0066 Relative % 100.00 32613339....84521184 931...435152 000...100189 32 100 C-S--- 1---i--* .......--- !--- !--- !--- !--- **` ' Fracture R em aining (% ) :; ;. X. :; \ \ ; . .____ i____ ,____ ____ . 1 ... i ____ .. .. , i ......... .-- I 600 700 800 900 1000 Tem perature (C ) Figure 3.12 Fluorinated Acrylic Polymer Thermal Destruction Profile. A bundanc 1 oooooo eooooo Ab undanct -1 O O O O O O 600000 A to u n d a n o o 1 oooooo 600000 A b undone *1O O O O O O 600000 A b undance *1 O O O O O O 600000 lor 6 9 . 0 0 < 6 6 . 7 0 t o 6 9 . T O ) : P M 6 0 - 2 . D i ,o ' i o! o o i s ! oo 20 loo 2 s .o o 30.00 3 s .00 /V ! ^*-- "T-- 3 .0 0 ,-----1 Io n ! y-- I 6 9 .0 0 < 6 8 .7 0 to 6 9.7" O>: P M 6 5 .D i iLi I------1----- , ...rri.nUTy ..r f lir V y - - r r -- -<------ ,-----i---- <------ 1----- 1----- ----- 1----->-- *1 0 .0 0 *1 6 .0 0 2 0 .0 0 2 6 .0 0 3 0 .0 0 3 6 .0 0 lor 6 9 . 0 0 < 6 3 . 7 0 t o 9 . 7 0 ) : P M 7 0 . 0 pm1, , , . i , ,-- S.OO *1 0 .0 0 *1 6 .0 0 2 0 .0 0 A r, , ....................!........-- .-- -- <-- ---- r 2 6 .0 0 3 0 .0 0 3 6 .0 0 lo r 6 9 . 0 0 < 6 6 . 7 0 t o 6 9 . 7 0 >: P M 7 5 . D -,___,___,____,, ____,------ ------ ,-- ,.5t..f--J--------------,----,--------------,----,----,---------,----,---,-- ,---------- 1 0 .0 0 1 5 .0 0 2 0 .0 0 2 6 .0 0 3 0 .0 0 3 6 .0 0 lor 6 9 . 0 0 < 6 3 . 7 0 t o 6 9 . 7 0 > : P M S O . I s .<DO~ 1 o !o O *1SI OO 2 0 lo 'o 2 6 !oO 3 0 . 0 0 3 6 . 0 0 Figure 3.13 Extracted60I0o,n65690,(70C0F,s7)5f0o,raFnlduo8r0i0naCte.d Acrylic Polymer at 600C 650C 700C 750C 800C 33 850C Abundance 44400000 i 230000000000 *ioooooo 4J 400000 320000000000 O*1OOOOO Ion 69.00 (68.TO to 69.70>: F=>IV190.D <~) 35.00 Ion 69.00 <68.7*0 to 69.7*0): FfVI95.0 <~) 44 0 0 0 0 0 43 0 0 0 0 0 200000 -I i oooooo*4 Ion 69.00 <66.70 to 69.70): FMV199-3.0 C*> Figure 3.14 Extracted Ion 69 (CFj) for Fluorinated Acrylic Polymer at 850,900,950, and 1000C. 900C 950C 1000C 600C 650C 4 0 0 0 0 0 0 -i 3000000 2000000 1 oooooo o i o n 7 7 . 0 0 < 7 6 . 7 0 t o 7 7 , 7 0 ) : P M 7 0 . D <*> 700C loloo"1 1s!ob 2 o To O 2 5 Too 3 0 .0 0 3 5 .0 0 4000000 23 00 00 000 0 000 0 -i ioooooo4 Io n 7 7 . 0 0 < 7 6 . 7 0 t o 7 7 . 7 0 ) : FIN/I7S.D <~> 750C 5 .0 0 -10 . 0 0 1 5 .0 0 2 0 .0 0 5.00 3 0 .0 0 3 5 .0 0 4000000: Io n 7 7 . 0 0 < 7 6 . 7 0 to 7 7 . 7 0 ) : F*A/l8Q.O <-> 800C 3000000 2000000 *1OOOOOO- O - Figure 3.15 Extracted Ion60707(,*6C50F2,7C0H0=,7C5H0,2)afnodr 8F0l0uoCri.nated Acrylic Polymer at 34 Abundance *1ooooo 80000 80000 O4200000000 Ion 77.00 (76.70 to 77.70): PM8S.D .trA J u 850C T im e --> A bundance 4OOOOO4 80000 I 60000 I 40000 I 20000 I T im e --> A bundance 1ooooo 80000 60000 O240-0000000 Ion 77 .0 0 <76.70 o 77.70): Frs/I60.D <> --^-1)1!" 1' I1 I' I I 'I*111-- I 1 > 'AI'"I_""LI-- . . .Vlu1~J''.'"I""SPB^I illaa. f^1" 5.00 *10.00 15.00 20.00 25.00 30.00 35.00 lor 77 .0 0 (76.7O to 77.70>: FIV19S.O <-> __ 900C 950C T im e --> A bundance 1000C *1OOOOO 80000 60000 O-240-0000000 T im e --=- Ion 77.00 <*76.7-0 to 77.70): (=>IVI98-3.0 <-> 5.00 lolob . I>t i-^i-- 20.00 25.00 * v -I--'T -v I 30.00 35.00 Figure 3.16 Extracted Ion 7875(0C,9F020C,9H5=0CaHn2d) 1fo0r00FlCuo. rinated Acrylic Polymer at Ab undanci 300000 200000 4 OOOOO T im e --> A to u n d a n c i 300000 200000 *1 O O O O O Ion *11 0 . 0 0 <1 *18.7-0 to "I 1 9 . 7 0 ) : PM 6 0 - 2 . 0 600C 5 .0 0 4 0 .0 0 *1 6 .0 0 2 0 .0 0 Io n *1 4 0 .0 0 < 4 4 8 .7 0 to 2 5 .0 0 3 0 .0 0 4 4 0 .7 0 ): P M 6 5 . 3 5 .0 0 650C I-- --yjTl|ii| "I 1 |..^1SJiVmli ,ffWjii, l' l' |illjm.ii-- !--.p',1I1 1""I 4 0 .0 0 4 6 .0 0 2 0 .0 0 2 5 .0 0 3 0 .0 0 3 5 .0 0 I o n 4 4 0 . 0 0 <4 4 8 . 7 0 t o 4 4 0 . 7 0 ) ? P M 7 0 . 700C A b u n d a n c< 300000 200000 400000 8 .0 0 4 0 .0 0 A- 4 5 .0 0 2 0 .0 0 2 6 .0 0 3 0 .0 0 3 5 .0 0 i o n 4 4 8 . 0 0 <4 4 8 . 7 0 t o 4 4 6 . 7 0 ) ? P M 7 5 . D 750C Awb u n d a n e e 2 0 0 0 0 03 0 0 0 0 0 5 .0 0 4 0 .0 0 4 5 .0 0 2 0 .0 0 2 5 .0 0 3 0 .0 0 3 5 .0 0 I o n 4 4 6 . 0 0 <4 4 8 . 7 0 t o 4 4 6 . 7 0 ) : P M S O . D 800C 4 OOOOO in o n -i 4 nr on 9a n n *an o n Figure 3.17 Extracted I6o0n01,6159(0,C7F020C,7F530),foarndFl8u0o0riCna.ted Acrylic Polymer at 35 A tou n d a n c o 25 0 0 0 20 00 0 *150 0 0 l o o *1*18.0 0 < 1 1 8 . "TO t o 1 1 9 . T O ) : P M 8 5 . D 850C TV A b undanc 25 000 20000 1500 0 1O O O O 50 0 o0 A"*V 'lW y - " Ir A bundanc* 25000 20 0 0 0 15 0 0 0 1O O O O SO OO 1 O loo I s T o O 2 0 l* --oo-- T Olo r 1 1 8 . 0 0 < 1 1 8 . to 25. O O 3 0 ..0-V 0 3-r^* 5jo e. 0 0 1 1 9 .7 0 ) : P M S O .D 10.00 15.00 20.00 .OO 30.00 3 5 .OO 1 8 .0 0 (1 1 8 . 7 0 to 1 1 9 . 7 0 ) : P M 9 S . D T im e -- A bu ndanci 25000 1 5 0 0020000 5.00 10.00 15.00 2 0 .0 0 2 5 .0 0 3 0 .0 0 3 5 .0 0 lo r i 11 8 . 0 0 <11. > .7 0 t o 1 1 9 . 7 0 ) : P M 9 9 - 3 . D 1O O O O 50 0 0 " T i m a ___O * n -i n or o oo o Figure 3.18 Extracted Io8n5101,99(0*0C,F925C0F, 3a)nfdor1F00lu0oCri.nated Acrylic Polymer at Ab undanci 800000 2 0 0 0 0 06 0 0 0 0 0 *4 -0 0 0 0 0 A bund anca 800000 2 0 0 0 0 06 0 0 0 0 0 -4 0 0 0 0 0 A b u n d a n co 800000 2 0 0 0 0 06 0 0 0 0 0 -4 0 0 0 0 0 A b u n d a n co 800000 2 0 0 0 0 06 0 0 0 0 0 -4 0 0 0 0 0 A b u n d ance -2400000000008 0 0 0 0 0 600000 T Olo r 1 3 1 . 0 0 < 1 3 0 . to 1 3 1 .V O ): P M 0 - 2 .D S.oo 10.00 t -P A a| 15.00 2 0.00 25.00 30.00 35.00 5 .0 0 lo r 1 3 1 . 0 0 <1 3 0 .7*0 t o 1 3 1 .70): P M 6 5 . D 1 O .OO .OO ii ut I 20.00 2 5 .OO 30.00 35.00 lor 1 3 1 .0 0 < 1 3 0 .-TO to 1 3 1 .T*O>: PM TO .D 5 .0 0 ______________ ... i, 11. .1. .i ..tl,, 1 0 .0 0 1 5 .0 0 2 0 .0 0 2 5 .0 0 3 0 .0 0 3 5 .0 0 l o r * 1 3 1 . 0 0 <1 3 O .VO t o 1 3 1 . V O } : P M T 5 . D -->------1-------------.---1---1 -i >-- -- ,---r- ----1---1----------1---1----'------'----1---r-"1---*r 1 0 .0 0 1 5 .0 0 2 0 .OO 2 5 .0 0 3 0 .0 0 3 5 .0 0 I o n 1 3 1 . 0 0 <1 3 0 . 7 0 t o 1 3 1 . T O >= P IVI 8 0 . 0 5.00 10.00 15-00 20.00 25.00 3 0 .OO 35.00 900C 950C 1000C 600C 650C 700C 750C 800C Figure 3.19 Extracted Ion601301,6(5C0F,72C00F,=7C50F,2)anfodr8F0l0uoCr.inated Acrylic Polymer at 36 A b undance 1 soooo 1 ooooo soooo T im o--=- A bundance *1 S OO OO 1 OOOOO soooo Abundance 1 SOOOO 1 OOOOO 50000 Abundance 150000 1 OOOOO SOOOO T lm a--=- 'Lr A tounda nce 1 SOOOO 1 OOOOO 50000 io n 1 6 0 . 0 0 (1 6 8 . 7 0 to 1 6 9 . 7 0 ) : P M 6 0 - 2 . D S.O O 1 0 .0 0 IS .O O 2 0 .0 0 2 5 .0 0 3 0 .0 0 3 5 .0 0 l o n 1 6 9 . 0 0 <1 6 S . 7 O t o 1 5 0 . T O ) : P M 6 5 . D 5 .0 0 m 1 0 .0 0 1 5 .0 0 2 0 .0 0 lo n 1 6 9 . 0 0 < 1 6 6 .7 0 to mUy-. 2 5 .0 0 3 0 .0 0 1 6 9 .7 0 ): P M 7 0 . 3 5 -OO n`ay-1 5 .0 0 1--I . . . . 1 0 .0 0 1 5 .0 0 V ~ 1 . ' '--'------1 '-- 2 0 .0 0 2 5 .0 0 3 0 .0 0 3 5 .0 0 lo n 1 5 9 .0 0 < 1 6 6 .7 0 to 1 6 9 .7 0 ) : P M 7 5 .D i----- 1------r - ' | i ' i----- 1------1-----) - r - * - i -- !{ " i " .oO 10.00 15.00 20.00 V " " -| ----- ------ 1----- i------1----- '----- '----- '----- 1------I----- '---- T 25.00 30.00 35.00 lon 169.00 <166.70 to 16 9.70): PMSO.D 600C 650C 700C 750C 800C Figure 3.20 Extracted Ion60106,96(5C0,F720C0F,72C5F0,3)afnodr 8F0lu0oCri.nated Acrylic Polymer at 3.2 Treated & Untreated Articles: PFOA, Fluoride, and Chloride Determination at 1000C wThaes raenaacltyozreedffflourePnFtOfrAom, fcluoomribdues,tiaonndtcehsltosroidfet.heNtroePatFeOdAan,dfluunotrriedaet,eadnadrtcihclleosriadteawteemrepdeertaetcutreedo. fT1h0e00C ndeetteacmtioounnlitmoiftsoamf PpFleOsAg,afsliufioerdidies,taabnudlcahtelodriindeTwabelree31.40.ngR/aLw, 1d0atpagi/nLc,luadnidn4g0thpegr/Lep,orertspperocvtiivdeeldy.byThe Exygen are provided in Appendix B. Fpinrljouevocirtdiidoeenvaaennridaflicychasiltsoiorcindooelofartinhmaeleyptsrryeios(rQforuersitkurCeltashteepmdroaMvritdiecetlhdeobcdoy1mE0bx-u1y0sgt9eio-n1n.2aT-t2h-1eA0a0an0nadlCy1swe0s-e1rw1e7ear-leQso7c-oc1no-dCnudfcuotcertdeflduusoairtniUgdeDflaoRnwIdto canhdlocrihdleo,rirdees.peNctoivdeelyte.ctSaebeleAapmpoeunndtisx oGf fflourodriedtaeila)n. dTchhelodreidteecwtioenreliombistesrwveedr.e T10h0e Jniegt/Lamfoorubnottohffsluamorpidlee gasified is tabulated in Table 3.4 and the analytical results are shown in Appendix B. 37 Table 3.4 Gasified Sample Masses. Sample Name UUnnttrreeaatteedd aarrttiiccllee 2l aannaallyyzzeedd aatt EExxyyggeenn UTrnetareteadteadrtaicrtliecllea3naanlyazlyezdeadt aEtxEyxgyegnen TTTTrrrreeeeaaaatttteeeedddd aaaarrrrttttiiiicccclllleeee 232l aaaannnnaaaallllyyyyzzzzeeeedddd aaaatttt UEUExxDDyyRRggIIeenn Gasified Mass (mg) 2222....15103345 222...644677 2.49 3.3 SIF4 Analysis from Fluorinated Acrylic Polymer Combustion Silicon tetrafluoride (SiF4) is not fonned by sample combustion but through interaction between hydrogen pt3if(fahn8ll.couu2ec5rloo5ryy0gerrlmaasiiitdncohsseeaieoprf1tswi(oec0cHwdloa0ytFmte0iamitm)cohbCrenaupyarn)seli,cdsistrcirolaoieitmtdgphsnuehoepbrtntleeeruytcSessivmtact-tissiscaveo.,htlernoaiatlnc.nhrpytoFdres.eomu,igtgAurherbfugaxeaursthcceesiioeengdstpuistno3petti(n.geftaf2iharuttc3aeeks8atseaen5fatdlndst0rudeaspaoaCimt3erlniil.a.ocno2okauaBw4r)tnam.eestrtcdhSeeaoaomaliaFifuwzcips4SnreeeydctdrFhltreaih4beemcteaywuipsonrpageoentysdaeslsrysgtowo(rimr6bfapaii0stetreteeheo0rdsrdbvcttHseoepoeamFemdmt8eap0fbmfpkeoo0ulrperrasamCertttmhieruo)aaaerantateisoufno.tslrfeund.eTseohftTpxarsriritboh,gnrolmeiahaegtctprtie3tfaeseeld.mmua5dckaolmpiaecroeanairinnrryndraealgt8tFaithuc5eifargdofeturosHrreF formed by combustion reacted with fused silica on the reactor surfaces to form SiF4. A bundance Io n 8 5 .0 0 (8 4 .7 0 to 8 5 .7 0 ): U T 6 0 - 2 .D 600C Time' 4000 O2000 iMtfrM.I.iflilfri 5 .0 0 T0 .0 0 1 5 .0 0 3 5 .0 0 650C 7O0C 6000 4000 O2000 6000 4000 O2000 Io n 8 5 . 0 0 ( 8 4 . 7 0 t o SS.VO> U T 7 3 . D 5 .0 0 1 0 .0 0 1 5 .0 0 2 0 .0 0 2 5 .0 0 3 0 .0 0 3 5 .0 0 Io n 8 5 .0 0 (8 4 .7 0 to 8 5 .7 0 ) : U T 7 5 .D 725C 750C Figure 3.2l Extracted Ion 85 (SiF3) for Untreated Article at 600,650,700,725, and 750C. 38 Faritgiuclreesco3m.2b2uasntidon3.t2e3stsshaotw60th0e, 6in5t0eg,7r0at0e,d7p2e5a,kanardea7s50ofCS,iFre4sepxetcrtaivcteeldy.ioNno85si,gfnoirfiucnatnret aiotend8a5npdetarekawteads observed for these materials, consistent with the low levels of F present in these materials. A ,bunda ne 4000 2000oU* T im e -----: 8 5 .0 0 (8 4 .7 0 to 8 5 .7 0 ): T R 6 0 -2 .D 600C 650C 700C 4000 2000 ndanc Io n eS.OO ( 8 4 . 7 0 t o 8 5 . 7 0 ) : T R T O . ! iMfuJfcltiftm .OO 2 0 .0 0 2 5 .0 0 3 0 .0 0 io n 8 5 .0 0 (8 4 .7 0 to 8 5 .7 0 ): T R 7 5 .D 3 5 .0 0 725C 750C 1 0 .0 0 -15.00 2 0 .0 0 2 5 .0 0 3 0 .0 0 Figure 3.22 Extracted Ion 85 (SiF3) for Treated Article at 600,650,700,725, and 750C. 3000000 2000000 5.00 lor 8 5 . 0 0 <84 .VO t o 8 5 . 7 0 ) : FIVI60-2.D 10 .0 0 *15.00 JL JL 2 0 .0 0 2 5 .0 0 3 0 .0 0 3 5 .0 0 3000000 2000000 *1000000 Io n 8 5 . 