Document MJ9OdN2e2ygZ2jDO0n4mwRqZ9

ARRRG -- 1367 'UDR-TR-03-00044 Final Report - LaboratoryScale Thermal Degradation of Perfluoro-Octanyl Sulfonate and Related Substances June 2003 002039 Final Report Laboratory-Scale Thermal Degradation of Perfluoro-Octanyl Sulfonate and Related Precursors "Thisreportcoversthe efforts perf byo thr eUnm iveersidtyofDaytonResearch Institute (UDR), EnviSrcieoncenanmdEneginneeritngGaroulp, Dayton,OH 454690132,duringtheperiodfromMarch2001toDecember2002.Thework wasconducted under aLetterofAgreementdatedMarch20,2001. Theworkwasadministeunrdeedr thedirectionofthe3MEnvironmentalLab,ET&SS, andtheProjectMonitor wasExicA. Reinerand Dan C. Hake. `The UDRI Program Monitors were Philip Taylor and Tak Yamada. Pukip H-Tagles Dr. Philip Taylor Gli3k3 Date lod Zener 05 Dr. Tak Yamada Date 002040 | TABLE OF CONTENTS SECTION PAGE Executive Summary viii 1 Background 1 2 Phase I: Objectives and Test Protocol 3 3 Phase II: Method Development 6 4 Phase IIT: Revised Test Protocol 8 5 Experimental Results 9 5.1 SO Transfer Efficiency Test 9 52 Laboratory Spike Analysisfor PFOS 9 53 Heated Blank Combustion Analysis 9 53.1 In-line GC/MS Analysis 10 532 OfflineGC/MS Analysis 1 533 Reactor/Transfer Line Extraction 12 and LC-MS Analysis 54 Combustion Tests 54.1 PFOS Combustion Tests 13 13 54.11 In-line GC/MS Analysis 1s 54.12 Offline GC/MS Analysis 16 54.13 LC-MS AnalysisofExtracts 17 542 54.1.4 LC-MS AnalysisofPUF Cartridges FC-1395 Combustion Test 18 18 542.1 In-line GC/MS Analysis 5422 Offline GC/MS Analysis 19 20 5.4.2.3. LC-MS Analysisof Extracts 21 5.42.4. LC-MS Analysis of PUF 21 543 FC-807A Combustion Test 2 543.1. In-line GC/MS Analysis 5.43.2. Off-line GC/MS Analysis 23 2 5.4.3.3. LC-MS Analysisof Extracts 25 5.434. LC-MS Analysis ofPUF 25 002041 | TABLE OF CONTENTS (continued) SECTION PAGE 5.5 2 Heated Blank Combustion Analysis 2% 55.1. In-line GC/MS Analysis 26 552. Offline GC/MS Analysis 27 553. LC-MS Analysis of PUF Cartridges 23 56 Transport Efficiency Tests for PFOS 23 56.1 1* Transport Efficiency Test 28 562 2% Transfer Efficiency Test 29 5.63 3" Transfer Efficiency Test 30 57 Sulfur Recovery Rate as SO, SOF, and SO:Fz 2 58 Extracted lon Analysis 34 6 Discussion 38 7 Conclusions a 8 References 2 APPENDICES 002042 FIGURE 21. 531. 532. 533. 534. 54.11. 5412. 5413. 54.14. 542.1. 5422. 5423. 5424. 543.1. 5432. 5433. 5434. 551. 552. 553. LIST OF FIGURES Schematicofthe System for Thermal Diagnostic Studies Inline GC/MS Ion Chromatogram for Heated Blank at 600C Inline GC/MS lon Chromatogram for Heated Blank at 900C Offline GC/MS lon Chromatogram for Heated Blank at 600C Offline GC/MS lon Chromatogram for Heated Blank at 900C In-line GC/MS fon Chromatogram for PFOS at 600C In-line GC/MS fon Chromatogram for PFOS at 900C Offline GC/MS Ion Chromatogram for PFOS at 600C Offline GC/MS Ion Chromatogram for PFOSat 900C In-line GC/MS Ion Chromatogram for FC-1395 at 600C Inline GC/MS Ion Chromatogram for FC-1395 at 900C Offline GC/MS Ion Chromatogram for FC-1395 at 600C Off-line GC/MS Ton Chromatogram for FC-1395 at 900C Incline GC/MS on Chromatogram for FC-807A at 600C Indine GC/MS Ton Chromatogram for FC-807A at 900C Offline GC/MS lon Chromatogram for FC-807A at 600C Offline GC/MS lon Chromatogram for FC-807A at 900C In-line GC/MS lon Chromatogram for Heated Blank at 600C Inline GC/MS lon Chromatogram for Heated Blank at 900C Offline GC/MS lon Chromatogram for Heated Blank at 600C PAGE 4 n n 12 12 16 16 17 7 2 20 2 2 2 2 25 25 27 27 27 002043 LIST OF FIGURES (continued) [FIGURE PAGE 554. Offline GC/MS Ton Chromatogram for Heated Blank at 900C 2 57.1. SO; Calibration Curve (Molar Number vs. Peak Area) 3 58.1. Total Ion Chromatogram and Corresponding HFID Signal for 35 Combustionof PFXS at 600C (off-line sample) 582. Extracted Ions (CF:H-51, SOF-67, CFy-69, CF:CF;H-101, and C:Fs-119) and Corresponding HFID Signal for Combustion 36 of PFXS at 600C (off-line sample) 583. HFID Signal for PFOS Combustion at 600C (off-line sample) 3 584. HFID Signal for PFOS at 900C (off-line sample) 37 002044 | LIST OF TABLES TABLE PAGE 3.1. Linear Fit Equations and Detection Limits 6 32. Transport Efficiency 7 S11 Transport Efficiency Test Results 9 521. Net AmountofSample Loaded 9 522. PROS Laboratory Spike Analysis 9 53.1. Flow Rate Profile for Heated Blank Analysis at 600C 10 532. Flow Rate Profile for Heated Blank Analysis at 900C i 533. Methanol Extraction Results for Heated Blank Analysis at 900C 13 534. PUF Extraction Results for Heated Blank Analysis 13 54.11. Net AmountofGasified Sample for PFOS Combustion Test 14 54.1.2. Flow Rate Profile for PROS Combustion Test at 600C 1 54.13. Flow Rate Profile for PFOS Combustion Test at 900C 14 54.14. Methanol Extraction Results for PFOS Combustion Test 17 54.15. PUF Extraction Results for PFOS Combustion Test 18 542.1. Net AmountofGasified Sample for FC-1395 Combustion Test 18 5422. Flow Rate Profile for FC-1395 Combustion Test at 600C 19 542.3. Flow Rate Profile for FC-1395 Combustion Test at 900C 19 5.4.24. Methanol Extraction Results for FC-1395 Combustion Test 21 5.42.5.. PUF Extraction Results for FC-1395 Combustion Test 2 00204s | LIST OF TABLES (continued) TABLE PAGE 543.1. Net AmountofGasified Sample for FC-807A Combustion Test 2 5432. Flow Rate Profile for FC-807A Combustion Test at 600C 2 5433. Flow Rate Profile for FC-807A Combustion Test at 900C 2 5434. Flow Rate Profil for Blank Analysis between 600 and 900C 2 543.5. Methanol Extraction Results for FC-807A Combustion Test 2 543.6. PUF Extraction Results for FC-807A Combustion Test 26 55.1. Flow Rate Profile for Heated Blank Analysis at 600C 2 5.52. Flow Rate Profile for Heated Blank Analysis at 900C 2 553. PUF Extraction Results for Heated Blank Analysis 28 56.11. Net AmountofGasified Sample for 1* Transfer EfficiencyTest 2 56.1.2. Flow Rate Profile for 1* Transfer Efficiency Test 2 56.1.3. PUF Extraction Results for 1 Transfer Efficiency Test 29 562.1. Net AmountofGasified Sample for 2 Transfer Efficiency Test 29 5622. Flow Rate Profile for 2* Transfer Efficiency Test 30 5.623. Methanol Extraction Results for 2 Transfer Efficiency Test 30 5.6.24. PUF Extraction Results for 2" Transfer Efficiency Test 30 563.1. Net AmountofGasified Sample for PUF Collection 31 563.2. Flow Rate ProfileforPUF Collection (PFOS Gasification with Air) 31 5.633. Flow Rate Profile for PUF Collection (PFOS Gasification with He) 3 5634. Reactor/Valve Transfer Line Extraction Results 31 5.635. PUF Extraction Results 2 002046 | LIST OF TABLES (continued) TABLE PAGE S71. SO; Calibration Results Using PLOT Column 2 572. Standard SO, Transfer Efficiency 3 573. Sulfur Recovery Rate as SO; 34 583. Integrated HFID Peak Area ofPFXS and PFOS at 600C Ed 584. Integrated HFID Peak Areaof PFOSat900C 37 002047 vi EXECUTIVE SUMMARY 3M requested that the Environmental Sciences and Engineering Group at UDRI evaluate the incineration of CsF17S0K5* (PFOS) and two Cy perfluorosulfonamides (FC-1395 and FC-807A), potential sourcesofPFOS to the environmentupon incineration. The overall goalofthis study was to determineifincineration is a potential sourceofperfluoroalkyl sulfonates, .&., perfluorooctanyl sulfonates (PFOS), which has been found in a numberofwildlife tissue samples (Giesy, etal, 2001; Kannan, etal, 2001). A laboratory-scale study simulating a full-scale hazardous waste incinerator was envisioned. Based on prior experience with halogenated compounds, initial plans were to use relatively modest conditions in the primary combustion zone (ca. 400C) to gasify the materials with more severe high-temperature (600 -- 900C), oxidative conditions representing a secondary `combustion zone. TGASofthe active ingredient indicated that higher temperatures (ca. 600C) werenecessaryto gasify this material. The sponsor also requested that the experiment be designed to detect low-levels (0.1%) ofPFOS in the exhaust gases. These factors necessitated the useoflarge amountsofmaterial (milligram quantities) and high-temperature, long duration exposures (ca. 1250C, 40 sec) in a specially designed pyroprobe to fully gasify the material. `These conditions, while representing quite severe conditions in the primary zone ofan incinerator, e.g., a rotary kil, are representative of the rangeofconditions that occur in a fullscale system. As such, the approach employed in the laboratory-scale combustion study is a reasonable extrapolationof a full-scale incineration studyofPFOS. Combustion tests for PFOS, FC-1395,and FC-807A were completed as requested by the sponsor. In-line and off-line GC/MS analyses, reactor effluent sample collection using PUF cartridges followed by LC-MS analysis, and chemical extractionof various transfer lines throughout the reactor system including the reactor itself followed by LC-MS analysis were conducted to investigate the following: 1)theextentofconversionoftheactive ingredients, 2) the formation of fluorinated organic incomplete combustion byproducts, and 3) the extentof conversionofthe sulfur to sulfur oxides. `The data presented herein clearly show that incineration of FC-1395 and FC-807A does not release PFOStothe environment. This conclusion is based mainly on the LC/MS measurements, but was substantiated by the extracted ion analysis that showed negligible 67-SOF ion indicating negligible amountsofvolatile sulfonate-containing degradation products. Sulfur recoveries were quite good, 100:25%. Thedominantsink for sulfur was SO;. GC/MS analysisofperfluorinated alkyl sulfonate precursors indicated that such precursors were not presentinthe reactor effluent. This finding is consistent with the LC/MS measurements, and strongly suggests tht the C-S bond was completely destroyed (and did not reform) in the combustion tests. High levelsof conversionofthe PFOS were observed from theincinerationtests. This conclusion wasbasedon LC/MS measurementsofthereactor effluent and athorough analysis of the transportofthe material through the combustion system. Sulfur recoveries varied from 50 to 60%, depending on the reactor temperature. The dominant sink for sulfur was SO. GC/MS. analysisofperfluorinated alkyl sulfonate precursors indicated that such precursors were not present inthe reactor effluent. This finding is consistent with the LC/MS measurements, and 002048 sctormobnugsltyisounggteessttss. that the C-S bond was completely destroyed (and did not reform) in the Flilmuiotreidnattoefdlourograonbiecnzientneer(meFdCi-a1t3e9s5wearned oFbCs-e8r0v7edAionnltyh)e,rCe,acotrorCe;ffflluueonrt.oalTkhaensees c(loimkeployupnrdosduwcetrse a1r3e9e5itohnelry)C.HHFi,ghCeFrs,moolreCcu;lFa)r,w1,e1i-gdhitflfulouorroientahteendep(olFycOySclionclay)r,omaantdic1,h2y-ddriofclaurorbooentshewneer(eFnCo-t observed. `iTnhceindeartaatifornosmytshtiesmlsabcoarnataodreyq-usactaelleyidnicsinpeorsaetoifonPsFtOuSdy ainnddictahteeCssthpaetrpfrluoopreorsluylofpoenraamtiidnegs.full-scale Itnhceiennevriartoinomnoenftt.hesWeitfhlutohreineaxtceedptcioomnpoofusntdasbliesCn;otalnidkeCl;y tfoluboeroacsairgbnoinfsi,cafnltuosroiunracteedoforPgFanOiSc: into intermediates materials. are alsounlikelytobeemittedfromthesefacilitiesduring the incinerationofthese 002049 6/19/2003 Laboratory-Scale Thermal Degradation of Perfluoro-Octanyl Sulfonate and Related Substances Final Report Prepared by: Takahiro Yamada and Philip H. Taylor Environmental Sciences and Engineering Group UniversityofDayton