0 0 <84.VO t o 8 5 . 7 0 ) : P M 6 S . D 5 .0 0 *10.00 *15.00 2 0 .0 0 2 5 .0 0 3 0 .0 0 3 5 .0 0 3000000 2000000 OlOOOOOO 9RlnDMM3tnc 5 .0 0 jIn /| 11io n 8 5 .0 0 <84.VO to 8 5 .7 0 ): R M V O .O 1 0 .0 0 1 5 .0 0 2 0 .0 0 2 6 .0 0 3 0 .0 0 3 5 .0 0 3000000 2000000 lOOOOOO o SMgpac ia n c a 10*1 8 5 . 0 0 <84.VO t b 8 5 , 7 0 ) : P M V 5 . D 5.00 1 0 .0 0 1 5 .0 0 2 0 .0 0 2 5 .0 0 3 0 .0 0 3000000 2000000 Io n A /V8 5 .0 0 <84.VO to 8 5 .7 0 ) : R M 8 0 .D lOOOOOO 6.00 10.00 5 .0 0 2 0 .0 0 2 5 .0 0 3 0 .0 0 3 5 .0 0 Figure 3.23 Extracted Ion 85 (SiF3) for Fluorinated Acrylic Polymer at 600,650,700,750, and 800C. 600C 650C 700C 750C 800C 39 Ion 8 5 . 0 0 ( 8 4 . 7 0 t o 8 8 . 7 0 ) : *=*/*& 850C 900C 950C 1000C Io n 8 5 .0 0 O t<= JS.T-O): Fl^/IS-3. O 4000000 3000000 2000000 /\ -|O O O O O O .. ^ .. , o[o0 ' -.Too ` ' ZO:<^ lo o 30.00 35.00 Figure 3.24 Extracted Ion 85 (SiF3) for Fluorinated Acrylic Polymer at 850,900,950 and 1000C. NormTaalibzleed3b.5y IMntaesgsrfaoter dthPeeFalkuAorrienaatoefdIoAncr8y5li(cSPiFo3l)ymer. Temperature (C) Peak Area Mass (mg) Peak Area Normalized by Mass 600 650 700 750 800 850 900 950 1000 5.85E+08 9.07E+08 1.51E+09 2.13E+09 3.27E+09 2.43E+09 4.30E+09 4.93E+09 5.28E+09 1.60 1.69 1.68 1.62 1.63 1.62 1.63 1.58 1.61 3.66E+08 5.36E+08 8.98E+08 1.32E+09 2.00E+09 1.50E+09 2.64E+09 3.12E+09 3.28E+09 an 3.5 109 -- 310s -- ------------- r------------- r c o g 2 .5 10s <<0>0 2 10s Q. Na> 1 .5 1 0 s CD zE k. - o 1 10s Q ....... - - 510" > j_______ i 500 600 700 800 _______ -- 900 1000 1100 . Temperature (C) Figure 3.25 Temperature vs. Integrated Normalized Peak Area of Ion 85 (SiF3). 3.4 Treated Article Gasification: XPS Analysis of Pyroprobe Cartridge Tipsfaehtmrehcepesrlnueetrafwcagacaerestorfoifdlfuagtotehor.eimnTseashmouenrpfsatlahecmeecpasclraoetmmr(i1dpp.glo1ees5ciutamisroetgnrd)idofwgboaetrastsirngueearafdstaiefcfdireeoadamrftwtiXceilrtPehpSgysaryaosnniltafyhilscyeiatssit.icisoTafnoiarwrbsloapense3eca.inb6falicaslhyanlozklewycdsafborttyhrrietXdhrgiPeselSasatttuniovddedyoenuteesrimngine tsscghhhaaeoorsbiwwsfoaiinmcnnapgictn,ioeopFmvnyiigrpddouoeuprsneerictostieboo3eon.d2faei6nCnp,cdo=3rspe0.i2art,io7soCecnade-nOdowdu,fhr3oCei.rl2-egaC8paO.,npailNacinenodcddofCflmSou-iHropctroohbiunmeonencdpd(osoFimson)igntbpi.uoethsnaTteksihocdiensaelrcetotervrcseiiadtadstgse.ieoendOntsifunonorlffryeaftilcChtuehe,oedOrcriuan,srrepaitnreniigcnddtgrtsShueaiemmuwXs.p.eelPredTeSgfhdoraeeersstrisefueaicllcmattaestitpdviiloseen. Table 3.6 Approximate Atom % Surface Compositions. Sample *T*STraeBrmealaptatenleedkdc21ansrdttridge C1=.60 45..82 for the treated C C991-...1O59 article was C-C11, .C2-H 4505..50 analyzed twice. O 6303..79 23.1 Si 21741..2.68 Figures 3.26,3.27, and 2.28 show XPS results for the blank cartridge, die first analysis of the sample cartridge, and the second analysis of the same cartridge, respectively. 41 Figure 3.26 XPS Result for Blank Cartridge. x 10s Figure 3.27 XPS Spectrum for Sample Cartridge (First Analysis). 4.7 x105 3.5 Telomer B Alcohol Combustion GC/MS Analysis In-line GC/MS analysis was conducted for Telomer B Alcohol thermal decomposition at 200 and 600C wmienxaatosrgrasfdcroetoerfmdstoaidmocenocpnol7efm7igrp(ma*osCsitfihFtia2ieoCtdniHoaon=nfdC7thtH7he2ef)o"ifrnTomterealgTotriemoalntoeemrdo"bep(sreXeBar-kvCAeaHdrlce2iCoanhHftooh2lre-CtihfonlenuFro2m7nr7+ianil)(a*dftCeuedcFnoc2aCmtcioHrpyno=laisClciittHpiyoo2.n)lyFnamoitgr2eum0rr0eacloa3imzn.2edbd9u6bss0hyt0ioomwnCast.sessTtishse pgrreesaetenrteadmionuTnatsbwlei3th.7i.ncTrheaesdinagtatesmugpgeersattsurthe.atRcoamwpDoautnadasrecopnrtoavinidinegd ithneA*pCpFe2nCdHix=CC.H2fragment form in 200000 Abuneittne 1 4000004 t aooooo 20.00./1 /v U -- r r .o o ty e .ro to rr.ro > s -ruiveo.o 200C 600C Figure 3.29 Extracted Ion 77 (aCt F220C0Han*dCH6020) fCor. Telomer Alcohol Combustion Temperature (C) 260000 Gasified1M.24ass (mg) 1.68 Norma31li40z74e21d7114P97e62a35k Area 3.6 Treated & Untreated Articles: Off-line GC/MS VOC Analysis at 1000C VuannOatrlCeyasztefedrdoumasniudnngttrroeefaaft-teledidnaearntGidcClte/rMecaoStmeadbnauarsltytiicsoilnse.caoFt mi1g0bu0ur0esstCio3,n.3rea0stpa1en0cd0ti03v.e3Cl1yw.sheToreawbcltoehlel3e.tc8ottesadhloiiwnonsactThheerdonlmaertataombgaoragumnatnoodff tscraoemrartpeesldepoagrnatdsiciftloieesda,i.irn,AdCilcl0as2ti,ixnagcnhdthrwoamtatvaeotrol.agtNrialoemofsltuahoreerronscieagarnrbilofyincisdanewntetprieceaankl.ostTwdheertreeeecotmebdsa.ejorvrepdeafokrs binotehauchntcreharotemdaatnodgram 44 Abundance TIC: VO C U T 1.D Abundance TIC: V O C U T 2.D Abu nda nee TIC: V O C U T 3 .D Figure 3.30 VOC Analysis for Untreated Article Combustion at 1000C. Abundance TIC: VO C TR 1 .D Tim e--> Abundance TIC: V O C T R 2 .D Tim e--> Abundance Figure 3.31 VOC Analysis for Treated Article Combustion at 1000C. 45 Table 3.8 Net Mass of Sample Gasified. Sample Gasified Mass (mg) TTTrrreeeaaattteeeddd AAArrrtttiiicccllleee 231 22..1284 2.09 3.7 Treated & Untreated Articles: CO and CO2 Analyses at 1000C uCsOinagnodffC-lOin2eaGnaCly/TseCsDfraonmaltyhseisc.oTmabbulseti3o.n9 oshfothwesttrheeatfeldowanrdatuenmtreoantietodraerdt,icwlehsicaht 1is0u0s0edCtwo ecraelccuolnadteugctaesd cwfugCeccooaoxanohrrnslhtliblriucuacefeoenumihcaennttstdreanettrerrddevcaae8coCattanioeolrnoOudbovfdnmore,TamrntoCnearyefaObdc.(alCalm2itetClzrOecLeae3oduand).lal9taduaeabnrmtdsntdytehhidndcaCteolshrtibweOthre2iye2ccssm,olausntennmhamaumducsembmsomc3pumboaalsbieterftbneiibroguowroTonasnoent,afs.iifibrmogrfmeCelinheosec.toopdlo3ellaeTveu.ssnc1semahdt0ormioeynvftsfhp,seaChCwellv4oyeOeOrsh.wtre.hiaalcCargaCnThontoedOihudlivCesuCgeCamhOOcanc0av2n6dalce2croc7irCbucnaonoolig0lcanTnllee2letaeeTncwcCbcdttaoelteOrbeebnadi2ldgatc.3ei,hseco.e3T9ntnond.rtuan9sradbmcahotisletinofebiohnfoweeott3pnhrrrw.rasste1ohotsi0smiefvnootmihsmonmdthehloeiooaeesldmrlwweasabnorshaglyulmmaantamhtsDuropibembnfsuleiiteuPenbtriwmdogedo,nreebbfatneoea.nntrfgidco, afl AcaprpbeonndcioxlDle.cted and carbon gasified. Raw data for the VOC, CO and C02analyses are provided in Noinveleeartrelfsyltoi1wm0a0rta%itoencsaobrefbftoohnreercetachroebvoseanrmyrepwclioanvsgeorabyntadmincaoeydllrefecosturiolbtnoftrthoimmuen.tthreeaetestdimanadtiotrneaotfegdaasrteixchleasu.stTvhoeluslmigehbt ased on _T_a_b_l_e__3_.9__F_l_o_wURsaetde fMoroCniOtoraenddfCorPC2ROeacnodveCry0i2nATnaablylesi3s.1(B0)a.s_e__I_n_fo__rm__a_t_io__n U nit In let 1 (m L/m in) Flow Rate In let 2 (m L/m in) M akeup Gas (m L/m in) T o ta l (m L/m in ) G a s ific a tio n Tim e (sec) T o ta l Tim e (m in) T o ta l V olum e (m L) Untreated 1 6.8 8.7 4.2 19.7 53.39 4.89 96.33 Untreated 2 6.8 8.6 4.4 19.8 54.86 4.91 97.30 Untreated 3 6.8 8.7 4.3 19.8 51.18 4.85 96.09 Treated 1 6.8 8.8 4.4 20.0 68.10 5.14 102.70 Treated 2 6.7 8.8 4.5 20.0 66.87 5.11 102.29 Treated 3 6.8 8.9 4.5 20.2 62.20 5.04 101.74 2 2Table 3.10 Carbon Recovery for Untreated and Treated Article Combustion at 1000C. Sam ple N orm alized CO Norm alized co T o ta l Gas V o lu m e CO C o llecte d co C o lle c te d Number of C Number of C Carbon Recovery Cone. Cone. (m L) (M ol) (M o l) C o llecte d G a s ifie d (PPm > (ppm ) (M ol) (M ol) (% ) Untreated 1 826 9712 96.33 7.09E-06 8.34E-05 9 .0 5 E -0 5 8 .9 2 E -0 5 101.4 Untreated 2 635 10165 97.30 5.66E-06 9.06E-05 9 .6 2 E -0 5 9 .1 6 E -0 5 105.0 Untreated 3 468 9756 96.09 3.85E-06 8.01E-05 8 .3 9 E -0 5 8 .5 5 E -0 5 98.2 Average 643 9878 5.53E-06 8.47E -05 9 .0 2 E -0 5 8 .8 8 E -0 5 101.5 Treated 1 351 9737 102.70 4 .0 8 E -0 6 1.13E-04 1.17E-04 1 .1 5 E -0 4 102.2 Treated 2 448 9485 102.29 5 .0 9 E -0 6 1 .0 8 E -0 4 1.13E-04 1 .1 3 E -0 4 100.2 Treated 3 321 10326 101.74 3.38E-06 1.09E-04 1.12E-04 1 .0 5 E -0 4 106.8 Average 373 9849 4.18E-06 1.10E-04 1 .1 4 E -0 4 1 .1 1 E -0 4 103.1 4 fi 3.8. PFOA Absorption Study 3.8.1 PFOA in Aqueous Solution The PFOA absorption and transport efficiency tests are summarized in Table 3.11 and 3.12. HThPeLaCb/sMorSp/tMioSn taensatlsysshisomweedastuhraetmPeFnOtAreqreuciroevdermyuflltuipctlueadtieldutbioentws efoenr t1h0e0satom2p8le0%to. bTehweiPthFinOAthe ccoalrirbercattliyonrercaonrgdeedoafnthdethinesrterbuymwenotu. ldInatchceouconut rfsoer othfethoebsseeravneadlyfsleusc,tuthaetiodniluintiorencsomvearyienso. t have been Test Absorption 1 Absorption 2 Absorption 3 GPaFsOifiAed (mg) 1.93 1.95 1.96 Table 3.11 Summary of PFOA Absorption Tests. W ater Volume PFOA Concentration J(ma rL1) J(ma rL2) J(amr L3) (Jnagr/L1) (Jnagr/L2) (Jnagr/L3) P(TnFogO/tLaAl) 60 60 60 79700 60 60 60 34600 1000 17700000 25671000 2480 10500000 10848480 60 60 60 3640 14100000 16900000 31003640 RePcFoOveAred (mg) 4.62 1.95 5.58 RPecFoOvAery (%) 239.4 100.1 284.7 rDtGee,usctoree(vtcsoeporetryhrceebtisavppseooelonydrd.oiPnnTFghtOoetotAareAlrsfebulcsulotoosvrrpaientrrieeyo.nsrheT1sohuwielntnseT,xinaWpbeTlirecaimkb3bl.ee1on1l3td)a.1lwT2soa.erstcTuahphneaaanlnsyaadzlmyemsdpei.lstehTwcohoadeslslercaecorsteneudddltuesdcsustcehrrdioinbwtgeodt6eh9iven.a3fAl%iurpaspttfeleaunbPodsFroiiOxnrpeAEtioannd rosdeaefcmstohcpvrelieibarneybgd.ssoiHynrpsoSttweieomcentvioteoecrnsc,tu2na.re1prae1prd.alyruan5tud0s%e.r tTohfhetihsceoinnPddFiictOiaoAtnesslotohafdattehdseisgwenatisefisrcteasc.notTvPehFreeOdpArionctooJcanordl3eu,nstsheaedtiorfionnrsutephasitsterseftaruomdmyoeifsxthtreaction _T_a_b_l_e__3_.1_2__P_F_O__A__R[eScaomveprlye aUssFedlu: oAribnseor(pWtiiocnkb1o]_ld__T__o_rc_h__A__n_a_ly_s_i_s_). Sample Jar 1 Sample Weight (1) 2.9fe9)28 W a(t2e)r(VmoLlu) me 60 Fluorine Weight (3) (1M9-.S4) Total Fluori(n0m.e3g(9)3) x [(2K1)] Jar 2 3.0200 60 1.2 0.02 Jar 3 2.9904 60 46.1 0.92 Total (mg) 1.34 Gasified (mg) 1.93 Recovery {%) 69.3 3.9 PFOA Transport Studies 3.9.1 PFOA Transport Study - Aqueous Sampling The transport efficiency test at 170C showed very poor recoveries and large fluctuations from 0.5 to 4fl.u4c%tu.atTiohne (tr1a4n.8sptoort20ef.6fi%ci)e.ncTyhteepstroatto3c0o0luCsesdhoiswdeedscimribperodviendSyeecttisotnill2p.1o1o.r recoveries and smaller 47 Table 3.13 Summary of PFOA Transport Studies. Test Transport @ 170C 1 Transport @ 170C 2 Transport @ 170C 3 Transport @ 170C B lan k Transport @ 300C 1 Transport @ 300C 2 Transport @ 300C 3 Transport @ 300C B lan k PFO A G asified (m g) 1 .6 8 W ate r V o lu m e Jar 1 Jar 2 (m L ) (m L ) 65 60 PFO A C o n cen tratio n Jar 1 Jar 2 (n g /L ) (n g /L ) 72400 0 1.71 65 60 6 0 4 0 0 0 0 1.9 65 60 6 6 2 0 0 0 7 4 .4 0 65 60 965 304 To tal P FO A (n g /L ) R ecovered P FO A (m g) P FO A R ec o v e ry (% ) 72400 604000 662074 1269 0 .0 1 0 .0 8 0 .0 8 0 .0 0 0 .5 4 .4 4 .4 N .A . 1.75 65 60 2 0 7 0 0 0 994 2070994 0 1.81 65 60 2 9 8 0 0 0 954 2980954 0 1.75 65 60 2 5 5 0 0 0 2 0 0 0 0 25 70000 0 0 65 60 212000 510 212510 0 .2 6 0 .3 7 0 .3 2 0 .0 3 14.8 2 0 .6 18.4 N .A . To further analyze these samples, two aqueous solution samples were analyzed for total fluorine using the Wickbold Torch method. The first sample was from the firstjar from the second JN transport efficiency test at 170C. The second sample was from the first jar from the third transport efficiency test at 300C. The results are shown in Table 3.14. The fluorine recovery was determined to be 9.8% at 170C and 45.9% at 300C. The PFOA recovery as total fluorine shows better results than the direct PFOA measurement. However, the low recoveries coupled with evidence of PFOA condensation from the total fluorine analysis of samples obtained from the absorption tests strongly suggest PFOA condensation in the unheated silicone tube transport li_n_e_._____________ Table 3.14 Wickbold Torch Determination of Total Fluorine.________________ Sample GasPifFieOdA(mg) oWf FeiinghPtFrOatAio CFGalulacosuriiflnaieteedd FlTiunooJtraailnre ReFco(%ve)ry FteFt1rrfii7aafrrn0nisscststiCppjjeaaoonrrrrcttooyfftstehesictrodant d 1.71 1.75 0.688 1(1M76._5________1i1t5is.2i 9.8 0.688 1204.0 552.9 45.9 e3f0f0iciCency test at FaTecxohctlerloaosrcwdtteiiianonmgng tfteoohxlettlhroiaenwciptetiirdoaolntbotywrcao5anlsmsdppLeoesrrocftfortiewrbmseatsdeteddirneatsofScteerriicrbnttisehoedentaah2ble.lo1Ptv1uFe.b1,Oi.snAtge5atwmrmahLniwcsophafoscwruotasneetnfedfericctwotieeaednsxctithynreattrceAotsdtTtshuRecsSheAdotTwoaRsnthSsietneswyaTmsaattbeefmlorerb3ue.a1bc3bhlers. 48 wofrnoelrmye 0tch.o1en7ds8yumscttegem.dT., Thexaebcmelepatj3of.1roi5rtytshhoeoftwPhFsirOtdhAeexswttreaaacsmteioxentxr.atrcTatcehtdeiodtnoutrraeilnsPguFltthOs.eAfOirrvescet orsvt8ee0ar%medoefxfrtotrhmaecttsihtoeenas.mteIwanmaasdedrxeittcriaoocvnt,eirotehndewas ptThyaerbotlopetra3ol.b1ae6m.woTaushnertionsusfemPdFowOfiAathlliwnthtareotedsrtueacanemdd aeinnxtatorlaytczhteeidoA.nsTARannSdetgpelysigtroisbyplsreoteabmme owinuanttheterosrfeiPntsFeesOtasAc. cwouanstrsefcoorvleersesdthasansh2o%wnofin Table 3.15 PFOA Recovered from Steam Extraction. ExStrteaacmtion 231nrsddt T45ottthhal CSo(lmtleeaLcm)ted 4.068 4424....123138935556 Rinse W(maLte)r 555 55 AT(mmootLau)lnt 7999....110393635586 9.285 PF(COnogAn/Le.) 19229175029570126000000000000 RePcFoOveAred (mg00000.)....000010000711204 0.178 Table 3.16 PFOA Recovered from Pyroprobe Rinsing. Pyroprobe Rinse 21nsdt 43rthd W(UmaseLted)r 100 111000000 P(CnFogOn/LeA.) 4269052 PFOA Recovered (WO00..41 00 00..00 T5otthal 100 0 00..50 3.9.2 PFOA Transport Study - Gas Phase Sampling TcaonhrderetphsrpeootlonascdtointlhgfroetoretPhwFiesOrteeAso.tbitTsahidneeesfdcirrfsirtbotemhdreidneirSaerceetcatisinowjnece2tr.ie1o1no.b2ot.af iPTnFeaOdblAfero3imn.1to7PtFshhOeoAGwsCtriainnntsjeepgcortaritoteenddptthoorrtaot.luigTohwndopieesayAksTtaeRrmeSa brPfTwrocuarrlbFaoeatintibtOrmnaoseelikrAesnoitaharhe3vfuiode.n(et1nw7hrtpf7soa0err.ngo-wetA1oehmvEe3dveicrao0.eteacGhu%rrhBpaesCrg,eyapbereUosiexlfneavaoPSpdjnkereeemkrErcoaaiftPknrmreioueoAdAtrenanh,nfasrewopelt1wl.roaaa93vrtse9Th1ter6snheearoa)oaen.vmPargdfemdFFepirdnrOilapsAgeeoltAesudivzba.cretealketoarrOdrsaanardnngb3yrkieesye.oe3arpvsPu2,ptoyehnee7rraseatas4tnwkketg.sdh3maahAar%s3soorirb.ewiuf3edolaig3aaeeefohnddn2stbkrhtt.ssaithoamwfan7eimwiesa4naApdpsl.etl3oTldhpfe%arreRetmfomrrteSmifooosfaomtftusartwoinshmcltiteichaiteeooohnebndnnifdlcnfaffcyiciotnragrhhsrwmkreertrtonayrhGtnumeshoeoCrnrvoaade.esbtlreiolarrutTyagemdanhicraennpaetactdemelscipednressemjecfpbheaocatiyocknerortwrdaittnayaohtnrdriokneeeovibiacnPnnoselosgaFfrvnOtekhrAey transport through ATRS and GC injection port, respectively. 40 A TR S R un #1 ATRS Run #2 ATRS Run #3 D irect G C 1 D irect G C 2 D irect G C 3 Peak Area from First (1)G C R u n 684994647 673277175 814730308 966189956 1030933423 1033245273 Table 3.17 PFOA Peak Area. Peak Area from B lank Run (2) 10510992 4069277 Total Peak A re a = (D + (2) 695505639 677346452 Sam(pm(l3eg)M) ass 0.44 0.45 289003 0 0 0 815019311 966189956 1 .0 3 1 E + 0 9 1 .0 3 3 E + 0 9 0.45 Average Peak Area 1 0.45 0.48 0.45 Average Peak Area 2 Transport Efficiency (% ) (Peak Area 1) (Peak A rea 2 ) x 100 Total Peak Area Norm alized by Mass = f(l+ 2 )*3 1 1580694634 1505214338 1811154024 1632354332 2147088791 2147777965 2296100607 2196989121 74.3 Abundance Abundance T im e -- Abundance 1e+07 8000000 eoooooo 4-000000 o2000000 T IC : P F A T 4 .D ATRS Run #3 4.00 6.00 8.00 10.00 12.00 14.00 16.00 Figure 3.32. Total Ion Chromatograms Obtained from PFOA Transport Test Through ATRS, 1 .2 + 0 7 1*07 8000000 6000000 <4-000000 OJ-2 0 0 0 0 0 0 T im A b u n d a n co T.2 0 4 -0 7 -I a + 0 7 8000000 6000000 4000000 2000000 o , ............-J|s> <4.00 6 .0 0 T I C : P F O C 1 .D TIC: P F G C 2 . D O TO OO T 14.00 T T.2a-*<07 T OT 8000000 6000000 4000000 2000000 O Tim -> T IC : FF=^<SO S .D T0 .0 0 T2 .0 0 Figure 3.33. Total Ion Chromatograms Obtained from Direct Injection. Direct GC 1 Direct GC 2 Direct GC 3 3.10 PFOA Calibration Curve and Detection Limit Studies TcahleibmraatisosnocfusravmepilsesihnotrwonduinceFdigaunrdet3h.e34co. rTrehsepoenxdtriancgtepdeaioknar1e3a1,arwehtiacbhuilsattehdeimn oTsatbalbeu3n.1d8anatnidonthoef the major PFOA ions, is shown in Figure 3.35 for 1.10,5.50,10.16, 50.80, and 100.40 pg injection. PFOA appeared at a 16 min retention time. A secondary peak emerged for 50.80 and 100.40 pg injection; phrAineeoplawFapktieeigsvvnuaeedrtlriey,xv3talFha.r3.eryg8imne. gaqBsursoeattsnheptnipettceyiotarankunsmtdiwmtsheehersoewhmiinsgathyaegpbnroeealataaertrldtiyrtiyaibndoudetfnesttduhicmetaoamltnpheaaedltytstetooerrn.dpReftiotaoerwnrtmhadienandtmeadtafheionesropatrhnepiadtsikossentaucriedonany.tdhiaseTrpydhreeeptseeseacenkcttosoerndaddsiuanserhytoowtnhe Table 3.18 PFOA Mass vs. Corresponding Peak Area. PFOA Mass (5j1i..g51)00 1501000...841060 Ion 131 Peak Area__________ 252159st43737813 25805163964623921958380 24n5d6475 2325787699993847329520 45606352 Av2e73r27a44g29e8219 42755997873161334001154 Abundance 600000 Ion 131.00 (130.70 to 131.70): DL1 .D 1.10 |Xg 400000 200000 Tim e--> O ' 1 1 1 i 1 1 1 1 i ..I~'""r..1"[ 1,1,1 1 1 i 1 1 1 | i 1 1 1 1 i " i 1 A bundance 5 .0 0 1 0 .0 0 1 5 .0 0 2 0 .0 0 2 5 .0 0 3 0 .0 0 3 5 .0 0 600000 Ion 131.00 (130.70 to 131.70): DL3.D 10.16 |Xg 400000 200000 Tim e--> 0 j-t~t Abundance 600000 | - r j * r x--i i--j--i-- i--i--r~-j-- Ft 4-!--r~ j-- i-- t - r ~i--j- ~ r T --r - r --p- T~ r -- 5.00 10.00 15.00 20.00 25.00 30.00 35.00 Ion 131.00 (130.70 to 131.70): DL4.D -|- r 50.80 (Xg 400000 200000 Time--> 0 ^ Abundance 600000 -H* ~T~r~rr~ 5.00 10.00 15.00 20.00 25.00 30.00 35.00 Ion 131.00 (130.70 to 131.70): DL5.D 100.40 \ig 400000 200000 Tim e--> 0 ~T ' 1 Figure 3.35. PFOA Extracted Ion (131) Chromatograms for 1.10,5.50,10.16,50.80, and 100.40 jig. Figure 3.36 shows the reference spectrum ofPFOA obtained from the NIST129K library (G1701BA V13e1rs(ioCnFB2C03F.0C0F, A2)g, i6l9en(t*TGeFc3h),n3o1lo(gCieFs)),.4T4h(eCfi0v2e),manodst9a3bu(Cnd3Fan3)t,iionntshsishoowrdneri.n the reference spectra are Finijgeucrteio3n.s3.7TshheoswpsecthtreafcuollntsaciannedPFioOnAs 1p3ea1k,6s9p,e3c1tr,aafnodr9th3e. 1T0h0e.s4e0c,5o0m.m80o,n10io.1n6s,w5e.5re0,uasnedd t1o.1e0stpagblish the PFOA detection limit. All of the PFOA peak spectra, from 100.40 to 1.10 fig, show major ions with similar abundance ratio to the reference spectra. However, the spectra for the 1.10 pg injection shows ion a1s8soascitahteedthwiridthlabragceksgt riooun,ndwthriaccheiws naotetrcionmthpeattiebslteswysittehmth.eTrehfeePreFnOceAslpiemcittrao.f Iqounan1t8itaistiwonat(eLr,OHQ2)0w, as established using extracted ion 13land is 1 pg based upon 1 pg as the lowest standard of calibration. The tl(hi1ma/6ti.tt6ho7ef)dsoiegftneLcaOtliQ(o1n3i(f1L)SOt/oNDno)ofiissLelOo(wDSe/Nirst)dhreaanftiinotheiedsLamsOocQrae..tP3h:Fa1On. A20f.uTllhsecraenfosrpee,cLtrOuDm cfoorul1d.1b0eplegsisntjheacntioonneshsoixwths Btlhimaesiaetrdotiofcngleatsshaepnh1da.1s3e00PptoFgO4li0Amsicetoconffcoqernuttahrneattipitooantliyocmanne(rLbceOoeQms)tb,imuosnatitaoednm.taeTssstysbp. aicTsaihslegoagbsatiasfiiinfcieacdtaitoiinonntthitmiismessetuwodfeyr3,e0th2se0ecdtoeptr3eo0cvtisiodencesfor 0.94 mL/sec x 30 sec = 28.20 mL synthetic air at 25C. The molar amount of 1.10 pg PFOA is l.lOxlO'6 / 414 = 2.66xl0"9mol, which gives gas phase volume of: [2.66xl0'9(mol)x0.0821(atm-l/mol-K)x298K]/latmx 1000mL/l = 65-lxlO-6mL at 25C. g1apsg-pPhFasOeALOcaQn panroddLuOceDgaasrep2h.a3s1eacnodnccean..tr0a.t3i5onppomf 5, 9re.2spxel0ct`6iv/2e8ly.2. = 2.31 ppm by volume. Therefore, the Figure 3.36. PFOA Reference Spectra Obtained from NIST129K Library. 54 nx. ..t- 100.40 jig 50.80 |xg 10.16 jig 5.50 pg 1.10 pg Figure 3.37. PFOA Full Scan Spectra for 100.40,50.80,10.16,5.50, and 1.10 pg Injection. SS <- 16.2 min nI 3.11FPluFoOriAnaAtendalAyscirsylfircomPoClyommebruUsstiionng ITne-sltisneofGtChe/MTSreAatneadly&sisUntreated Articles and the The ion chromatograms obtained from the actual treated and untreated article combustion tests shown in bsstSrteeeealtcanewttcdieetoadeenrdnda3nfr1.od1e4rfuweathnrneeitdrsrneeca1aeen8txealmadilbymiarsnariinstrwiyecbadlesespctomceacouiotmsdrneeubinmtiuotti.srwfteyiFadostinbhgteeuthecrepsaetouslsats3eraegn.t3ett6h9isa0itlsa0bne,iaxsd6siwe5s3dt0.he4,eon07rnc0eset0hPhao,Fenw7Odc2aeA5qlx,uibtiaarsrnnaaecdttixtiteo1ypdn0eo0ciwof0teonPdCrF1kt.O3oi1AnTehcl.SuheetIrecoeotlnumiuont1anid3oteo31nrg.9wtrtihamaamesnessde ftohre the GC PcetTphoxeehentaaerskdkaepissctepitcaoeaeopdknarpksriae.esotalnaNar1rt6a1eoe.t3d3fP11o5wF6rcmOi.hPt3hriAF5onaO,mp1irsAe7aetat.feob1kengar0wters,aan1eatmdci7sve.usde7splef0ypooteearniccdntttehedervneuda1tmfil7afluu.tii9aenoa5tdriltoiimahnmnseaiointCNtefeadoItHtShfatTeFdceireumrlyti,emblpbicrecaaatrispsraoyseotnud.lsyropoemefsnc0eott.rrh3faea56wtN0p60hpI0,iSm0c6Th.t5oal0Firb8,ie7rg0a0su0rh0ryoeC,.swaNan3nn.do4idnn178e5Fa50oin0gfdCuttohr3.ee.N413o20o.t04nhs03ehe.oroCwf. Tbinehdtewicreaeet-ineoxn6a0om0fiPtnoaFtO1io0An00ofofCrtmhweaititiohonn8c5ah%trtohemexcasuetosbgs-rpaapimrm. floervtehlefoarcttuhaeltchoremebsuasmtioplnetsessttusdsiheodwast tthheatteth'mepreeriastnuore *6 AbuodAn Ion 131.00 < 1 1A. OO 1 .SO O IS.SO IS.OO IS .S O 1T.OO 131.00 <130.70 0 13 1. 7 0 y . TF 1*3 600 C 650C Abundanc t IS.SO IS.OO IS .S O 1 7 .0 0 131.00 <130.70 to 131.701: T R 7 0 .D 17. SO 700C >.t>urct 1 4 .0 0 1 4 .SO IS.OO SI.OO <130.70 tc 1S.SO 1 7 .0 0 1.7 0 >1 r w r a .D 17 . SO 725C .00 14.e IS.OO IS.SO IS.OO IS .S O 1 7 .0 0 lor 131.00 <130.70 to 1 3 1 .7 0 >1 TPtOO-1 .O 1 7 .SO *1000C s.o o 1c s.oo 1 17 .0 0 17. Figure 3.39. Extracted Ion 131 for Tre7a0t0ed,7A25r,tiacnledf1ro0m001C4.to 18 min Retention Time at 600,650, A bundanc 6000 4000 2000 14.00 Abundanc *1* Ion 131.00 <130.70 1 .70): 0 7 6 0 -2 .0 IS.OO IS.SO 16.00 1 6 .SO 17.00 17.s o 131 .OO <13 0 .7 0 to 13 1 ,70): UT65-2.D 600 C 650C 14.00 6000 4000 14.00 1- i s .00 ie 16.00 1 6 .60 17.00 17.SO Ion 131.00 <130.70 *0 131.70): UT70-3.D 1 4 .SO 1S.OO I.S.TS*.