Research Institute 300 College Park Dayton, OH 45469-0132 In response to a verbal and written request from: Eric A. Reiner and Dan C. Hakes 3M Environmental Lab, ET&SS US-MNSP02, 0002-03-E-09 P.O. Box 33331 St. Paul, MN 55133-3331 002050 | 1. Background dTohmeidneastterducbtyiotnheeftfeimcpieernacytu(rDe,E)toifmep,rifnucelip(awlasotreg)aaniirc mhiaxzianrgd,ouasndcofnusctliatiuernsttso(icPhOiHomCest)ryis(excess a1i9r9)1e).xpeNruimeenrceodubsycatlhceuPlaOtHioCnssainndtheexpheirgihmteenmtpsehraavtuersehzoownnesothfaitnecmiinsesriaotnosrsof(uDnedlelisntgreory,eedt,al, TrerseindhuoallmP,OeHt Cals, a1r9e8k4i;neDteilclailnlgye,rn,oettatlh.er1m9o9d1)y.naAmiscaalrleysuclotntarcoclulreadte(TassasnegssamnedntSohfaPb,OH19C82; temhiesrsmioodnysnraemqiucireeqtuhielrimbarliusmtacbaillciutlyatteisotnisn.g and cannot be accurately modeled based on aSnimdptleempceornacteuprteuailn atnhedpmoosrte-fcloammeplzeoxnecsoomfipnuctienremraotdoerlsscionndtircoaltethtehartelgaatsi-vpeheamsiessriesoindsoenfcmeotsimte mPoOlHecCusle(sCleanrtke,rictngalt.,he1f9l84a;meDezlolnienogefra,netianlc.i,n1e9r8at6o;rDaerlelidnegsetrr,oycteda.co1m9p9l1)e.telTyhitso tishebercmaoudsyenaalmlic efancdilpirtyo.duOcntcseanind tohnelpyotshte-fmlianmuetezofnrea,ctgiaosn-epshcaaspeitnhgetrhmealfldaemceomzpoonseiitsioacnturaealcltyievimtiytiendthferopmretsheence offotrmhaetmiaonjoarndgadse-spthrausceticoonnosftiptruoednutcsotfsotfhiisnczoomnpelceotnetrcoolmtbhuesrtaitoenof(PPIOC)H.C destruction and. eIfxaplelrPieOnHceCstheinsaamgeivpeonswt-afsltaemestgraesa-mphaaresevorleastiidleinzcede attimaep,ptreomxpiemraatteulrye,tahendssatmoeicrhatieo,mtehteryywhiilsltory t(rrealvaetrisvee tchoinsczeonnter)a.tiTohnisos fmePaOnHsCt,haotxgyagse-np,haasnedtohtehremramlasjtoarbigliatsy-opfhaPsOeHcoCnsst(iatsuednettsearsmitnheedPuOnHdCers a standardized setof conditions) may be used to predict their relative incinerability. The utesmepdeprraetvuiroeusfolry 9to9r%andkestthreuctthieornmaatl 2s.t0absileictoynodfs PgaOsH-Cphsas(eTaryelsoird,eentcaelt,im1e9,90[)T.oO(t2h)(e"rC)r]eshiadsenbceeen itnidmiecsatoer tlheavtelaslotfhdoeusgthraubcstoilountemaPyOHbeCuDseEd taordeedveepleonpdeanrtanukpinogn,tiHmoewaenvdert,emlpaebroartautroer,yrdealtaative TDaEySloarreanldarDgeelllyiinngseern,si1t9i8v8e).toOtnhetsheepoatrhaemrethearnsd,(sDteoilclhiionmeegtterayr.,bas19b8e4e;nGsrhaohwanm,foetbeala, s1i9g8n6i;ficant variable in determining Taylor, etal, 1991). relative stability (Graham, etal, 1986; Taylor and Dellinger, 1988; tEhxaptemriamyenctaaulseanredstihdeuoarletPiOcaHlCcSontsoidbeeraetmiiotntsedsufgrgoemsta tfhaactilviatyr.ioTusheflmaomsetzpornoemifanielnutroe fmtohdeesse eaxriest utnhderemranloqmuiennaclheixncgeassndaiwracsotned/iatiiromnsi,xipnogorfawialsutree/maoirdemsi.xiEnvgeonr tthhoeurmgahlaqfuaecnilcihtiy nmgazyonbeesodpuereattoing pdeosotrruhcetaitontriasnslfoewr aatndinPciInCerfaotromrastuirofnaciessfwaivlolrerde.sulCtoninsecqounednittliyon,sitwhisebreelitehveerdattehaotfgPasO-HphCase tPhOeHrmCalresltaatbiilvietiynacsincehraarbaicltieyrized under oxygen-starved conditions is an effective predictor of 002051 | f`TuhrethUerDdReIvetlhoeprmmaelntstpaubbillitsyh-ebdasiend19i9nc1in(eTraaybliolri,tyetraaln.ki1n9g90w;aDselinliitnigaelrly, peutballi,sh1e9d91i)n, 1T9h9e0 wUiSt-hEPA has evaluated the UDRI gas-phase thermal decomposition kinetic rankings onboththe pilot and 1 : f1u9l9l2-)scoalfeaanscalbeavseins-fcoormdpeotneernmtinhianzgarPdoOuHsCwaisnctienemriaxbtiluirtey.unPdielrott-hsecramlaelstfuadiileusre(Caanrdrowlolr,sett-alc.a,se tceomnpdeirtaitounrse(,elnacrogmepracshsairngge tmharsese,faanildulreo-wperroHmo/tCiIngractoiondtihtainontsherebsausletliinngeisnetloowfecronkdiiltn-ieoxnist) both pgarso-dpuhcaesdestthateirsmtailcalsltyabsiilgintiyfriacnaknitncgosr.reFlaotritonhse tbheetrwmeaelnfparioludruectteestmsi,scsoirornelcaotnicoennstarbatoivoentshaen9d9t%h.eir ccoonmfpiodneenncet ihnatzearrvadlouwserweasotbesemrivxetdu.reFiunlld-isccaatleedstthuadtitehse(rDmealllifnagielru,rectanadl,wa1s9t9e3/)aiorfamisxeivnegn-failures eaflfsiocipernocdiuesce(dDRstEaSt)is,titchaelldyastiagniinfdiiccaanttedcotrhraetlabtoitohnst.heBmaisxeidngonamndedtihaenrmdaelstfrauiclutrieomnoadnedsrpermoodvuacled stthaetrimstailcasltlaybisliigtnyifriacnaknitngcso.rrelations between product emission concenirations and their gas-phase 3thMerrmeaqludeesctoedmptohsatittihoenEonfvtihreonfmoelnltoawlinSgcifelnucoersocaanrdboEnn-gbianseeedricnogmpGoruonudps:at UFDC-R8I0e7vAalaunadteFtChe1395 (toCsdepteerrflmuicnreoiafilnkyclinseurlaftoinoanmiidseas)p,otaenndtiCalsFsio7uSrcOe5oKf*pe(rPfFlOuSo)r.oocTthaenyolvesruallflongaotaelso(ftPhFiOsS)s,tuwdhyiwchas `hTahsisbreeepnorftoduensdcriniabesnuthmebeexrpoefrwiimlednltiaflesttiusdsiueesosafmPplFeOsS,(GFieCs-y8,0t7Aa,l,an2d00F1C;-K1a3n9n5a.n, et al, 2001). e`Txhpiesrrieepnocretisn ibnrcoikneenraitnitooneriegshetarscehc,tipohnsa.seTI:hethfeirisntitfioaulrtseestctpiroontsocdoelscarnidbeprtohjeebcatcokbjgercotuinvedos,fpohuarse d11e:sctrhiebemetthehoedxpdeerviemlenotpamlenretswulotrsk,faolnldopwheadsbey IaIn:inttheerprreevtiasteidontoefstt hpreotroecsoull.ts,Serecstpieocntsivfeilvye.andsix Sreefcetrieonncesse.veAnngaipvpeesncdoinxclcuosnitoanisnsatnhderfeoclolmomweinndgaatuixoilnisa.rySiencftoiromnaetiigohnttphraotvpiedretsaianslstto oalfl oefxtpheeripmheanstes Ic,opnhdausceteIId, ianntdhipshasstuedIyTTisntculduideisnagntdhtohseeiancvtoulavlidnagtPesFoOfSthienccionemrbautsitoni:on1t)esatst,im2e)line rSeapmoprtlaendderscarwiptdaitoan,s4a)ndthCeeprthiafsiecaItIeotfesAtnparloytsoicsol(aCondfAad)defonrdPumF,O5S)tshaemp3leM, a3n)atlhyetipchalasreeIporftinaanld 6)a spreadsheet linking the UDRI combustion tests with the 3M Analytical results. 00052 | 2 2. Phase I: Objectives and Test Protocol The objectivesofthis program were the following: 1. DocettaenrymlisnueliffonCastepe(rflPuorFoosruplOrfeocnSuarmsio)dressofforpemrcfolmubouros-toicotnanpyr!osduulcftosnatthea.t eitherare perfluoro- 2. Determine municipal the extentof conversion waste incineration, of PFOS under conditions representativeof hazardous or 3. Identify the major fluorinated combustion products, 4. `Daentde/orrmtihnieoniyftlhfelusourlifduer(prSeOsFen)tainndthseulPfFurOylSfilsuqouraindtei(taStiOvFel)y actonhviegrhtteedmptoersautlufruer,difuoexli-dleean combustion conditions. `rTehaectdoervsedleovpemleonpteodfatthUeDtResIt ptorosttoucdoyltwhaesthbearsmeadlosntatbhieliutsyoeofofrbgaatncihc-cmhaatregreidalcso(nRtuinbueoyuasnfdlow. Cmaatrenreisa,l1(9t8yp5i,cRalulbyelyesasntdhaGnra1ntm,g).198T8h)e. sBarmiepflley,atnhdesitessdyesctoemmpsosaictciepotn aprsomdaulcltsquaarnetivtolyaotiflized, mthiexseadmwpiltehvfalpoowrisngardertyhaeir,matlrlaynssptorretsseeddtuhrnoduegrhcoanhtirgohllteedmcpoenrdaittuiroensqoufatritmzet,ubtuelmaprerreaatcutroer,wahnedre ecxhcreosmsataiorgrleavpelh.y/Tmhaessmastpeercitalrsomseutrrvyiv(iGnCg/tMhiSs)exspyosstuermefaorreatnhaleynspiasssed onto an in-line gas `nQouna-ndteisftircuacttiionvoefcopnadrietnitonssp.ecTiyepsiicsabllays,epdroodnucttrsanasrpeorqtuaanntdifaineadlyussiisnogftkhenorewsnpoqnusanetifatciteosrounfdtehre panaarleyntticcaolmfpoocuusndwiolrl tbheemidaejntoirfpiacarteinotnocfosmtpaobulendfsluiofrifnraotmedaocrogmanpilcexinmtiexrtmuerdei.atIenstahnisdstthuedy, the qSuualnftuirfiqcuaatnitoinfoicfatsiuolnfuwrilolxbideepseirnfaonrmaetdtuesimnptgotarmeacsovsesrel1e0ct0i%voefdtehteectionrit(iaMlsSuDl)f.urCionnstihdeersaamtpiloen. `Hwoawseavlesro,gidvuenttootthheeuunsievoerfsaalsnualftuurr-esopfetcihfeicMdSeDte,ctior,thiatst arbeislpitoyndtos doentleycttobostulhfsuurlaftuormas.nd felxupoerriinmaetnetdso.rganic compounds, it was decided that the MSD would be satisfactory for these Eesvtearbylissahimnpglethperetessetntpsroittoscoolwnceunntieqreudesaertooufndchtahleleinsgseuseo.fIntrtahnespcoarsteaboiflPiyF.OSSp,ectihfeicuanlklyn,owns in `tarnadnstphorrotuignhgtthhee sanaamlpyltiecatlo stuhbe-rseyasctteomrsf.rFoomrtehxeasmapmlpel,eitinileltiakenldytthheatprthoedutcetsst sfarmopmlethweirlelactor to ddeeccoommppoossietiroanthperrotcheasnsecvaanpobreattreaansnpdorthteedcuenntdrearl aicscseupetbaebcleomceonsdiwthieotnsh.erCothnesepqruoednutcltys,from this developing the test protocol transport and analysis. for the 3M samples focused on the issuesofsample feed and product 002053 3 The first step inanygas-phase thermal stability analysis is converting thesample into avapor `where it is mixed with the desired carrier `gas and transported through the reactor `system by the (cbsuoilmtkrmofoglenonwpoorrfatchhteielciepurtmoo)cpaeetsrsmfosostrprmheeaarm.ethsWetrhomeodngertwaeovrrimkmieintnergtihwceiattnheamlapysreeirlsaat(tuiTrvGeelAry)aunnigcnehoanxreiadecidtzeeidrnigtzo(eagdiarss)aimafypnldtehs,erittis sample. This preliminary information was used to determineifthe phase change is imple `evaporation or decomposition and to determineif the sample deposits a non-volatile residue. With the temperature range needed to gasify the sample established, a seriesofrelatively scuple ftelsotws wreaasctpoerrcfoonrdmietidtonos.deWtheirlmeintehieftshameplgaesiifnilctatsiyosntpermosduocfttshceoUuDldRbIeretarcatnosrpsorctaendbuendreorutnionmeliynal `heatedto 400C (with transient`heatingas high as 600C), the `sample transport linestoand from ctohnedrietaicotnosrsmoarsettoyrpgiacanlilcycloimmiptoeudntdos2o5f0i-n3t0r0esCt. cEaxnpbeeriternacnesphoarstesdhwoiwtnhotuhtatiunndudceirntghtehseermal reactions thereby preserving the fidelityofthe samples flowing from the inlet system to the reactor and the product stream flowing from the retaotc heat nalo yticr al sub-systems. Akey 1iosstuheethoibgeh-etveamlpueartaetdurinertehaicstsotruadnydwfilrlobmeththeerteraacntsoprorttootfhtehaenaPlyFtOicSalfrsuobm-tshyestgaesmisficationsystem `The System for Thermal Diagnostic Studies (STDS) was used to perform the incineratiosn tudy described herein. An overall schematicofthe system is shown in Figure 2.1. The STDS is a p`mroodcuelsasre,scaonndtipneurofuos,rmine-xlhianuesrteiavcetoarnaslyyssteesmofthtahtealoluotwpurtesfeoarracbhoerust toones-itmeunltahtethienccionsetroaftfiuolnl-scale tests. The instrument consists of several `major components: a thermal reaction compartment; a transfer line; an analytical gas chromatograph (GC), a mass selective detector and acomputer `workstation. The STDS has been used to `perform many typesof combustion studies. The STDS. ahlalsobweienng pvreiroyrskuncocweslsefdugleatofptrheedicrtisiknsg aasisroecmiiastseidownistfhrboumrntihnegiancgiinevreantiwoansotfe.hazardous materials, Stem tor ThewmaoDrnt Suen ] L_[="" EHE=MH=EE Figure 2.1. Schematic of the System for Thermal Diagnostic Studies 002054 4 TInoitsiaaltliys,fythteheAdanvaalnytciecdalTrheeqrumiarlemPehnottsolfyotriPcFROeaSctdoerteScytisotnemby(LATCP/RMSS)awnaalsyssieslaetct3edMfor this study. `Emngv,ihraodnmteonbtealgaLsaibfoireadtionryt,hewaectdueatleerxmpienreidmetnhatts.relTahtiisvealmy oluarngteoafmsoaumnptlseofwassammpulce,h0l.a5rgteorstehvaenral AinTiPfaRlSl.y esPtriemlaitmeidna(rcay.e1x0petroim1e0n0tpsagl)saonddemcoounlsdtrnaottebdetghaastihfiiegdhewrigtahstihfeiciantlieotnatveaimlpaeblreawtiutrh(e>tshe `4e0q0uiCp)pewdewriethneacheisgshar-ytetmoperarpaitdulryegpaysriofpyrtohbeeftlhuaotrcoacnargbaosni-fbyamsieldlsiagmrpalmesq.uaAntsistuicesho,ftmhaeteSrTiDalS,,was selected for the actual combustion tests. (Ien.gt,heno-roicgtiannacl).prSoutbosceolq,uewnetloyr,igitinwaalslydpeltaenrnmeidnesdamtphalteacsoumbbsutisttuitoenwwaisthneacleisqsuairdyhbyedcraoucsaerbthoen