-Oy& t, 16.00 16.60 17.00 1 7 .SO 6000 4000 Ion 131.00 <130.70 to 131.70): U T 7 3.0 700C 725C 14.00 A bundanc 14.60 1S.OO IS.SO ` 16.00 16.60 17.00 1 7 .SO !000C 6000 131.00 <130.70 to 131.70): UT99-1.0 4000 2000 . 1O4`.i01r0-->--i-1"*4".iS"O* --<--IS--. Or--Or---.--'--ISi--.S>-O------16.--.0|---0.------1-*6--.i-6*-'0--*a-1-f7-v.0--0--i---i--1i--7.t --SO '--r* Figure 3.40. Extracted Ion 131 for Untreated Article from 14 to 18 min Retention Time at 600,650, 700,725, and 1000C. 57 Abund 400000 300000 ton 131 .OO <13 0 .7 0 to 131 .70): PMTO.O 1 ooooo 1 4 .0 0 14.SO 15 .00 1 3 .3 0 1C 13.30 17.00 17.4 400000 300000 200000 1 OOOOO T >m 1o4' .i0 0 1 --4 .r3-0-- 131 -OO <13 0 .7 0 to 131 -70>: Frv17S-0 17.00 750C 800C 400000 300000 ton 131 .OO <13 0 .7 0 to 131 .7 0 >z P M 8 0 .0 200000 1 OOOOO 1o4-h.-0---0.-- 14.30 Figure 3.41. Extracted Ion 131 for Fluorinated Acrylic Polymer from 14 to 18 min Retention Time at 600,650,700,750, and 800C. 4000 3000 2000 14 .0 0 to n 1 3 1 .0 0 (1 3 0 .7 0 t o 1 3 1 .70>* PMBO.C 90 1 0 .0 0 to n 131 .OO <13 0 .7 0 t o 1 3 1.70 ): P MOO. O 850C 900C 2000 1 OOO 1O4l.,.0-! .0a.i.t, r *1u 4,-*.f3 0 1 3 .0'r0iTii .OO 1 3 .0 0 1 7 .0 0 1 7 .0 0 3000 2000 o n 131 .OO <130.70 t o 1 3 1 .7 0 ): PIS4B .O 950C 1000C Ion 1 3 1 .0 0 <130.70 t o 1 3 1 .7 0 ): PMOO-3. D 3000 2000 1OOO W3- 13 .0 0 Figure 3.42. Extracted Ion 131 for Fluorinated Acrylic Polymer from 14 to 18 min Retention Time at 850,900,950, and 1000C. SR At>une)i*M Figure 3.43. Spectra for th6e0P0eCakisnaFti1g6u.r3e53,1.471..10,17.70, and 17.95 min at SO 4. Discussion The purpose of this study was to investigate the thermal degradation of a polyester/cellulose fabric sceuoxbncsestesrsravtaeaitr(iv"leaevrlyteilcr.leepT"rh)eetsreternaettaientdegdwtyaiptrhtiiccfalleul omisruornteeialcsoiopmnaealrbw-lbyaasesteexdpceoaccmtreybdluitcsotpoborelcypomrnedesiretiunontndisneormfluatibnmoiceria,pttaoelrmywpcaeosrtnaedtuaitrsieod,niassncdarded ttfehluxeottirrloeetaeotlerodpmaaeprrtei-rcb.laeTswehdehraeecnfroyitrleiics, tpihnoecliypnmreirnearct,iepadan.ldfSTocueuplospmloeefmrtheBnistAawrlycoorskhtuowdlaireasswtoexmdaeamtteeirnrmieadilntaoentahusensitesrnet avintiertodhneamritneictneltera,plrtfheaettaetioofn of the experimental observations for the treated article. T(gfeaYrxvahospeaemiremfatriegi6camsae0dtt0aetpieonratmntoonst.pdco1oec0TTrno0aahdl0tyseiutlrCuiosoetsrun,feodos2df.ir0ew1a0sT0e3mhe0r,mee0eGrasumCrnilamaa,holtgiearleadmagxsrprt-,ytepeo2pahr0tiitaemc0hsra2oeelo)snr.mevetessTduriwenhdavieeepcernrpimlecporeaoopthlxgteiewidrmmnaafveascoittormoeenrfleieyd2ntcur.c2ei0cicnntsseteaeedctnrceaa.arstlettoyi8snrnsi5oidcgs%neoow-nmfefclaxbaefslcumutuesioemstsirseoriedenana(aitrGccoteotwioddnraaredmsuftiiedtaunim,tosee2enprt0diseha0rewfla4osti)rut.hraelalsn wuCt9drn9eeoett.amre9reter%ebmacdutoiecsanmdotnainopdatvinlroueteinttnrceestldsoireote.f,snat4Thf,t)eoeh2drde)cteaodhftroneeetirtlcctlemerolrenewmia,ntritia3naent)tdgiaiodtoaoinenorbttnoejioecrfofmclteffthi,limeuvntoaehcatsreojiioodwnurnecnepetroirnroeofetnraadcadtauietndrcidborttseohnasneroostiefm1fcdi0Plna:e0Fsc,0soO1abm)nCAaddpletialtentehnestectrteshmefcesfliouoneamoraftrfttb1holiuou0eteens0tlnt0rooiteomffaCnrttehoearfemdt-obrt1aaea0tnsmhl0dlee0pdtueteransCrecttasarrtf,eytuoeaalrrditnecetdhadfpone5ord)lymer articles. The temperature for 99.9% destruction of the treated and untreated articles was 725C. This temperature regime (700-750C) for 99.9% conversion is consistent with the results of prior tests of hydrocarbonbased materials using UDRI thermal instrumentation systems (Dellinger, et al. 1984; Dellinger, 1989; Taylor, et al. 1990). The temperature for 99.9% destruction (T99.9) of the fluorotelomer-based acrylic polymer was 1000C. The T99.9value for the fluorotelomer-based acrylic polymer was slightly higher tThhaen dthifaftemreenacseumreadyfboer orethlaetredflutoortihneatleedvemlsatoefreiaxlcseusssinaigrtphreesseanmteinetxhpeerriemspeencttailvaepcpoamrabtuusst(iGonratheastms., 2002). Combustion tests with the fluorotelomer-based acrylic polymer used 85% excess air, while previous tests with other fluorinated materials employed considerably higher excess air levels. Excellent carbon mass balances were obtained from the combustion tests ofthe untreated and treated awoermbatsispcelloroevbsyesed(e1drv0vti1oead.9dGueaCntned/rdMemr1Sit0nhi3een.s6tthe%heec,pocrrneoedsmspietebinocucntseistvioeowflnyah)steeaacsvtatsir1ebo0ro,0fn0tlhemseCsot.vnreooTaxlhtaieetddieloe.annflFyldulpuourornoirtnidrnaeutaacetttdeedodbfoyairrpntgricacoonldemiusccp. btlsIey.ntpe-NrlocinoodenmuecGbtwsCusew/tMrieeorSne wtnhoaastt bidyepnrtoifdiuecdt.sAinddthiteiognaaslleyx,hoafuf-sltinfreoGmCth/Me S10w0a0sCemtepsltosyoefdthtoe dtreetaetremdinaendthuenptrreeasteendcaerotifclveosl.atNileonfeluworeirneated identified. tChoemtrbeuastetidonartteicsltes ocofmthbeufsltuioornorteesloumltse.r-Abats1e0d0a0crCy,li9c9p.o9l%ymdeesrtwruecrteiocnonodfuthcetepdotloymfaecrilwitaatseoinbsteerrpvreedt.atBioanseodf uifnlpucooinnroettrheailtsoormrecseourn-lbtd,aittshieoednfsal.ucorAyrolnitcaelplyoosmliysemor-febtrahsieneddreicaaacctrteyodlrictehfpefolufloyernmmt efarrtoiwomnouaolddfdabitevioadnreiaeslttyrcoooymfebcdouumsntipdooenur tnteydspstiscaoat lftemthmuepneircaiptuarles 6n blieblroawry1o0r0m0aCnu. aMl manayssosfptehcetsrealcionmteprporuentadtsiocno.uAldsnaortebseulitd, eanltiimfieitdedusniunmg beietrhoerftchoemNbIuSsTtiomnaesxspsepreimcteranlts uwneirdeencotinfidaubclteepdeoankst.heTTheeloexmpeerriBmAenlctsochoonlfriarwmemdatthearitasletloectrteydtoiodnestewremreintehethseaomreigfionrothf tehpeoselymer and balycporhoodluicntdsifcraotmingthteheciormorbiugsintiownaos finthdeeefdluforroomtetlohme teerl-obmaseerdfuacnrcytiloicnpaloitlyy.mPerowteenrteianl ovtoalantailleyzceodm. bustion tAHOrePnfaaLatldeCydds/iMiatsiroStfino/cMarlelPSitFnoaOtendArdeetsieintnr-wmclioainnsmeetbGoiufCdsietn/iMtcoeinrSnmetwerisnaettesrieowoncfhootenhftdhetrueterrcaetPteaeFdtde.OdaANratnoiwcdldaeuesstnefmtocrretaamaybteelbeddelaaaesrvtsaieoclruloeerscfauePtlFot1oOf0Pf00cFoOwCmAabususidnisnetttigheoerbnmoeotinhnfvteihdreo. nImt ecnant. tfohlfuePoreFrofOoterAleobwmeoecur-olbdnacbsleeuddfoeardcmrtyheladictfurponomdlyemrthteeyrp.iniccainl emrautnioicnipoaflawtaesxtteilienocirnpearpateironsucbosntrdaitteiotnresanteodswiginthifiacant quantity In addition, transport efficiency tests for PFOA using aqueous sampling (followed by HPLC/MS/MS brbhatntrcsahheeanhunoyauesamvdrdbtuscdoeebrpltttimeivtrholvlinseaqiineria)dndrnudvtsaDigeaosiiocnrnnfn(gBaweledsgcdvrtder-aeiiet5tentgprlthdhifaogahFneocnsaH)eiatra-As.gbrppPPfat.ssTeeihApLFotl2mrralRrOCo.aPslpp1pSirneF/Atln5yeMigaOPes)oruc.acainFSAtsonmotei/OTulto.nbMmueprhndAlermlPepetSaeisoneFcnnrPboaregtOtsaFaishnsfaostu(OpAaet2uifnipolso3roAuypwbnel5fnnslosesoaiolheitrsorCoswnwetsbtpfae(shetepyrptfh1ideoermfshe7otneddbhe0edhcuayntesctuyhbciiCyhrvciplesenilea.eoeodc-sc-ndmlrtolpAyathpiinrstopneetalrtmeitnietsranohleaistnlsnsGyrradpespnalruwppCaoaonysrenotrab/siiidcdMtlrnfsvtotoeaeguettxSrelifrhlsunatfafyleihifamiennnc,niendsecsgiinetae)pniabretlnot-sqodhyynulcurunuiiscbitnpsdeigreiisteipoiesncen)risouosngeGogwtrscltosbftuCette.sfhelramri/aeagetnnMeCmswcnrdjsicetreSnpeiyaoatcto-elhthottntilnneieeniaagdonrsngoetuatnetthenbsnch2temoGirstaau0ceaeflAnC%spdnyrtPivee.sTt/7nFeMrpmeu0gRaAOdoso%tpSSAriuqbfAnetruaTeivr(gtenaenedtieRwtntoAsoaeneuSttultfertoTsyreese4earrsRmstnsem0nihtsSa.dawePicCyanFtegtnh,eorOaddeersA Based upon the combustion product analyses, it was clear that carbon-fluorine bonds were severed at wmuae1nxn0oadat0turmr0eiliodaxiCnnt.bea.ecdAthiToeanrxrhnoatpimlisoycelfaswceitdtsooeaigdfuftforlet1adror0pefr0hflenou0ystrousmiCrnleitdcdhbiteinyyicoidatotnhrtrnesoeadgpo(fiepoffnlnirtudnmhfoigelcaruatiteohdtixioreevipndege[eFoaro`isf[]mfeHfHboleFueunFlo]storabfweilonyfarfeamlrpuneapaeaataotnclirymtotaitnitoisnuc)nsa[aiFwlnpq]drui.coeteohtFvoemhilucduybtseoiduodbrrsinuotncibglleoiubemnaelnetstioretasasmsv.stfassotiSoloalaulrfowbbetwlshheheeeaiqidgtntuhrhbetelahynyapettpserceaedoamnacmepntdibldviutneosgtatinhoedn hdfs(HlaiougmwFoh)pr-nitlwdseetemirdteghpiadeemtnhrnaeeootrutasfrititlenehiddceraiefmcragaocirtdmteoopudrcopidoiesnimdp(tS,broehuifs0ostet2hwni,oeceSnevri.eeOoarXcHf, tfPi)onlSurod.oifacrTtniahnahteeeliysrosseiiniasgscntvohtieofefrirtycshsauuelnrirkftpfaeaeyclctryeceo.h.pdirRunSoegetbrmteooonofctgvtahhareeetlrvriareidednagaedccenttsvicooieusrnsiscbeouoldfernfhtfaeoiycxrdmcear,omiomnngitgnaoeainstnhttifiontslhunoeotoartbiefdlstyeht e iif(nnSlucteoFrrer4poa)rstweeetlaaowstmiiootehnbrs-iwbneracavrsseeeoaddbsaaitnsacgiranytebleidymcpfpprrooeorlmdyautmiucnrte-eril,nianctteohtneeGmssCiesp/ttMeeernsaSttstuw.torieTttashhlbeiineostcniwrgecneaheasrnlionrm6eg0sayp0tiooeanglndsrdaesm1foo0sfr0Hf0SrFoFCma4.ttshhSheioiglwcihcoeeomrdntbaeteumntsreptaiaeofrrln-ualtoiounrfreiedtahere hGarirgiashihnlaygmffl,ruo2om0r0inc2aa)t.rebdIonnmt-haflteueotreirasilntsesuybssoitnenmgd ,hbicrgeaharb-ktoiennmg-fp.leuSroarFtiu4nreheabfsuobsneeddebnsrieolaibcksaienrrgevaedcdotoienrsspo(rcYecvauimro.uasIdnacosaumnmdbmuTsaatryiyolo,nrtt,hee2s0tfs0lu3oo,fride fsoilrimcoendtfertoramflucoarrbidoen.