fuel olbitquaiidn hsytdoriochciaormbeotnrifcueolxiodraitgiionanlalyndpritopwoassedimrpeoqsusiirbeldeatomumacihntlaairgnetrhaemroeuqnuitroefdorxeysigdeennc(eaitri)mteo of l1o-w2essetccohnedmsiicnaltohexreyagcetnorduenmdaenrdostfoiacnhyiohmyedtrrioccaorrbeoxncefusesal iarndenivsiarsoantmiesnftacst.oMrey trhepalnaechemaesntt.heWe hdeycdirdoegdeninssotueracdetotousceonmvetehrFatnetoaHsFa,foutehleifrtwhiesesfaumepllweilils nhoytdrboegienntrdoedfiuccieednttoatnhderreeqaucitroers.. (I6n0t0h,e7o5r0i,giannaldp9r0o0toCc)o.l,Pwreelialmsionaprryopcoosmebdusttoicoonntdeusctts wciotmhbussetveiroanltseasmtsplatesthirnedeictaetmepdertahtaturmeasny combustion byproducts were formedat600buttCho,se combustion byproducts were not otbhesseervheidghaetrhtiegmhpeerrtaetmupreersawteurree (v7e5r0y sainmdil9a0r.0TCh)eraenfdotrheeitGwCa/sMdeScitodtealdtihoantcthwrootmeamtpoegrraatmusrefosrare sufficient to analyze the combustion phenomenaofthe selected samples (600 and 900C). 002055 | 5 | 3. Phase II: Method Development `The following method development tests were performed in phase Il: 1. Verifythat PFOS canbe gasified andtransportedthrough the UDRIthermal instrumentation system. 2. Establish recovery efficiencies and detection limits for stable sulfur compounds and PFOS precursors. The sulfur compounds wouldincludebut not be limited to SOs, SOF, `and SOF. PFOS precursors would include but not be limited to perfluoro-octane sulfonyl fluoride (POS). 3. Establish recovery efficiencies and detection limits for volatile C;-Cs fluorocarbons. 4. Develoap quantitative method of sampling the reactor effluent. ORBO PUF cartridges (Supelco, Inc.) will be used for sampling PFOS and its precursors frtheoreacmtor effluent. `STOhiZsFs,ecPtOioSnFsuamnmdaCrsiFzes(htehxearfelsuulotrso.prCaolpiebnreat(iHoFnPc)u)rhvaesveabnededneteescttaibolnislhiemdi.tsTfhoer StOrasn,spSoOrtF, efficiency for each compound through the STDS was also examined. Verification that the Cy `perfluoroalkyl sulfonates can be gasified and transported through the system was performed following the completionofthe combustion tests. This decision was made based on the potential contaminationofthe system had the transport ests been done prior to the combustion study. PUF cartridge samplingofthe reactor effluent was established as partofthe revised phase III protocol. HEP was selected as the surrogate volatile fluorocarbon due to the lackofavailability of CF4 and CF3H from gas suppliers. The linear fit equations for each sample, thir linear correlation coefficients (R) and detection limits are tabulatedin Table 3.1. Furtherdetails regarding these calibration curves are available in the Phase II report. Sample Name 5S0OF;: SOF; POSF HFP `Table 3.1. Linear Fit Equations and Detection Limits Linear Fit R Detection Limit (: peak area, X: concentration (ppm) (ppm) Y = 5.8813E3X% - 3.8541ES 0.9971 785 Y=8333SE3*X-7.0267E4 099941 303 Y= LO33IEA*+X 1827386 0.99708 201 Y = 1.0423ES*X ~ 84043ES 10 141 Y = 14975E4*X - 2.8253E6 0.9997 39 `The transport efficiencyof each standard was estimated by comparing the measured sample peak area obtained when the sample Was injected into injection portinGC1 and passed through combustion reactor and transfer line (system transport) with that obtained when the sample was injected directly into the injection portof GC2 (direct injection). 002056 6 `Table 3.2. Transport Efficien : [1 SistemTmmnspor | ~~ DirectInjection | Efficiency| [| PeakArea | PeakArwa | (%) | [SO |9130332| 8980717| 9055525|11952302|11762267 11857285] [SOF,|25244357| 25203780| 25224066|24862639|24773683|2481161| [SO:F;| 86850304| 85572809| 86211557|84435720|70738316 82087018] [POSE| 1280370 1228718| 1254544| 1064431 1067947]1066189] [HEP ]148679354 |143606343|147142849|148372504|142271896[145322200 764 101.6 1050] 117.7 101.3] As illustrated in Table 3.2, the transport efficiencies for SOF2, SO andF HFPw, ere within awnaaslystliicgahltleyrrhoirg.heArn, buuntceirstnaoinnettyhoefles1s0ac%ceipstraebales.onaTbhlaetffoorrtShiOs;tywpaesofaarnoaulnydsi7s6.%.ThTahtefoSrOP;OSF standard was analyzed as a two-component mixture with SOF. Since the transport efficiency f`aonrdStOraFn:sfweraslinneesa.rlBye1c0a0u%s,e tShOe;reissuelxtpseicntdeidcattoebseomoneeosafmtphleemlaojssoerscfoomrbSuOs;titohnrobuygphrotdhuectresa,cwtoer will repeat the efficiency test atheonofstheeacttualcombustiontests (see section 5.1: SO; `Transfer Efficiency Test). We will estimate a SO; correction factor based on SO; efficiency test orfetsuhletsitnoitcaolmcpaelnibsraatteiofnoranitdstmreaansspuorretdecfofinccieenntcryattiesotnsdcuarninbgetfhoeuPnhdaisnetIhlelPshtuadsye.IIFurretphoerrt details provided in the Appendix. 002057 7 4. Phase III: Revised Test Protocol `The combustion tests consisted of separate tests as listed below: 1. SO; Transfer Efficiency Tests, 2. 3. LHaebaotreadtBorlyanSkpiCkoembAnuasltyisoins TfeosrtP,FOS, 4. S. CHeoamtbeudstBiloannkTeCsotmsbfuosrtPiFonOSTeasntd(trewpoeaCt),perfluorosulfonamides, 6. 