-fluorine bond breaking reacts with the silica surface of the test apparatus to form 5. Conclusions This study reports the first known studies to investigate the thermal degradation of a polyester/cellulose fpcleaoavbpneresilerc..rTsvTuhabtehisevttrrereealfaytoeterr(eed"p,aartrrehttseiicecplnleert"iinni)scgtrriepteyaaapslteoifcdnoaacwlbumilstyhuoenfaxitcfphileipuscaotwlreoidontrectkolionwbmeeareasprt-ritbooeansdesceenotdtenirandmcirmtiyinouleinnctsihpcoeiopfleaytnilmmvwieerar,osutnteenmmdaepesnredtraliaalstbcfuoaartreread,teoaodnfrydtthecexeoxttincrldeeesiaotstieroadnirs article when it is incinerated. LasPu(eatecfcsFarfcrecebOlyuduaaolArtenirteacanod.dtttepAoaeaiornnsxqnylaadcyud-mleismeycuscopzasneaulettrliaesrenfwideogrsiaetanrltmhermcePeavideFnptectOaelhlloiasrronAntbaoidgdtoc.i.fulro(e8afTcTn)ot5troehls%aaldretnonyu.dwsdi-dnpsCeie1cdeotdoae0sircmlc0tbeoat0eyibtffioeunftCondhiscfcteiflti(ini-heofmtlelanrinurneticaotate9yterfti9oeHsoto.etdtrn9PsesP%altLfooirFrnCftmoidOgtcm/heeMlAisreen-6ts,Srbdae0uu/ainM0nccmsa-atteli1Sratdyoee0tsneadaa0irtncsw0etirahaudyalleCsyslsaiisinrcdfanitogsoci-pc)rlheoiilasningeleny-eanvalmdsiosne-natpidedenmreha-t)msahl.ptaiseAlnitmeiteenfnmdrplgeGauelpsilottCnyioeerdgscr/obeMiattsfaneteoubSocltlrolehlfeeomaesttnwhlieemmoaerevlf-yeodreb7sesslba2sitaossy5coefwtdfo2Car.0s GC/MS analysis was 0.35 ppmv in the gas phase. Euasarnxtmsiccueplclellceseesnasutstnfc1uda0lre.0br0oFtnhlCuem.soeraFiscdlsouebnofadroilirnatminaotceneedsds.acwpAopemterteeabmruossbptttiotaosihnntoaebvdryeepfcrrroeooavmdceutrtcehftdlseurwioanpreciirnideneleynfrorawottmiiootbhntshtteheeresvctessoidmloifcfboaturhssecutoitrormfneabactteueesssdttosiaofanntsdhoHeufnFttehtrsweetseasertyeesdtem. The detection of SiF4 in the reactor effluent is a strong indication of the likelihood of this interaction. pTohleysme erersiusldtsesdteromyoendstarnadtentohadtettheectpaobllyeeasmteor/ucnetlloufloPsFeOfaAbriiscftorermateedd uwnidtheratyflpuiocraoltmelounmiceirp-baalsiendcianceiryaltiicon cdoisnpdoistieodnso.f iTnhmeruenfoicriep,atlexwtailsetse aannddpinacpienretrraetaetdedarweiethxpseuccthedatfoluboerodteesltormoyeerd-baansdednaoctrbyelica psioglnyimfiecarnt source of PFOA in the environment. fo 6. References AEnSvQiro(AnmmeenritcaalnDSaotaciCeotyllfeocrtiQonuaalnitdy)E.n1v9i9ro4n. mSpeenctaifliTcaetciohnnsolaongdyGPuroidgerlaimness. fAorNQSuI/aAliStyQSCysEt4es-1m99fo4r. Milwaulkee, WI. BCaonmkms,eRrc.Eia.l,ASpmpalrict,aBti.oEn.s,,aPnldenTuamtloPwre, sJs.,CN.e(wEdYs.o),rkO,r1g9a9n4o.fluorine Chemistry: Principles and Dellinger, B., Torres, J., Rubey, W., Hall, D., Graham, J., and Cames, R., Hazard. Waste Hazard. Mater., 1984, 1,137. HDeelmliinsgpehre,rBe.P, uinblH. aCzoarrpd.,AWssaesshsimngetnotno, f Chemicals DC, 1989. Current Developments. Vol. 6, J. Saxena, ed., DQiSmAiRtroinv,ESn.v;iKroanmmeennstkaal,RVe.s;eWaraclhke(2r,0J0.4D),.;1W5(1in),d6le9,.W.; Purdy, R.; Lewis, M.; Mekenyan, 0., SAR and UG.iSra.u,"d2, 0R0.,4", CinopmrebpuastriaotnioOn.perating Conditions for Municipal and Medical Waste Incinerators in the GTrreaahtaemd,WJ.i,thOLveordayllnTeh2e0r1m0a,lFOinxaildRateiopnorTt eCsitbinagSopfecLioadltyynCeh2e0m10icaalnsdCaoPrpaopreartiSoanm, Nploevember 2002. Hekster, Floris M.; Laane, Remi W. P. M.; de Voogt, Pirn, Reviews ofEnvironmental Contamination and Toxicology (2003), 179, 99. Kissa, E., FluorinatedSurfactants andRepellents, "Marcel Dekker, New York, 2001. POyhrtoalnyis,iHs ;HTasnudgbeo, oSk.,""MDaergcrealdDateioknkeMr"e,cNhaenwisYmosrko.f Condensation Polymers." Polymers in applied Radlein, Process, JDA.;APPis(k1o9r9z1,)J,.;1S9c,4o1tt., D., Fast Pyrolysis of Natural Polysaccharides as a Potential Industrial Schultz, Melissa M.; Barofsky, Douglas F.; Field, Jennifer A., Environmental Engineering Science (2003), 20(5), 487. ASt.o, cEkn,vNiraoonmmieLn.t;aLl Sacui,eFnicoenaanKd.;TEecllhisn,oDloagvyid(2A0.0;4M),a3r8ti(n4,),Jo9n9a1t.han W.; Muir, Derek C. G.; Mabury, Scott Taylor, P.H., Dellinger, B., and Lee, C. C., Environ. Sci. Technol, 1990, 24,316. TKainyelotirc, PA.nHal.y; sTisireoyf,PDat.hAw.a; yDsetlolinFgoermr, aBti.,on"TohfePHericghhl-oTreom-apryerlbateunrzeePneysr,o"lyCsoismobfuHsteioxnacahnlodrFolparmopee(n1e9:96), 105.486. TCaoymlobru,sPti.oHn.a; nTdirFeyla,mDe. A.; Dellinger, B. (1996), 106. 1. "The High Temperature Pyrolysis of 1,3-Hexachlorobutadiene," PTyaryololyr,siPs.oHf.T; eTtirraecyh,lDor.oAet.h;eDneel,l"inCgoemr,bBu.s,ti"oAnCaonmdFprlaehmeenJs1iv9e96K)in1e0ti4c,2M60o.del of the High Temperature TTariyclholro,rPo.eHth.e;nTei:reFyo,rDm.aAti.o;nRoufbCeyh,loWri.nAat.e;dDAelrloinmgaetri,cBS.p, e"cDieest,a"ilCedomMboudsetiloinngSocfietnhceePaynrodlyTseicshonfology, (1995) 101, 73. TCiormeyp,oDu.nAds.;fTroamylothre, PP.yHro.;lyKsaissnoefrT, eJ.trHac.;hDloerolleinthgyelre,nBe.,,""CGoams bPuhsatsioenFSocrmieantcieonanodf CTheclohrnionlaotegdy A(1r9o9m0a),ti7c4, 137. UO.fSfi.cEePoAf .EEnvPiAroRnmeqeunitraelmInefnotrsmfoartiQonu.alWityasAhsisnugrtaonnc,eDP.Cro.ject Plans (EPA QA/R-5). EPA.240/B-01/003. U.S. EPA Method 8000B, Section 8.4.9, p 39, "Determinative Chromatographic Separations", revision 2, 1996. WCTeoecphhprnmeorelSoiepgrey,cA(i1e.9s;9Li8ne)Cn, o3hi2lro,,2rDi7n.4a; 1tSi.oidnhaun,dS.CSo.n;dTeanyslaotri,oPn.RHe.a;cRtiuobnesyo,fWA.cAet.y;lKeneett,"ruEpn, vAir.;oDnmelelinntgaelrS,cBie.n, c"eRo&le of Yamada, T. and Taylor, P. H., "Laboratory Scale Thermal Degradation ofPerfluoro-octanyl Sulfonate and Related Precursors," Final Report, 3M Company, UDR-TR-03-00044, July 2003. Appendix A Experimental Condition (Temperature, Flow Rate, and Pressure) and Total Ion Chromatograms for In-line GC/MS Analysis A -l Appendix A FIGURE LIST OF FIGURES Al Total Ion Chromatogram for Untreated Article Combustion at 600, 650,700,725,750,750 (duplicate), and 1000C A2 Total Ion Chromatogram for Treated Article Combustion at 600, 650,700, 725,750,750 (duplicate), and 1000C A3 Total Ion Chromatogram for Fluorinated Acrylic Polymer Combustion at 600, 650, 700,750, 800, 850,900,950,1000, 1000 (duplicate), and 1000C (triplicate) LIST OF TABLES TAttTF. A l Flow Rate at Different Temperature A2 Experimental Condition of Untreated Article Combustion Test (Before and After) A3 Experimental Condition of Treated Article Combustion Test (Before and After) A4 Experimental Condition of Fluorinated Acrylic Polymer Combustion Test (Before and After) A-7 A-8 A-9 PAGE A-3 A-4 A-5 A-6 A-2 Table A I. Nominal Flow Rate at Different Temperatures T(emC)p 660500 777025500 898900550000 1000 (mInLl/emt i1n) 1122..18 11111110....5204 1990...620 8.8 (mInLl/emt 66i2n..14) 555...865 54454.....28064 A-3 Table A2. Experimental Condition of Untreated Article Combustion Test (BBUUBSBUUBBUUBBUUBBUUBBUUUBBUballllllTTCllTlTelTTllTTTllTTTTTaaaamaaaaaaaaaafnnnnnnonnnnfnnnnpakkkkkkkknkkkkkklfedt(()"baitfeitfo))ns S6666666677777777777777771111C0005055500020222e55555555000000000000000550550t00000000000T0000b Fm.LR/m. Iien 11111111111111111811188118112222222111111111000..0.00.119689........................118999231953143491999990 Fm6666666655555555555554455454.............................151L4440780777575566556664244R/m. 2idn were monitored and logged (Before T3323322333332223223322333233C0090099000009909990099000090I1900099001000991999019900092e and T3333333333333333323323323333C000000000000000000090900090021110100010000011020911091109e A fT3333333t333333333333333343555Ce20210124424374777346644940233r5253399855141756740680769792`) T6666676667777777777777771111C005005052000222255555554000041111100502225664000000090000'1000 before and after the experiment. T3333333334444333433433335566C424435458111188817819788118955833009727350614614604160842' Blank: T3332333333332222223322223443C000091101109919919999199000661530715326550537549777806662" I----------------------------11111111111111C11111111111111T22322223222233222222222222225555750058555008755555985373 blank experiment PaAAAAAAAAAAAAAAAAAAAAAAAAAAAArt.........m........e...........PPPPPPPPPPPPPPPPPPPPPPPPPPPPs*............................ before cboRmebacutsotirosne,tUteTm:puenrtarteuarteed article cdefRIMInnelelaeeacttst2u1orrffellpodorwwetesrmsraautptreeee,raAtuPr:eaatmt eoascphhperoiscitpiorenssure A~4 Table A3. Experimental Condition of Treated Article Combustion Test BBS(TTballRReaamfnn/pakklfet(()8bafetf)) B lank BTTRlRa n k "Plank RTTRlRa n k R lank BTTRlRa n k R latik BTTTTRRlRRa n k "BTTaRRRlClaaonnkknditions .wS6666666677777777777777C111100005555e0e0002222555555000000000000r00t0055550000000000Te0000bm _____________ oFmn11111111111111111111811888.2222i22221111L11110100...10.tR......9.98.9.....o..8.89.1.8..00../054543222990909m.reIiden anFm666d66666555555555555545444..............3..3.3L.4.2.l2...20.27..7985544R6666555o544/m.g2gianed (Before and T32223332222333322333323C22209990009999000099000090999I09990009991190099000e092999 T33232333333233332323333233C00900900000090020909000009010911090101019229090100B090 AfT33333333t33333333333333555C541e2110112323777574555533333130159r22638932144944366254)____T66566666777777777777771_111c000954550000252225555540000_10019900102107175411000000_1102____T333333333334344433333_36666C26323333661611719999919_11157044525851014314056188922_4' ____T322333333333222222222424_44C09900100101909999999299132_658715051389568498997597904_' ____I--------------------------11_111111C1111111111111T111112223222222222222232222222255505853585855365508555557 PaAAAAAAAAAAAAAAAAAAAAAAAAAAtr.m............e..........P.PPPPPP..PPPPPPPPPPPPPPPPPPPs...................f......, before and after the experiment. Blank: blank experiment before combustion, TR: treated article bReactor set temperature 0defRMIInnelelaeeacttst21uorrffellpodorwwetesrmrsaautptreeee,raAtuPr:eaatmt eoascphhpeoriscitpiorenssure A-5 Table A4. Experimental Condition of Fluorinated Acrylic Polymer Combustion Test ______________________________ (Before and After)_________________________________ Sam ple" S e t T b F . R . l c F . R . 2 d T 1* T2` T3e T 4 T5e T6e T7` Presf (b ef/aft) C m L /m in m L /m in C C C C C C C atm B lan k (bef) 600 1 2 .8 6.5 250 250 304 602 334 305 -1 2 5 A .P . B lan k (aft) 600 1 2 .7 6.4 251 250 299 600 327 312 -1 2 5 A .P . PM 600 1 2 .7 6.3 250 250 295 599 314 309 -1 2 5 A .P . PM 600 1 2 .9 6.3 250 250 293 599 313 306 -1 2 7 A .P . B lan k 650 12.1 6.1 251 251 295 651 328 295 -1 2 5 A .P . B lan k 650 1 2 .0 6.1 249 249 294 650 329 297 -1 2 8 A .P . PM 650 1 2 .2 6 .2 250 250 295 650 330 308 -1 2 5 A .P . PM 650 12.1 601 250 250 295 650 330 301 -1 2 8 A .P . B lan k 700 11.5 5.7 249 251 307 700 357 307 -1 2 5 A .P . B lan k 700 1 1 .6 5.8 250 250 310 702 357 303 -1 2 4 A .P . PM 700 11.4 5.9 251 251 314 700 358 310 -1 2 5 A .P . PM 70 0 11.5 5.8 249 251 314 701 360 309 -1 2 8 A .P . B lan k 750 1 1 .0 5 .4 249 250 318 750 374 312 -1 2 5 A .P . B lan k 750 1 0 .9 5 .4 249 251 323 750 379 311 -1 2 5 A .P . PM 750 11.0 5 .4 250 251 331 750 385 317 -1 2 5 A .P . PM 750 10.9 5 .4 249 251 332 748 387 303 -1 2 7 A .P . B lan k 800 1 0 .4 5 .2 251 250 356 801 416 310 -1 2 5 A .P . B lan k 800 1 0 .6 5.1 251 252 357 800 420 307 -1 2 6 A .P . PM 800 1 0 .4 5 .2 251 250 361 800 423 305 -1 2 5 A .P . PM 800 1 0 .4 5.1 250 251 362 800 424 310 -1 2 6 A .P . B lan k 850 10.0 5.0 251 250 361 849 436 296 -1 2 5 A .P . B lan k 850 10.0 5 .0 251 251 369 850 444 296 -1 2 8 A .P . PM 85 0 10.1 5 .0 251 250 388 851 458 318 -1 2 5 A .P . PM 850 10.1 5 .0 249 250 390 850 462 315 -1 2 7 A .P . B lan k 900 9 .7 4 .7 250 250 411 900 491 321 -1 2 5 A .P . B lan k 900 9 .6 4 .7 250 252 414 899 492 326 -1 2 8 A .P . PM 900 9 .7 4 .7 251 250 420 899 500 296 -1 2 5 A .P . PM 900 9 .6 4 .7 251 249 425 900 505 297 -1 2 6 A .P . B lan k 950 9 .2 4 .7 251 250 443 951 530 302 -1 2 5 A .P . B lan k 950 9.3 4 .7 250 250 449 948 533 320 -1 2 4 A .P . PM 950 9.3 4 .7 250 250 456 948 540 331 -1 2 5 A .P . PM 950 9 .2 4 .7 252 250 461 948 545 332 -1 2 8 A .P . B lan k 1000 8 .9 4 .4 251 250 486 1001 579 334 -1 2 5 A .P . B lan k 1000 8.9 4 .4 252 250 492 1001 586 328 -1 2 3 A .P . PM 1000 8.9 4.5 251 250 499 1001 589 349 -1 2 5 A .P . PM 1000 8.9 4.5 250 251 505 1002 595 352 -1 2 3 A .P . PM 1000 8.9 4.5 256 250 524 1002 601 359 -1 2 5 A .P . PM 1000 8.9 4.5 256 250 520 1001 606 369 -1 2 3 A .P . PM 1000 8.8 4 .5 250 251 520 1001 607 360 -1 2 5 A .P . PaCM onditions w1e0r0e0mon8it.9ored and4l.o5 gged 252 before 251 and after 525 1001 the experiment. 610 Blank: 363 blank -1 2 3 A .P . experiment before combustion, PM: fluorinated acrylic polymer bReactor set temperature cM et 1 flow rate dM et 2 flow rate eMeasured temperature at each position fReactor pressure, AP: atmospheric pressure A-6 Abundance 1 ,5e+07 1e+07 05 0 0 0 0 0 0 T im e --> Abundance -I----1-- I-- I-- r~ 5.00 10.00 TIC: U T 60-2.D 15.00 20.00 25.00 30.00 35.00 1 ,5e+07 1e+07 05 0 0 0 0 0 0 T i m e --> Abundance T IC: UT65.D A 5 .0 0 10.0 0 15!o O 20 !oO 25^00 3 0 .0 0 3 5 .0 0 1 ,5 e + 0 7 1e+07 05 0 0 0 0 0 0 T im e --> Abundance A 5.00 TIC: UT70-3.D i --i-- --i--*11 , ^ --i--i--i--i--i--i--i--i--1--i--i--i--i--1 r 10.00 15.00 20.00 25.00 30.00 35.00 1 ,5e+07 1e+07 05 0 0 0 0 0 0 T i m e --> Abundance A 5.00 TIC: U T73.D I T-!"' '|1 -i--i--i--\--i--i--i--i--|--i--i--i--i--| i i i i r 10l00 15^00 20i00 2 5 .0 0 3 0 .0 0 3 5 .0 0 1 ,5e+07 1e+07 05 0 0 0 0 0 0 T i m e --> Abundance TIC: UT75.D 1 -- I I - I -- I-- I 1-- I-- I-- I-- I-- I1 " I " 1-- 1 1-- r -- f - 1 -- T-- 1-- I-- |-- I 1 1 I I i I I I I I r 5.00 10.00 15.00 20.00 25.00 30.00 35.00 1 ,5 e + 0 7 1e+07 05 0 0 0 0 0 0 T im e --> Abundance TIC: UT75-2.D --t--i--i r r i --j--i--i--i--i--|--i--i-- i i i \ i 1 i 1 1 1 1 I 1 r 5.00 10.00 15.00 20.00 25.00 30.00 35.00 T IC : U T 9 9 -1 .D 1 .5e+07 1e+07 05 0 0 0 0 0 0 A >i111 '"-r 5.00 10.00 15.00 20^00 25^00 30.00 35.00 T iFmigeu--r>e A l. Total Ion Chromatogram for Untreated Article Combustion at 600,650,700, 725,750,750 (duplicate), and 1000C A-7 Abundance TIC: T R 60-2.D 1e+07 5000000 T i m e --> 0 *t- r Abundance -I--I--i--i--I--I--i--r *M,~y jMM^-^ T `n --'--r~ 5 . 0 0 1 0 . 0 0 1 5 -OOj j q ? t r 6 5 d ' 3 0 . 0 0 3 5 . 0 0 1e + 0 7 5000000 /iJIi/ \\\\ Abundance 1e+07 ' ' 5.00 A Yoloo ,, 1s l o o ^ f g ^ i o o | I i "> i i 'i..r-i--t 3 ; 35 00 5000000 T i m e --> 0 Abundance 5.00 10.00 1e+07 IA\ L^ 5000000 v Abundance 1e +07 --i--i--r 5.00 C\ 10.00 I\ 5000000 J - r - i--i--i--r "i--1--i" 1 5 .0 0 y |q 9 t R73^D-30 I 1 1..r_I~ 1 5 .00y|Q? -pR75D'33 I ` 11 1 I '.. 30.00 35.00 i i r 11 'i.."i i | ' * T' 30.00 35.00 T i m e --> 0 Abundance 1e+07 '-->--i--i ~r""ni--i--\ i i i i | i > ^ r1"1 ' 1 1 r 1 1 1 1 i 1 1 ' 1 A 1* 1 5 ' ^ r 5.00 f\ 1 0 . 0 0 1 5 -0Ch c l T R 7 5 - 2 CD 3 0 0 0 3 5 0 0 rJ5 0 0 0 0 0 0 / A T i m e > 0^-1--1--I--i--I--i'T -- 1--i--I--l--i--i--i--I--r-- i--r T f~h--i l i I r--i i i I i i l I I I I I Abundance 5 . 0 0 1 0 . 0 0 1 S . O C j . , ^ TM g _ ^ D0 0 3 0 . 0 0 3 5 . 0 0 1e+07 If\\ 5000000 TTFiiimmg ueer----e >>A 200. Ti l\ oitai l \ iIo| ni Ci hfro` mi ai to' gir ai ml / '"f'o-imr T1reia1te1d1A1r.t..i.c..l.e....C...o..m. b' u`st`i_o1ni a1t 16 01T0`,615' 0 , 7 0 0 ,7 2 5 , 750,750 (duplicate), and 1000C A-R Abundance 2e+07 AT ibmuen--d a>n c e 2e+07 TAibmu en--d a>n c0e 2e+07 TA ibmu en--d a>n c e 2e+07 TA ibmu en--d a>n ce 2e+07 TA ibmuen--d a>n c e 2e+07 TAibmuen--d a>n c e TIC: PM60-2.D i ... , 5 . 0 0 1 0 . 0 0 1 5 . 0 0 T IC2 :0 .P0M0 6 52.5D. 0 0 3 0 . 0 0 3 5 . 0 0 S.0 1 0 .!0 0 ,, 1 5 .!0 0 T I i C21:0 .P0gM0-iV7i-0,r2--l5D-T. 0-r0-T'- i3 0 .I0 0i.......3.. 5 . 0 0 ~~~i5 . 0 0, i11i 1 0 . 0 0 1 5 . 0 0 T I C2 :0,..r^=acsra,--,--... .P0M0 7..5.2...5D.r0 01 1 3"r0~.i0 i0" r 3 5 .i010 ~r5 . 0 0 1 0 . 0 0~l--'--'--1 ... 1I5I. 0--0 iT--iI--C2I--:0 .I--P0rM0-1--8 0I--2.I--D5 |.-0.0 . 3 0 . 0 0 3 5 . 0 0-I -| r i- r , - 1 . i 5 . 0 0 1 0 . 0 0 1 5 . 0 0 T IC2 :0 .P0M0 8 52.5D. 0 0 3 0 . 0 0 3 5 . 0 0 5. 0...0.........1..0| .i0 0i i li1 5! . 0 0 T IC2 :0 .P0M0.s\.9 0i2.f5D1.i0' 0i 3<0 .i0 0 3 15 .l0 0 2e+07 TIC: PM 99-3.D TAibmuen--d a>n c0e 2e+07 5 . 0 0 1 0 . 0 0 1 5 . 0 0T IC2: 0P.M0 09 9 -245. .D0 0 3 0 . 0 0 3 5 . 0 0 TAibmuen--d an c e 2e+07 T i m e --> 5.00 ^_ t? A n 10.00 4 a A rt 1 5 . 0 0T IC2: 0P.M0 09 9 -255. .D0 0 /I( 30.00 35.00 Figure A3. Total Ion Chromatogram for Fluorinated Acrylic Polymer Combustion at 600, 650,700,750,800, 850,900,950,1000,1000 (duplicate), and 1000C (triplicate) A-9 Appendix B Experimental Condition (Temperature and Flow Rate) and Results for PFOA, F, and Cl Aqueous Solution Analysis B-1 Appendix B LIST OF FIGURES FIGURE_________________________________________________________________________ 2AGE B l Fluoride Analysis Result at UDRI B2 Chloride Analysis Result at UDRI B-5 LIST OF TABLES TABLE___________________________________ __________________________________M S I B 1 Experimental Condition o f PFOA, F', and CF Aqueous Solution Analysis at 1000C (All Under Atmospheric Pressure) B-3 B2 Aqueous Solution Analytical Results from EXYGEN3 B-4 B-2 Table B l. Experimental Condition of PFOA, F , and Cl' Aqueous Solution Analysis at Sihaemf/paflet'8l SCetTb Fm.LR/m. 1in Fm.LR/m.2in TCP TC2e TC3e TC4B TC5e TC6e TCT ECxit* BSBUUBBUUBBUUBBBBTTBBTTBBTTBBBBSTTBBallllTTllTTllRllRTTRRllaRRallaallaaRlaRlaaaallmaaaaaaaannnaannnnnnnmnnnnnnnnnnkkkkkkkkpkkkkkkkkkkkkpl((ebalefeftf)of)orrEUX111111111111111111111D1111111111111000000Y00000000000000000000000000000000000000000R00000000000000000G0000000000000000000000000000000000I0000EN8888888888888888888888888888888.888...........'......87...88..99.988.8...88.99.8.9.8..89889899898877777 4444444444444444444444444444.................5.55.5..4.45..45.5.5..55555544444444444 444444......555544 233333333333333333333333233390000000000000000000000090001921201222131022121020009022 333333333333333333333333333300000000000000000000000000001100232212103121220101200222 445555555555555555555555555537123233333434444444444444441316802468189303333333333333 99111111111111111111111111119900000000000000000000000000890000000000000000000000000011013222103121223112232222 555666666666666666666666666620590111111111111111211121111581178356777899999909999099 333333333333333333333333333301201222333444555556666666661254034608340578899000110000 322322333333333333333333322209090990000000000000000090993391919911100111021123209099 22222222222222222222222222224444444444444444444444444444 333333000000110002 223323909009119199 444555588022599504 111111000000000000111000 555556477089515594 333343740789117080 333333000000533222 222222444444 combustion, UT: untreated article, TR: treated article bReactor set temperature cdefTMMMeeemeattps21uerrffeallodtouwwtreermraaatptteeethraetudroewantsetarecahmpoosfitaiqouneous ' solution vial exhaust line B-3 Table B2. Aqueous Solution Analytical Results from EXYGEN* Sam ple ID PFOA r cr Notation UUTTBBKK11--12 UUUUTTTTB11B--KK1222--12 UUUUUUUUBTTTTTTRRRRRRKTTTTTTTT1BB223BBB1BBB31------KKKKKKKK11112212341234--------11112222 TTRR22--12 TTTTRRRR3B3B--KK1233--12 BTTRRKBB2KK44--12 NNDD NNNNDDDD NNNNNNNNNNNNNNNNDDDDDDDDDDDDDDDD NNNNDDDD NNNNDDDD NNDD NNNNNDDDDD NNNNNNNNNNNNNNNDDDDDDDDDDDDDDD NNNNDDDD NNNNDDDD NNNDDD NNNNDDDD NNNNNNNNNNNNNNNNDDDDDDDDDDDDDDDD NNNNDDDD NNNDDD 1stjar for blank run before 1stuntreated article combustion 2211nsnsttddjjjjaaaarrrrffffoooorrrrb1b1slsltataununnknkttrrrreueuananttebebdedefafoaorrrtrteieicc2ll1enesdtccuuoonnmmttrrbbeeuaausttsteetididoonaanrrttiiccllee combustion combustion 22211nnnssttdddjjjjjaaaaarrrrrfffffooooorrrrrb2b2blnnlladaadnunnuknkkntrtrrrureuuenannatbtebbeedeedfffoaooarrrrretteeiic3c23llrendreddcucuuononnmtmtrtrrebebeauaautstetsetedtiddiooanaanrrrttiticicclleleecccooommmbbbuuusssttitioioonnn 222H2221111111nnssnssssnsnnPtttttttddddddjjjjjjjLjjjjjjaaaaaaaaaaaaaCrrrrrrrrrrrrrfffffffffffffwooooooooooooorrrrrrrarrrrrrbbbb23t1bbb321esnllllrrnllsdltaaaarddtaaadtnnnnubttrnnnutrrkkkknerlkknkeeaeatrrarratrnarrtrruuuuetteuuuketeennnnaednnanddtdtbbbaeabbeaaafdeeearfdeerrttfffrtettiffaoooetiiacoorirccrrrrcrltrr3lleeeeti3leeeeicrecrd23c1ld2cc1lecnorsueoodsnutdomtndcmtmntcmttrtrotrrbtoerrebbeermbeeuamaeaauuauatstabttssetbettseetettueidtdeuiiddodidsoodsoantaaanntiaanrriaorrtrortttrintitiicnticicciccllclleelleeleeeccccccoocoooomommmmmmbbbbbbubuuuuususssstststtiittiiotoiiooioononnnnnn 22211snnnsttdddjjjjjaaaaarrrrrfffffooooorrrrrb3bb3lrrlldadaantnntrkrekkeararrututueennnddabaaafrfetrtteftieiorccrlr3le3eerrdcd3ctortordrmemetarabbteteuuaedstdstetiaidaororntnatiicrctllieecclceoocmmobmbuubsstutiisootninon HPLC water blank aND: compound not detected, < 10ng/L. R-4 Ngroatdaetiownast:erH, P1LstCanBdl2anndkb,oEtFtxlpeigsBuolarfneakqBlu,leE.oxuFpsBlsuloaolnurktiid2o,enTAfrolnr-a1b,llyaTnsrikls-r2Ru,neTsarut2l1-t10a,00tanUCdD,T1Rrs2tI-a2ndco2r"rebspoottnledstoofHaPqLueCous solution for 1sttreated article combustion at 1000C, and 1st and 2ndbotdes of aqueous solution for 2 treated article combustion at 1000C, respectively. Figure B2. Chloride Analysis Result at UDRI Notations: HPLC Blank, ExpBlankl, ExpBlank2, Trl-1, Trl-2, Tr2-1, and Tr2-2 comespond to HPLC grade water, 1st and 2ndbottles o f aqueous solution for blank run at 1000C, l s^and 2 bottles o f aqueous solution for 1st treated article combustion at 1000C, and 1st and 2n bottles o f aqueous solution for 2ndtreated article combustion at 1000C, respectively. B-6 Appendix C Experimental Condition (Temperature, Flow Rate, and Pressure) and Total Ion Chromatogram for Telomer In-line GC/MS Analysis C-l Appendix C LIST OF FIGURES FIGURE________________ ______________ __________________________ ______ C l Total Ion Chromatogram for Telomer Combustion at 200 and 600C PAGE C-3 LIST OF TABLES TABLE________________________________________________ C 1 Experimental Condition of Telomer Combustion PAGE C-3 C-2 S am ple" (b ef/aft) B lan k (bef) B lan k (aft) T elo m T e lo m T elo m T elo m S e tT b C 200 200 200 200 600 600 F. R. l c m L/m in 24.1 2 3 .8 2 3 .3 2 3 .7 12.8 12.7 F. R. m L /m in 1 1 .7 11.3 1 1 .6 117 6.5 6 .5 T 1' C 149 151 151 150 150 151 T2e C 151 151 151 151 149 157 T3e C 133 134 133 133 150 170 T 4' C 199 201 201 201 601 601 T 5* C 157 161 148 149 205 232 T6e C 134 139 150 149 154 151 T7e C -1 2 5 -123 -1 2 5 -1 2 7 -125 -1 2 8 Pres* C A .P . A .P . A .P . A .P . A .P . A .P . combustion, Telom: telomer sample bReactor set temperature cdefRMIInnelelaeeacttst21uorrffellpodorwwetesrmsraautptreeee,raAtuPr:eaatmt eoascphhpeoriscitpiorenssure Abundance TIC; TLM20.D Time --> Abundance TIC: TLM60.D Time--> Figure C l. Total Ion Chromatogram for Telomer Combustion at 200 and 600C C-3 Appendix D Experimental Condition (Temperature and Flow Rate) for VOC, CO and CO2 Off-line GC/MS Analysis J D -l Appendix D LIST OF TABLES TA BLE__________________________________ _-- ------------------------D1 Experimental Condition of Off-line GC/MS VOC Analysis (All under Atmospheric Pressure) PAGE D-3 D-2 Table D l. Experimental ConAdtimtioonspohfeOrifcf-PlirneessGuCre/)MS VOC Analysis (All under S am ple3 S e t T b F . R . l c F . R . 