7. TSurlafnusrfeRreEcfofviecriyenAcnyaTleysstisfoarsPSFOOs,S, 8. Extracted Ion Analysis. lSipneeciGfCic/aMtStenantailoynswisa,sPbUeiFng(pgoilvyeunrettohtahneesfaomapml)incgoollfecPtiFoOnoSfdtuhreinrgeaicntcoirneerfaftliuoenn.t aInn-dlicnheeamnicdaolffPexUtrFacctairotnroidfgtehsearnedatchteoreaxtnrdacatsssowceiraeteddeltirvanesrfeedrtloin3esMwfeorreancaolnydsuicstoefd.PFIOnSthebylaLttCe/rMtSw.o tPerstiso,rtthoe tlhaebosraamtoprlyescpoimkbeuasntailoynsiasnfaolrysPisF,OtShewtarsanpsefrefroerfmfeidci.enAcyhfeoartSedO;blwaansk rlien-eaenxaalmyisniesdwaansd tpheerformed aatnatlhyesiosnsweatsofptehrfeorsmaemdp.leTcroamnbsfuesrtieofnfitceisetns.cyAtfesttesrftohrePcFomObSuswteiroenpteerstfso,ramneodthaetrthheeactoendclbulsainoknloifne stuhlefcuormrbeucsotvieroyn rtaesttes.asDSuOe;twoarsesroel-uatniaolnyizsesdueussirneggaorfdf-ilnignethGeCi/n-MliSneansaalmyptlicianlgraepspulrtosach, the aFuprptehnedrixdettaoitlhsisarreepporrot.viTdheed i3nMthaenaPlhyatsicealIIretpeosrttpr(oLtoIcSolNaonsd. a0d2d-e0n8d2u0m,tEha0t2-a0re82g1i,veEn02in-0a8n22, 0E90127-,08E3092,-0E90226-,08E4002,-0E90628-,08E6072,-0E90629-,08E9052,-0E90720-,08a9n6d,EE0022--00987918), iE0a2l-s0o8p9r9o,vi0d2e-d0i9n1a6n,aEp0p2e-ndix PtoUtFhicsarretproirdtg.esI.t sShpoiukledraelcsoovebreiensoftoerdPthFaOtSthweePrFeOcSa.d8at0a%wweirtehn|otucgoardrdeicttieodnfoofrthreecsoevecroymfprooumndthse and ca. 90% with 10 ug additionofthese compounds. 002058 | 8 5. Experimental Results 5.1. SO, Transfer Efficiency Test The SO; transfer efficiencytests conducted in PhaseIIwas repeated in PhaseIII to confirm the Phase ITresults. The results are component mixture with SOF. shown in Table 5.1.1. TheSO; standard`wasanalyzaesd SO; transport efficiency was 83.7%, slightly higher than atwo- previous results, 76.4%, which gives average valueof80.1%. The transport. efficiency for SOF, `was again nearly 100%. Table 5.1.1. Transport Efficiency Test Results EE -- YS-- C7 [[sS0O,F[|21s3s4o309s80||2mwsi0s9s7e0a3n||soswsaesreisots|| 1roo6r1s2a7ras7|1 szoosoasssor| tzoooosmssoswars|| t3o7rs]] 5.2. Laboratory Spike Analysis for PFOS PFOS was dissolved with 10 ml methanol (Aldrich, HPLC grade) and 1 ulof solutionwas placed into a reactor (4 mm (id) x 6 mm (0.d.) x 7 cm length) and dried by blowing high purity `nitrogen. The amount ofsample used is shown in Table 5.2.1. Afthtede ryir ng process, the transfer lines were assembled and also used to dissolve the samples. the samples were extracted using 5.5 ml of methanol that was Sample PFOS Net Weight (mg) 10.02 Table 5.2.1. Net Amount of Sample Loaded Solvent Amount Amount Injected Net Amount.of Sample (ml) (ul) Loaded (ug) 10 1.0 1.0 `Table 5.2.2 shows the extraction results for PFOS laboratory spike analysis, respectively. The combined first and second extracts recovered 188%ofthe PFOS. This single spike result suggests that an error likely occurred during preparation, extraction or analysis. Nevertheless, this spike result confirms that PFOS can be extracted from reactor/transfer lines. Table 5.2.2. PFOS Laboratory SpikeAnalysis Sample Extracts PFOS (pg/pl) _PFOS (ug) PPFOFS 1"EOxtracSts T' 243025Bm0e1%.6 s 5.3. Heated Blank Combustion Analysis "The heated blank reactor/transfer tubing was analyzed contamination (including background levelsof PFOS) to examineifthere was any system for the reactor temperature at 600 and o9f0f0-gaCspsraiomrptloesearnaileyssoifs,coofmfb-luisnteiGoCn /teMstSs.anFaoluysriasnuasliynsegsT,eidnl-alrinbeaGg,Ca/nMdSre`aancatloyrs/itsr,aPnsUfeFr cloilnelected 002059 9 esxytsrtaecmtieoxnotrfacctoionndeunssiengdmpehtahsaenmoaltewreirael wcoenrdeupctreedp.areTdhaenPdUsFenstatmop3leMcEonllveicrtoinomneanntdalmeLtahbaonroaltory ftohrananCaslycsoesm.poTuhnedsina-lnidneofGfC-l/inMeSGwCa/sMmSaiwnalsyuusseeddftooralniaghltyezreccoommppoouunnddssienqculaulditnogoSrOh;e.avPieUrF rseaamcptlore/tarnadnsmfeert-hlainnoelcoenxftirgaucrtastwioenr,eaanndaleyxzpeedrifmoernPtaFlOpSrodceteedcutrieonf.olTlhoeweedxptheeriPmheanstealIIsetteuspt, protocol. The Phase I test protocol and addendum can be found in the appendix to this report. 53.1. In-line GC/MS Analysis aTnaabllyesi5s.3a.t16a0n0da5n.d3.920s0hCo,wrtehsepfelcotiwvperloyf.ilOeftahned ctaortarliegrafslfolwovwo,l1ummle/umsiendwfaosr ithnethreoadtuceeddbltaontkhe oifnf--lliinneeGaCna/lMysSesa.ndAthseimrpelmeai1n/d1e6rini.nttereowduacseudsteodeaitshetrhethfelPowUFsplciatrtterr.idAgeirorwatshefTleodwleadrtboagboftohrthe npeycreospsraorbyetaonpdurregaecttohre dpuyrrionpgrothbeetaenstdetxocpeeprtfdourrmintghethien-llaisntetGiCme/pMeSriaonda,lywshise.reAhHelPiSu8m9w0aAs/ T5e9c7h0nBolsoegriieess,GICnc/.M) SwawsituhseadDfBo-r5thMe Sin-claipnielGlaCry/cMoSluanmanly(se3s.m0Tlheengitn-hl,in0e.2G5 mC/mMiS.dw,aAsgiolpeenrtated oatpecroantsetdanatt parnesesluercetr(o1n0mpuslit)i.plTiheresMetStinwgaosfa2u0t0o0-tiunnetdhewistchanpneirnfglumoorodterisbwueteypliamnignea (mPasFsTBrAan)gaend from45 t0 550 w/z. Figures 5.3.1 and 5.3.2 show total ion chromatograms for reactor atenmdpneroactournetsaomfi6na0t0ionanwdas90f0ouCn,drfeosrpeecittihveerltye.mpTehreatcurher.omTahteogbraacmkgsrhoouwnsdonnoliysbeadcrkogprpoeudntdonaonise aupspeadrienntanzteircoiplaetvieolndouefa thoitghhebraelcaktgirveoluyndhingohissieglneavlelthtrheasthaorlidse(s25f0r0o)m. tThheipsrheisgehnctehorfessihgonlidfwicaasnt acomnosuinsttesnotfwcitohndtehnesleadrgpehaamsoeucnotmsboufstfilounorboycphreomdiuccatlss. thTahtiwseerxepeicntjaetcitoend winatso ctohenfciormmbeudstainodnis system. Table 5.3.1. Flow Rate Profile for Heated Blank Analysis at 600C Tim(eePce)riod RRaetacet(ourlFmlionw)_ PRyarotper(omblemFilno)w Total(FmUlmoiwn)Rate VoTlouulme VSoalmupmlee*d 0-120 105 050 1130 (mi) (m] 280 2060 113200--114300 110055 0804363463 1131055131463 22:16192395 140-160 903 453 (Hel Toul Vo1l33u5m6e (al) 42 419 __3130__2913 LanidneTaerdilnacrrbeaagseco(lslpepcrtoixoina.mate). > Switchedto helium for sweep.