2 d M a k e u p * T 1^ T 2 f T 3 ` T 4 ` T 5 f T 6 * T 7 f (b ef/aft) C m L /m in m L /m in m L/m in C C C C C C C B lan k (b ef) 1000 8 .8 4 .3 6.7 300 302 399 1002 486 292 302 B lan k (aft) 1000 8 .7 4 .2 6.8 301 302 425 1002 507 297 303 UT 1000 8 .7 4 .2 6.8 301 302 425 1002 507 297 303 UT 1000 8 .6 4 .2 6 .8 300 300 439 1001 513 304 303 UT 1000 8 .6 4 .4 6.8 300 300 43 9 1001 513 304 303 UT 1000 8 .7 4 .3 6.8 301 302 435 1002 517 311 302 UT 1000 8.7 4 .3 6.8 301 302 435 1002 517 311 302 UT 1000 8.7 4 .4 6.8 302 301 440 1002 522 319 302 B lan k 1000 8 .9 4 .5 6.8 301 301 398 1002 4 8 4 282 308 B lan k 1000 8 .8 4 .4 6.8 302 301 416 1000 500 297 304 TR 1000 8 .8 4 .4 6.8 302 301 416 1000 500 297 304 TR 1000 8 .8 4 .5 6 .7 300 302 425 1001 508 307 303 TR 1000 8 .8 4 .5 6.7 300 302 425 1001 508 307 303 TR 1000 8 .9 4 .5 6.8 301 302 432 1002 514 312 302 TR 1000 8 .9 4 .5 6.8 301 302 432 1002 514 312 302 Ta RConditions w1 0e0r0e m on8 .i8tored an4d. 4logged b6e.8fore a nd a3f0t1er th3e0 1exp e4r3im7 en 10 t. 01 51 Blank: 8 b lan 3 k 18 300 experiment before combustion, UT: untreated article, TR: treated article bReactor set temperature cInlet 1 flow rate dInlet 2 flow rate eMakeup gas flow rate fMeasured temperature at each position D-3 Appendix E Experimental Condition (TTeemstpaenradtSuyrestaemndSFteloawmREaxtter)afcotrioPnFOA Transport Efficiency E -l Appendix E LIST OF TABLES TABLE El Experimental Condition of PFOA Transport Test (All under Atmospheric Pressure) E2 Experimental Condition of Steam Extraction (All under Atmospheric Pressure) PAGE E-3 E-3 E-2 Table E l. Experimental Condition of PFOA Transport Test (All under Atmospheric Pressure) Sam ple" S e tT b F .R . I e F . R . 2 d Makeup T 1 ` T 2 i T 3 ` T 4 * T5` T6* T7* (b effati) C m L /m in m L /m in m L/m in C C C C C C C B lan k (bef) 170 1 2 .6 6.5 6.9 171 169 170 170 214 159 165 B lan k (aft) 170 1 2 .7 6.5 6 .9 170 171 170 170 214 158 165 PFO A 170 12.7 6.5 6 .9 170 171 170 170 214 158 165 PFOA 170 12.8 6.5 6 .9 169 169 170 171 214 158 165 PFOA 170 12.8 6.5 6 .9 169 169 170 171 214 158 165 PFOA 170 12.9 6.5 6 .9 171 170 170 170 214 158 166 PFOA 170 12.9 6 .5 6.9 171 170 170 170 214 158 166 PFOA 170 12.8 6 .4 6 .9 170 170 170 171 214 158 166 B lan k 300 1 2 .7 6.3 6 .9 171 172 221 201 205 300 295 B lan k 300 1 2 .9 6 .5 6.9 169 169 221 299 305 302 295 PFOA 300 1 2 .9 6 .5 6 .9 169 169 221 299 305 302 295 PFO A 300 1 2 .9 6 .4 6.9 169 170 222 302 306 305 296 P FO A 300 1 2 .9 6 .4 6.9 169 170 222 30 2 306 305 296 P FO A 300 1 2 .7 6 .4 6.9 169 170 225 30 2 306 30 0 296 PFOA 300 1 2 .7 6 .4 6.9 169 170 225 302 306 300 296 Pa FCOonAditions w3 0e0re m o n1 i2t.o8 red an6d.4logged b6e.f9ore and a1f6t9er th1e71expe2ri2m5 ent3. 01 306 298 296 Blank: blank experiment before combustion bReactor set temperature 0Inlet 1 flow rate dInlet 2 flow rate eMakeup gas flow rate f Measured temperature at each position Table E2. Experim ental Condition of Steam Extraction (All under Atmospheric Pressure) Sam ple" S e tT b F. R . I e F. R . 2 d M akeu p' T l 1 T 2 * T 3 ` T 4* (b ef/aft) C m L /m in m L/m in m L /m in C C C C 1st E x tr a c t 300 4.1 8.2 7.9 300 300 299 300 1st E x tr a c t 300 3 .8 8.2 7.4 301 300 300 299 2 nd E x tr a c t 300 3 .8 8.2 7.4 301 300 300 299 2 nd E x tr a c t 300 3 .9 8 .0 8.1 299 300 300 299 3 rd E x tr a c t 300 3 .9 8.0 8.1 299 300 300 299 3 rd E x tr a c t 300 4 .6 8.4 8.0 300 300 295 301 4 th E x tr a c t 300 4 .6 8.4 8.0 300 300 295 301 4 th E x tr a c t 300 4.1 7.7 8.3 299 300 290 301 5 th E x tr a c t 300 4.1 7.7 8.0 299 300 290 301 a5tCh Eoxntdraitcitons w3e0r0e mo4n.i1tored an8d.0logged b8.e1fore and a3f0t0er th2e99expe2ri9m1 ent301 . bReactor set temperature cInlet 1 flow rate dInlet 2 flow rate eMakeup gas flow rate f Measured temperature at each position T 5* C 311 311 311 305 305 305 . 305 305 305 307 T 61 C 296 294 294 300 300 305 305 305 305 305 T 7* C 298 302 302 298 298 296 296 303 303 305 E-3 Appendix F Experimental Condition (TemDpeerteacttuiroenaLnidmFitloSwtuRdyate) for PFOA Calibration and F -l Appendix F LIST OF TABLES T A B L E _______________________________________________________________________ FI Experimental Conditions for PFOA Calibration and Detection Limit Study PAGE F-3 Table F I. Experimental Conditions for PFOA Calibration and Detection Limit Study S am ple* fbefi'aft) B lank (bef) B lank (aft) PFOA lfig P F O A l|xg P F O A Ifxg P F O A lp.g B lank B la n k P F O A 5|ig P F O A 5|ig PFO A 5pg P F O A 5|Xg B la n k B la n k P F O A lOpg P F O A lOpg P F O A lOpg P F O A lOpg B la n k B la n k PFO A 50pg PFO A 50pg P F O A 50|ig P FO A 50|ig B la n k B lank P F O A lOOpg P F O A lOOpg P F O A lOOpg P F O A lOOpg B la n k B la n k S etTb C 300 300 300 300 300 300 300 300 300 300 300 300 300 300 300 300 300 300 300 300 300 300 300 300 300 300 300 300 300 300 300 300 F. R. I e m L/m in 19.6 19.7 19.6 19.6 19.7 19.6 19.8 19.7 19.8 19.7 19.6 19.7 19.8 19.7 19.7 19.8 19.8 19.8 19.7 19.7 19.8 19.7 19.9 19.8 19.8 19.7 19.8 19.6 19.8 19.8 19.7 19.6 F. R. 2d m L/m in 9.8 9.6 9.8 9.6 9.7 9.7 9.8 9.8 9.8 9.9 9.8 9.7 9.6 9.8 9.6 9.7 9.6 9.7 9.9 9.8 9.8 9.9 9.8 9.8 9.6 9.7 9.7 9.8 9.6 9.6 9.8 9.7 T Ie C 301 300 300 300 300 301 299 301 300 300 300 301 301 300 301 302 301 300 302 301 300 301 299 300 300 300 300 302 299 298 300 299 T2e C 300 301 301 302 302 301 301 302 302 302 300 300 301 302 302 301 299 301 300 300 301 299 300 302 301 301 302 301 301 300 302 301 T 3" C 270 270 270 270 270 270 271 270 269 269 270 270 270 270 270 269 270 270 271 270 270 269 269 270 270 269 268 268 270 270 270 370 T 4' C 302 301 301 299 300 299 301 302 300 300 301 299 300 302 300 299 302 301 301 300 301 300 298 300 302 300 298 302 300 299 298 299 T5e C 299 299 299 298 301 300 301 301 301 301 301 300 299 299 299 300 299 300 300 301 300 300 301 301 298 298 298 298 301 300 299 300 T6e C 301 301 301 300 301 300 301 301 301 301 300 300 300 299 302 301 300 299 301 301 301 301 299 299 301 301 301 301 301 301 301 302 TT C -125 -125 -125 -125 -125 -120 -125 -123 -125 -124 -125 -123 -125 -125 -125 -125 -125 -125 -125 -128 -125 -122 -127 -125 -124 -120 -125 -128 -125 -122 -125 -124 Pres1 atm A .P . A .P . A .P . A .P . A .P . A .P . A .P . A.P. A .P . A .P . A .P . A .P . A .P . A .P . A .P . A .P . A .P . A .P . A .P . A .P . A .P . A .P . A .P . A .P . A .P . A .P . A .P . A .P . A .P . A .P . A .P . A .P . a C o n d itio n s w e re m o n ito re d an d lo gged before an d a fte r th e e x p e rim e n t. B la n k : b la n k ex p erim en t b efo re co m b u stio n . b R e a c to r set tem perature 0 In le t 1 flo w rate65 d In le t 2 flo w rate e M e a s u re d te m p era tu re at each p o sitio n f R e a c to r pressure, A P : atm o sph eric pressure F-3 Appendix G General Description of ATRS Standard Procedure, Wickbold Torch Methods for Total Fluorine, and QuikChem Method for Fluoride and Chloride in Water G -l Appendix G TABLE OF CONTENTS SECTION G1 Thermal Decomposition of Organic Materials Using the Advanced Thermal Reactor System G2 Wickbold Torch Method for Total Fluorine G3 QuikChem Method 10-109-12-2-A, Fluoride in Water (0.10 to 5.0 mg F/L) G4 QuikChem Method 10-117-07-1-C, Chloride in W ater (0.1 to 10.0 mg Cl'/L) LIST OF FIGURES FIGURE G1 General Schematic of the Advanced Thermal Reactor System (ATRS) G2 Wickbold Oxyhydrogen Torch Apparatus PAGE G-3 G-7 G-9 G-9 PAGE G-4 G-7 G-2 G l. Thermal Decomposition of Organic Materials using the Advanced Thermal Reactor System pTcesineaorhsorrneitlderdyuuUsuwmccwnttoiseiivnrnteehkgtvrawasottihilhtaoveysinergomcdshofy-afnDssrlptodseaemutmyaectbdtstoehinlgtdeioatRuytsshestcmeisunhredemrgayaorasamctulhhsardeyetIeosnmtchtgseoeetrmmianrtmptupschtaooeo.ls'nfSsdistoiei(inosrUccgtnoiDeanmongRthifpcoIpeo)fnmosEtilthtaynhitemoveenitreErhirooaeEslnfrsGmumossroeihegngnadacrtsnaeaiindlvc1eEib9mmven7eveag1ltetoirenbrpiraeceeigeagdaerlinsinancan[ogsl3iyenn-Grzt8giaer]eio.rwsnuceiopotrhfsn(snEa[p1eEse,ctcGtu2iead])d.lyhiTizanohesndisbteheen RBeagcakrgdrloesusnodf the material being studied a similar overall approach to measuring the thermal pdfrettehlefaeomfaerciwcecorptnaiimoeenttrrengpsaicpootsgyuesfac)ricosetoiaisexlo(nlsinn(eddwoacaiprntshtmerideuoodarspdnealerulnidoytcshd.dtdessuTairrcgnayhatnraestaeilefiysardiaozrc)eme,eaftdaneoopnrtxxlb)medii.y,ddiDswinaGwztaeehiCedtodaip/ncb.MtihFysitsShoctc.ynarroonTepemugixhbcglppeeiahgaolfalrisarybiaunghlctregaaiet)sgiksGohwelwniCnqtietho/uahMmefitdrdppSeeaaovetaarreraeianrrsntoaouiitlbnslryistcedisaprne,ireenseiacgseasitrdceaitenhtskaaogeetrtrren.ethmmexTiamgcatahehlpirelnseeyesilerrnavxatttgheathiumivpa(sroedueptlresysyeitszprutllaerioenctduauwta,civrlltmeliiryanoseilgnaxlr(cewetotqhdohfueretwihrrieeetsh temperatures on the order of 800C with a mean residence time of 2 s. Tetixmhceeesedsxipsatoirrsibu(iurnetieocxoncnaednsisdt,ioannemsaroa-rrseetopgirceehncieoirsmaellemytrediaces,fuipnryeerdooblfyyesxitsch)ee.sWms aeitiahrn(aetdeqemuqipuveaartlaeetnumcreee,trharoetisdoid)deemnvaceyelotbpiemmdeee,nfatinnthdeedl.erevTsehildeoenf ce ttteiaexmkmpeeopnse(uMararsetRbutTereei)mnaigpssessdurueamfttfeuiircnrmeigeiininsdtelmeydaelnfargaosraumrsroebwtdhehetahatfavltothiowperl)rureagaatncefdlto(otmwrhmeemavisdaou-ylrpuebomdeineaattsoursfosutiomhnmegedratee.atmThcehtporiemsrr.aiosTtcuhaorneeupraaeplnespdi.drToceophnrrecrieaemtcteeitmeaadnsestroudemistsihtpdreitebirnoeucnateicfoto.norris MTsssiaahmmmReiTppllaellseerv,lea(etalsshssoocstufauhglemacxhnuicnsleoaogsntlseciddtoahsmiferrmopofoamlreydrtetefnhlruoceoiotidrfnbsm1ve(0eeleriasasqessiuocuiil.nrdyeFstdioonarfntClrlodoOowdng2uga,rcseHaeert2edsMO)st.io,RsTeTtehthcssee.t)tierhmaesetnaaicpdmtetlorduaertgfliasorfoytnliomsvtoweeftmhcaeoesxanscctucehamesensfmpitaxrtiiaiecortdainfolornsoarhstxseoyoo.uglfTliedodhnxbesydaengemocemhpmnaeleiancnsnkdadeilosdf. the mTsaGemtAhpoldedasitbsaytoohbeetavaitanipneogdrtuahtneedmsemratathlael qfsiuaxamendetirctaioetnes.doTitfihotehnersasotaefmospaflmeevpualsepionsrgizaeati,opanytmrforoopsmrpohbtheere,eap, radonebvdeihcceeaadnteibnsegigernasettdeim.toatveadpuosriinzge ASytsytpemica(lAfTloRwSr)esahcotowrnsyinstFemiguurseedGflo. rTthhiesrmsyasltedmeciosmupnoiqsuiteioinn rtehsaetatrhcehdiesstihgenAaldlvoawnscoedptTichaelramccaelsRsetaoctthoer rtasiaiihnnneynnaelstsaderurctlotmeytllsdaoimtqaituirseclucisdainditodnliceeo-dtslcnpnhuyeochadspomlatteoeefspspnsmeghuodtawossrseseaitn-cotom,ihtocolilopynhnniuqlned.ceusemeAosiic,pnndisteacgte-rn,nsadothdlodhlvoerrleaeeiwnsadastomnacalsamtuiaioncdnlmprdrt-yispFl-pecohpmiloggeaiunnauesiintypenrnreeoiolsbcecsGdaetteimsuenlc;dcitponttaeithlnlrooeelefdosnattuwA,chwaceren-Tthe.vedrRaiTdoecchSlahhtaueocettmcmtrehoor,reaeinroagyasintgchnhibdestlronteteotesrertumfaooaifgntoupsfthsserseafedhrtemmhraerewteaaubalitticclrteenyehotdreosincsartstioprlnryaasneoss.nscaltsTlsiedieesafmhdmtdelseirsptbii.onlfrloiloTyftnonrbaheowaetsedtnos.htudrhTecfecorroiahtnmoirnceoluvttianohrgnelelerehnoyaftfcteihotgeoenadsrsae-ils hhacoecauotsmetrdamcwoeiddthattioenpriertseavcoetwonrntscsaomsoallalrlregtgueiboaenssf2uwcrmnhaecirnee dareniaadmcmteotareyprrbaonedduinc2dt5secpmmeanlydoenbnget.llyToshhteetahetxreohduatguohst1c,lo2inn0ed0efCrnos.maTtihtohene.furTerhnaecatcoercisan G-3 cryogenic interface is a shell and tube design in which the shell can be cooled to near liquid nitrogen tiTenemcdoplnaedrreasntausmraepbsllee(-cp1or9ol3ldeucCct)ito.s,nTthbyiapsgicpsaeflrolmyr isctesaprtbahroeantcemoalolnenacoltyxiosidnise.oTafnhadlelmabnueatthltyhatneicela,ilgcshaytnesbstetemrecaouclslteeodcrtpoednroatdhtuetchAtesT.eTRxhhSeaiussat vHeenwt ilnett FPEaDckaanrdal5y8si9s0o/5f9th7e0 rGeaCc/tMorSp/rFoIdDu.cTtsh.eFGuCrthoevrednectaainlsboefftihtteedAwTRithS daurealpcroesluemntnesd fionrGsirmahualmta,neetouals. M[9S]. and Figure G l. General Schematic of the Advanced Thermal Reactor System (ATRS). Generalized Standard Operating Procedure System Preparation Pthraiot rthtoe dinetsriordeduceixnpgetrhime seanmtapllceo,nadcittiivoantse aseret-epsotianbtlsisfhoerdt.he various temperatures and flow rates to ensure Analytical System 1. Panreaplyasriestphreoignr-alminse (GteCm/FpIeDra/tMurSe parnoaglyratimca,lsscuabnsnyinstgemraningeas,stdaentde-cbtoyrmseondseitwiviitthy,theetca.)psperot pasripateer manufacturer's SOP. . Inlet. Exhaust Line, and Cold Tran Temperatures 2. Ceahcehckcotnhterosellteprotoinetsnsounrethtehaint ltehteytemarpeeprraotupreerlcyocnytrcolilnlegrsa.bOoubtsethrveeirtrheespinedcitcivaetesdettepmoipnetrsa.tures of 3. Check the dial settings on the variable transformer controlling the exhaust line heaters and the exhaust line temperature to ensure that it is stable. G-4 4. Check the dial settings on the variable transformer controlling the cold trap enclosure heater and the cold trap temperature. Observe the indicated temperature to ensure that it is stable. Reactor Gas Feed Rate 5. Ca hbuecbkblteheflosewttimngesteornatththeeflcoowldctoranptrovlelnetr.sAtodtjhuestitnhleettochtaalnfnloelws.asMneeaesduerde ttohethtoetadlesfliorewd rvaatleueu.sing Reactor Temperature 6. Cenhseucrke tthheatstehtepcooinnttroonlltehreisreparcotpoerrtleymcpyecrliantugraebcoounttrthoellesre.tOpbosinertve the indicated temperature to Cold Trap Preparation and Effluent Collector 7. Cdehwecakr wcoitlhd tlriqaupindintriotrgoegnepnu(rogreoitsheorncsotaonladn-tbyas(rmeqetueirriendg).vCalhveectkwtohetucronlsdotrpaepn)t.emFiplletrhaetucreo.olant Adjust nitrogen flow so that the cold trap temperature is correctly set 8. Attach a Tedlar sample collection bag to the system exhaust port. Check the sampling valve is in the VENT position. Reactor Operation Once the system is ready, the sample may be admitted and a test conducted. Test Monitoring 9. Wlevheill.e tAhlesosammopnleitoisrbtheeinrgeaacdtmorittteemdptoertahteurAe.TRS, monitor the cold trap temperature and coolant After the sample has been introduced to the system, continue the test monitoring for 2 minutes to ensure complete transport of sample through the system. Post-Test Operations 10. Continue to monitor the coolant level and cold trap temperature. 11. Set the Tedlar sample bag valve to VENT, stopping the collection of exhaust. 12. Switch the reactor carrier gas OFF and the helium purge system ON. Wait for 2 minutes before proceeding. ' 13. Switch the analytical system from stand-by to active and hold at initial conditions. 14. Seal the cold trap vent. Observe the rise in total system pressure and adjust the flow of helium so the initial pressure is correctly set. 15. Initiate analytical system data acquisition program (i.e., switch from hold to active). G-5 16. Switch cold trap coolant OFF. 17. Monitor analytical program as per manufacturer's SOP. Td[1eh0ve,eAl1o1Tp]R,edSthoams ebeetetnhuesreedqutoirecmonednutsctosfeCveartaelgporroygHraImansdfoIVr thQeuUal.iSty. EAPsAsuuranndceerPorpoegrraatimngPglaunidse(lQinAesPPs) References 1. WAn.aAly.sRisuobefyS,ta"bDileisziegdnPooflayaScyrsytleomnitfroilreSFimibuelrt,a"nReoepusorTthUeDrmRoI-gTraRv-i7m1e-2tr8ic,-SGeapsteCmhbroerm1a9to7g1r.aphic 2. W. A. Rubey and D. S. Duvall, "Description of Apparatus for Conducting Isothermal Aging - E19v7o2lv. ed Gas Analysis Tests with High-Temperature Polymers," Report UDRI-TR-72-01, December 3. Dan.dSR. DeluavteadllPaensdtiWcid.eAs,."RUuSb-eEyP, A"Lraebpoorratt,oEryPAE-v6a0lu0a/2ti-o7n6-o2f9H9,igDhe-Tceemmbpeerra1t9u7re6.Destruction of Kepone 4. W. A. Rubey, "Design Considerations for a Thermal Decomposition Analytical System (TDAS)," US-EPA report, EPA-600/2-80-098, August 1980. 5. DJ.eLc.oGmrpaohsaimtio, nWP.rAop. eRrutibeesyo,fBT.oDxieclliOnrggearn, iacnSduRb.stAan. cCeasr,n"ePsr,o"cDeeedteirnmgsinoaftio19n8o2fSthuemTmheerrmNaatlional Meeting of American Institute of Chemical Engineers, Cleveland, OH, August 1982. 6. WDUen.ciAte-mG. RabusebrCe1hy9r,8oI2m..Bat.oFgirsacpuhsi,caSnydsJte. mL.,"TRorerpeos,rt"fDoersUcrSi-pEtiPoAn ,anCdooOppeerraatitvioenAogfraeeTmheernmt CalRD-8e0c7o8m1p5o-s0i1ti-o0n, 7. TJ1.9hL8e.4rm.GaralhRaemac, tWor. SAy.sRteumb,e"yR, aenpdorIt.fBo.r FUiSsc-EusP,A"D, CesoiogpnearnatdivEevAalguraeteiomneontfCthRe-P8r0o7to8t1y1p-e01P-a0c,kMagaerdch 8. WDi.aAgn.oRsutibceSytuadnidesR,". ARe. vGierawnto, f"DSceiseingtnifAicsIpnescttrsumofeantMs.o5d9u.l2a6r5In,1s9tr8u8m.entation System for Thermal 9. mGroanhoacmh,loJr.oLb.e,nBzeernme.a"nJ,.JP. hMo.t,oacnhdemD.ePllhinogtoebr,ioBl..,A"H: iCghh-eTme.m. 7p1e,ra6t5u,r1e9t9h3er.mal-photolytic oxidation of 10. J. L. Graham, B. Dellinger, J. Swartzbaugh, "Category III Quality Assurance Project Plan for DJuelyve1lo9p95m.ent of A Photothermal Detoxification Unit," Cooperative Agreement No. CR819594-01-0, 11. PMJ.hLaor.tcoGhthr1ae9hrm9a6ma.l, TBr.eDatemlleinngteorf, HJ.ySdwroacratzrbbaoungVh,ap"CorasteUgsoirnygIMVeQrcuuarlyityLAamsspusr,a"nCceonPtrroacjetcNt oP.la6n8-fCor2-0108, G-6 G2. WICKBOLD TORCH METHOD FORTOTAL FLUORINE 1. Introduction "qfoTurahmneteictaaasrtubivoreen"m-faelnunaotlroyinfsiefslbuooofnrfidlnueiosirneinxoecreginpatnoioircgnaacnlolimycpsctooruomnnpdgos, uainsndd"sc.eox(mKtrbeisumssaet,iloy1n9v9iing8o)arnoTuohsxeyc"homynddoristotigovenignsoafrlroaeumnse"e"etdereecfdhenfriorqerudeto as the Wickbold torch. (Kissa, 1998) 2. Apparatus A typical configuration for the Wickbold oxyhydrogen torch apparatus as described by Sweetser (1956) is shown in Figure G2. Figure G2. Wickbold Oxyhydrogen Torch Apparatus. G-7 3. Method Description The sample size for the standard sample boat is up to 20 mg for a solid or up to 5 mL for a liquid. With the oxyhydrogen torch in operation, the sample is pyrolyzed or vaporized with a Bunsen burner mtihnoetvhoiexnysgagomennp-alheryatdoilrfoblgueeolonrwifdleathmieoenv.cohlTaahmtielbizreearstoiuoplnteinrcaghtaifnmlugboaertird.uepTithooenavipsapparboosrxsoimrabnaedtdepliyynr2toh0ley0s0cioslCplertcootdiomuncitntsoearwareelirzsecwotenhpteat iftnhluirnoogruignhe water or an alkaline solution. The absorbed fluoride ion is measured via fluoride ion-selective electrode or ion chromatography. Tmexhgee/mkrgep)pl.iofirTetehddeblayicmtcoiuttraoalcffyqluuooafrnitnthietiasvtmiaolenutehfsoordotffoo7ta5rl.d3fe5ltu%eormrtionine7a5vt.ii8oa4nt%hoeffWtoortiacPlkTfbFlouElodrwiTniotehricknhnfmoluweotnrhintooadttaeisldf0pl.uo5olpyripmnmeerc(so0in.s5tent of 76.0%. (Sweetser, 1956) 4. Safety Considerations Uhshasizeealroddfi.nhgSyadafnreodogepelnearbpaortieroasnteenotssfatfaheeptyootdxeeynvhtiiycadelsrfoibrgeyeanwntedolrle-cxthrpailisonsaeisdosnpuerherasdzoabnrynde.thlUeatsueaseqooufafolxsipfyiegecdeinalalpibzroeersdaetenoqtrsuyia.ppmoetnent twiailthfire 5. References KMChiasersmcae,ilsEtD.rye"k-Ak2nenradlSyEusdirsfiatoicoftnaAn, ntRiSoecvniiiescneFcdeluaSnoedrirniEeaxst,pevadnoSdluuemrdf,aece7tda3int,et1sd9,"b9y8C.JhoahpnteCr 8roisns.Anionic Surfactants: Analytical CSwomeebtsuesrt,ioPn. BM.e"tDhoedc,o''mApnoalsyittiiocnaloCfhOermgiasntricy,Fvluool.r2in8e, pCpo.m1p7o6u6n-d1s76b8y,1W9i5c6k.bold.. Oxyhydrogen Flame G-8 G3. QuikChem Method 10-109-12-2-A, Fluoride in Water (0.10 to 5.0 mg F7L) - Principle Fluoride is determined potentiometrically using a combination fluoride electrode and the Lachat jwQunhuciickthiCohanepimsotoFefnlotthiwaelIainsnjneducetlviaeorlnoliApqeundiadlb-yjyzuefnlrcu.toTiorhindeetyflipuoeonsrai.ndTdeheeenlecrceltofresoredesentchceoencfesluilslotisrsidoaefA-asgela/nAnsitgthiCvanle/uCcmrly- sfclteuallol..riTdheecrreyfsetraelnacceross - Interferences - 1. T(1h,e2-pcoylcylvoahleexnytlceanteiodnins,itSriil4o+t,eAtrla3c+,etaincdaFcied3)+,isinatderdfeedretobyprfeofremreinntgiaclolymcpolmexpelsexwtihthesfelucoartiidoen.sCaDndTA Felei3m++in/Lat.e this interference when these concentrations do not exceed 3.0 mg Al3++/L and 20 mg 2. NFoPrDUESSumseornsidtoertienrgmbinugt iTsontoatl roerqTuoirteadl DfoirssSoDlvWedAFmluoonriidtoer,inthge. Bellack distillation is required for G4. QuikChem Method 10-117-07-1-C, Chloride in Water (0.1 to 10.0 mg Cl'/L) - Principle tTaThbhheseioopcrcrbaeyalsainebnncraecateetiisoioonpfnrfcoeiusprrrovliicrebtieiioosrnannat,oelfdnrtoe-fleritnohtehmeaiocrm.hc.yleorarcniudaretiecciotohnnicofeconyrtmaranstaittoheneb. hyFietghrhreilcyfotchromilooacrtyeioadnnfaeotrefrisacobltsuhobirolbecsymsatnerraoctneug,rlioycfacwth4hloi8cr0ihdnethm. eI.n - Interferences - 1. tShuiobssutalnfactees).which reduce iron (EH) to iron (II) and mercury (HI) to mercury (H) (e.g. sulfite, 2. iHnatelirdfeersewnchei.ch also form strong complexes with mercuric ion (e.g. Br, T) give a positive 3. mstIhfuaesagpnsneytaecnqsteiduudaemrsidntisitooemnnrfsouermsfitinanbgyteemprpfrareeetrcrpeiiaxnpr.cieteIadsftetiahnrieiftshptewer,eoicsnaectleniubrtrfrvieanertisisnoudgnfiffmcifcueairrtevrsnieixtgscnisnoihfnsoitcceueaalnnddttrlboyaeft,ipiotnhrneew.pnaattrheeerd.reCiniaswlcinaiutteemrrfaeanrneddnicne,thaend G-9