<Sampled volumeforPUF 002060 10 Time PerioTdableRe5a3c.t2o.r FFllooww RaPtyeroPprroofbieleFlfoowr HeTaottealdFBlloawnRkaAtenalysiTsoalt 900SCampled Ge) Rate(ulmin) Rate(mlmin) (mimin) Volume Volme* 0-150 7.60 070 @) 30 075 1835 150-160 160-170 760 760 0703463 46 83051223 1223 mo 1s 206 187 170-190 654(He) 4.53 (Hel Toul Vo1l1u0m7e (ml) 369 _28.19 336 _2502 "aLnidnTeeadrlianrcrbeaagseco(lslpecptriooxni.mate). *~ Switched to helium for sweep. Sampled volume for PUF wee i ey Figure 5.3.1. In-line GC/MS Ion Chromatogram for Heated Blank at 600C Figure 5.3.2. In-line GC/MS Ion Chromatogram for Heated Blank at 900C 53.2. Off-line GC/MS Analysis Awit0h.i5nL1Temdilnaurtbeasgaf(tSeKrCc,ollIencc.t)iowna. sTuhseedftloowcoplrloefcitletwhaosffi-dgeanst.icaTlhteo stahempilne-lsinweerGeC/anMaSlyazneadlysis | `HaPndS8P9U0FA/co5l9l7ec0tBiosnereixecsepGtCt/hMe SlawtittihmSePpEerLi-oQd,PwLhOicTh (wPaosronuostLnaeyceerssOapryenfoTruTbeudllaarr) bcaogluanmanly(s3i0s. mopelreantgethd,i0n.t5h3emcomnsit.adn.,tSfulpoewlcmoo,dIencw.i)twha2s8umsle/dmfionr tsphleitanfalloyws.es.ThTehMeSoffw-alsinaeuGtoC-/tuMnSedwwaisth perfluorotributylamine (PFTBA) and operated at an electron multiplier setting of 1600 in the 002061 i . shceananittnogecmado.d5e0 s-w6e0epCiwniagthmahsesartagnugentforommin3i5mtioz5e5c0omn/zd.eTnhesaToetdniltaohrnebbaagsgswuerrfeacmeosd.er1amtelly ssahmopwlteotvaolliuomnecshwreormeationgjercatmesd ufsorintgheahgeaast-etidgbhltasnykriantg6e0(0Haamnidl9t0o0nCCo,.)r.espFeicgtuirveel5y..3.3Laarngde5p.e3a.k4s raessspoeccitaitveedlyw)i.thTahierrweewraesonboseortvheedrapte0a.k6s5oabnsedr0v.e7d5, mwihniucthei(nadrigcoatneasntdhecalracbkonofdaionxyidmee,asurable contamination. Figure 5.3.3. Off-line GC/MS Ion Chromatogram for Heated Blank at 600C Figure 5.3.4. Off-line GC/MS Ion Chromatogram for Heated Blank at 900C 5.3.3Reactor/ Transfer Line Extraction and LC-MS Analysis tFhoellroeawcitnogr/PtrUaFnsfsearmplilnee ctoulbliencgtiwoansapnedrifno-ramneddo.ffT-hleirneeaGctCo/rMwaSsancaultysiinshaaltf9p0r0ioCr,toextthreacetxitornacotfion. Twheerseeecxotrnadctheadl.f FofutrhtheerreadcettaoirlasnrdetgahredtirnagnstfheerelxitnreascbteiotnwpereonctehdeurreeaacrteoprraensednstwediinttchehvPaihlavnseeg1II ; gtersatdep)r.otoTchoel.exTthraectesxtwrearcetiaonnsalwyezreedpfeorrfPoFrOmeSdattw3icMe Eunsvinigro5n.m5emnltaolfmLeabtohraantoorly(.AlTdarbilceh,5.H3.P3LC rsehaocwtsort/hreanasnfaelrytliicnaelerxetsrualctts.inAthveefriyrsstmhaelaltaedmobulnantkocfoPmFbOuSst,i0o.n08tespti.g, Twhaesafmoouunndtinftohuend igs Yo2062 12 ethqautalcotu0l0d.h0a1v6e%obfeetnhfeormmaexdifmruommaamnoyounftththeatflcuoourlodchheamviecpaalspsreoddutchtrsouagthletvheelssyasdtdeemdaisnPthFeOS or ``wcaosmbbuesltoiwondetetsetsc.tioTnhleimaimtso.unt of PFOS extracted in the second heated blank combustion test `Table 5.3.3. Methanol Extraction Results for Heated Blank Analysis at 900C PFOS (pga) 149 _PFOS (ug 010 `cToanbtlaem5i.n3a.t4isonhowwass the analytical detected. results forthetwo PUF sample collections. No cross `Table 5.3.4. PUF Extraction Results for Heated Blank Analysis Temp (C) 600 _PFO<S10.(0pg/ul)__PF<O0S2(5ng) 900 <100 <0.25 T5h.4i.s sCecotmiobnupsrteiseonntsTtehsetcsombustion test results for PFOS and two Cy perfluorosulfonamides, FC-1395 and FC-807A. 5C.o4m.b1.usPtiFoOnSpCroodmubcutsatniaolynseTseswtesre performed at reactor temperaturesof600 and 900C. Four diins-tliinncetGaCna/lMysSesanwaelryseiscoanndducoftfe-dlifnoerGeCac/hMtSesta.naTlwysoisGCus/iMngSTaendallayrsebsagwse.rTehceocnhdeumcitceadlat UDRI: eexxttrraaccttieodnastotfhteh3e MreEacntvoirrtornamnesnfetralliLnaebs.weTrheepeexrpfeorrimmeednattalUDseRtIu.p,TrheaectPorU/Ftracnasrfterri-dlginees:were coopnefriagtuirnagticoonn,diatnidonesxfpoerritmheenitna-llipnreoacnedduorffe-lfionleloawnealdytsheesPwhearseeItThIetsesatmeproatsotcholo.se uTsheedGfCor/hMeSated blank analyses described in Section 5.3. cInhatmhebseerciosmcbounsstiidoenrteedstasn,atlhoegosuasmptoletsheweprriemafirrystcvoolmabtuisltiizeodnicnhaapmyrboeiprrnobaen cinhcaimnbeerart.orT.hTihse greaascetsoro,raanidr-aedndtirtaiionneadlptarratniscfuelratteumbaitngtearntdheanvpaalvsesetdotPhUroFugcahrttrriadngsefse.r tTuhbiengh,eaatheedarteeadcttourbuislar cinocnisniedreatroerd.roughly analogous to a secondary combustion chamber or afterburner in a full-scale: `pTraobblee w5.a4s.1w.1eisghhoewdsnbeeftorae amndoaoffuersantmhpetlceomgbaussiftiieodnftoerstPs.OS combustion tests. The sample 13 002063 | Table 5.4.1.1. Net AmountofGasified Sample for PFOS Combustion Test Temperature Usage Loaded Remaining Net Amount "0 M(amgs)s (mg) ofSGaamspilfieed _-- 600 PUR 047 002 m0e4)5 900 TB" 048 010 PUF 050 000 038 050 *1o-line GENE aly s 0d TB 050 oFga collection using PUF. 000 *Offi 050 GUMS analy sing Tedlar Bag. Tables 5.4.1.2 and 5.4.1.3 show flow rate profiles used for PFOS combustiontestsat 600 and 900C, respectively. "TimeTPaebriloed5.4.R1e.2a.ctoFrloFlwoRwat_e PPryorfoiplreofboeFrlPoFwORSalCeombusTotuilonFlToewsRtaatte600VoClume (se) Rate (mbmin) Air (ml/min) (ml/min) Air CH, (am) 600--6850" 903060 0080s0 002010 1000802 1000902 18557--115677 99.8866 085083546 002211 109210921470 123.1140 167-177 77-197 9.386 sel 463 021 4SIHO' 000 1870 1314 245 438 Tot`aToltavlovloulmuempeaspsaesdsetdhtrhoruoguhgrheaPcUtoFr((mmll)) 3320..9192 *System opened duTetootsaamvpolleumienseursteiodn.foArsofsumliinneg 0G0Co/uMlSe fSlOo;w.quLainnieaatiinvcereaansael(yaspipsr(omxilm)at_e). 222S.w0it7ched to pahsseedltfhorirosuwugehempP.UF*s.To*talVcarro ierufslleodwvtooulcuamluemtlhtaetetpoatsalseamtohurnotuogfhtShOe;rreecctoovrere*duTostianlgcaorfrifeirneloGwCv/oMSlsuysmhtaeetm. Time`PTearbiloed5.4R.e1a3c.toFrlFolwoRwate PPyrroofiplreobfeorFlPoFwORSatCeombuTsottailonFlToewsRtaatte90V0olCume (2) Rate (m/min) Air (m/min) Air CH (ml/min) (ml 06-0-6805" 07.0102 0060s0 001060 070903 070903 8157-91-17899 771122 0650365463 016 016 793 7B 24 16 189-199 7.12 46 016 1191 199 199-219 6IS(He 453(He' Total volume pas0sed t hro ug h r1e0ac6t8or (ml) 32.75.655" Total volume used or ofline`GTotMal SvolSuOm,eqpuasasneidttihvreouagnhalPyUsiFs ((mmll)) _2_41.9.36221 Shyestlefoipsewuneeemdp.Gus*T(o0tsaalmcaprlreieirnfslerotwivoon.luAmsetshatupma5s0isoednutlrgoulgowh.h*eLeisnceiaori.ncTreoatsae a(apipreoxilmaotwe)v.o@lSuwtmihaecthetdo pasidtrough PUFs. +Volumeused 1 calculate totalamountof SO recoveredusing of lineGCMS sysem. 002064 14 Identical combustion conditions were repeated for PUF collection with in-line GC/MS analysis and off-line bottom) is t hGeCs/umMmSatainaolnyosfisalflorfelaocwhstteepmsp.erAatufrleo.w The of 1 first tot ml/min awlavsolaluwmaeys(3s"urppolwiefdrtoomththee i n- bliynesuGbCtr/aMctSiosnyosfttehm.e vTohelruemfeorteo,tthheeivn-olliunemeGpCa/ssMeSdtshyrsoteumghfrtohemPthUeFtoctaarltvriodlguemceanpabsesecdaltchurloautgedh ththreoruegahctPoUrFas isnhToawbnlein5.t4h.e1.22"carnobwefroobmtatihneebdoatstofmol.loFwso:r example, the total volume passed 32.99ml - 1 mlmin. x (197 - 85) sec. / [60 sec./min.] = 30.12 ml sToucpalpcultliaotteehtdeheint-oltianleaGmCou/nMtSofsySsOt;emreaclosovenreeeddusstiongbetchoeuonftf-eldianesGwCel/lMaSs tshyestveoml,utmhee cvoollluecmteed fbryoTmedtlheartobtaagl.voTlhuimsetpotaaslsveodltuhmreocuagnhbtehecraelaccutolra.tedThbey lsausbttrlaincetiinonoTfatblhee5f.i4r.s1t.t2icmaenbsteepobvtoaliunmeed by subtracting the first time step volume (10.92 ml)fromtotal volume (32.99 ml). AItmitnheutoenspertioofrtthoesaemxppleerigmaesnitfi,catthieonm.ethMaenteh/aainremwiaxstuirnetrwoadsucfeldotwoedsutphprloyuhghydtrhoegeenntitroe csoysntseummefor seyxcsetsesm fwlausortinheenduorpienngecdotmobiunssteirtonthaensdaamlpsloetporsoebrevewiatshainfutehle spoyurrocper.obTeh.e Aptyrtohpartobteimlet,ratnhsefreerwlaisne n1o25a0ppCr.eciDaubrleinggasanfdlofwoltlhorwoiungghtthhies gsayssitfeimc.atTiohne, smaemtphlaenwea/sarthfelnowgsaswiefpitedthfeorga4s0ifsieecdopnrdosduatcts fflroowmratthee pwyarsop1r.o0b6emtLo/tmhienreaatct2o3r.CFfoorr tIhemi6n0.012Csceocm.buAstt2i6o0ntCe,st,thfeorteemxpaemrpalteu,retohfe tmhetehoanvee/nair pcyonrtoapirnoibnegatphperpoyxriompartoebley, 1t.h3etmiemtehsa.nHeo/awiervefrlo,wtwheou4l0dsehca.vheeeaxtipnagndtoed12to50swCeetpo gtahseivfoyltuhmeesoafmtphlee during this flow period would have also forced approximately 1.9 pyroprobe volumesofgas tfhreorme wthaesplyirkoeplyroablesotaottehmeproeracatroyrb. aDcukrifnlgowcoofolaiinrignftrootmhe12p5y0roCprtoob2e6a0stChefoglalsopwriensgsguarseifiincsaitdieonit, idnrcorpepaesde.d Ttootphuermgaextihempuymrorpartoebaen/tdrhaenlsfdefrorli1ne0s,elco.woTfhaeiprytroopthreobpeyrwoapsroabddeictihoanmablleyrpwuarsgetdhewnith 2H3efCoran2d0tshece. HeFofrltohwew6a0s04.C5c3ommUbmuistni.oTnhteestt,otfaolrveoxlaummpeloef,tthheeapiurrfglionwgrmaettehwaanse,4.ai6r3, amnLd/min at helium was 2.78 ml at 23C, which corresponds to 5.0 ml at 260C, Since the effective volume oIfthpreoptyorcoolp)r,otbheics hvaomlubmeerwciotmphlettheeslaymfpllueshpersotbhee piynrseorptreodbies c1h.5acmmb'e3(r.3botimtoesft. poTahgmies p1u0irgniPngh.ase procedure was applied for the combustion test at 900C and the blank between 600 and 900C. dFuorriinng-ltihneeeGntCi/reMcSomabnaulsytsiios,ntpheerhieoaddtoofctohnceeGntCractoeleufmflnuewnatsgahseltdhaattwtahse tienmtpreordautcuedreaotf|-m6l0/mCin flow rate. The GC/MS temperature programming was started after the final helium purge. 54.11. In-lineGC/MS Analysis 9F0ig0urCe,s r5e.s4p.e1c.t1ivaenldy.5.A4.1s.i2ngslheoswultfoutraldiiooxnicdheproemaaktwoagsratmhse foonrlPy FidOeSntcifoimabbulestpieoankaftor60b0otahnd combustion tests. Tetrafluorosilane, a common intermediate in the other combustion tests, was 002065 1s not observed for the PFOS combustion tests. It is not clear why the total ion chromatograms for PFOS `source combustion might have at 600 suffer and 900C differ so dramatically from the other ed fromalossofsensitivity due to the repetitive, results. heavy- The duty MSD use. No attempts were made to clean the MSD source betc he ca leanu ingpsroce ess requires MS signal tuning and the recalibration this stageofthe testing. ofall standard gases previously conducted, which was not feasible at | Figure 5.4.1.1. In-line GC/MS lon Chromatogram for PFOS at 600C ot ermono r= e] o--ven]s]] Figure 5.4.1.2. In-line GC/MS Ion Chromatogram for PFOS at 900C 5.4.1.2. Off-line GC/MS Analysis Figure 5.4.1.3 shows the total ion chromatogram for off-line GC/MS analyses for PFOS combustion at 600C. The largestpeak atthebeginning is associated with air. The second peak at di 1.0 min. was oxide. Figure identifiaesd 1,1-difluo 5.4.1.4showsthetotal rocthene. Thepeakat ion chromatogram for 3.0 min. off-line was GC/ identified as MS analyses sulfur for PF OS 002066 16 `combustion at 900C. Similar results were obtained. The largest peakatthe beginning is : associated with air. Thesecondpeak at 3.0 min, corresponds to sulfur dioxide. }' szaemse)ed || Sr rarorr 22oee! | gE Figure 5.4.13. Off-line GC/MS lon Chromatogram for PFOS at 600C "Figure 54.14. Off-line GC/MS Ion Chromatogram for PFOS at 900C 5.4.1.3, LC-MS AnalysisofExtracts Tofarbelaeco5r./4t.r1a4nssfheorwisntehetuabnianlygtaifcaelrrtehseul9t0so0ftChteesrtesacutmorm/etdratnosfoenrliynaeboeuxttr0ac.t0i4o%n soaftmhpleesP.FESx.tracts added. Table 5.4.1.4. Methanol Extraction Results for PFOS Combustion Test Extraction TM PFOS (pg/ul) 154 _PF0O.S11(ug) 2 8.61 0059 002067 1" 5.4.14. LC-MS Analysis ofPUF Cartridges Table 5.4.1.5 shows the analytical results for the PUF sampling cartridges. The amountofPFOS captured in the PUF was 0.49%ofthe PFOS added at 600C. Only 0.07% was captured by the PUFsat 900C. Surprisingly, somewhat larger amountsof PFOS were extractedfromthe second PUFin a two-PUFseriesatboth600Cand900C.Thissuggeststhatsome PFOScould have passed completely through the system, but in the third transfer efficiency tests, much larger amountsofPFOSwerecapturedinthe first PUF in the seriesshowingthatthe first PUF typically collects more. An amountofcarryover equivalent to 0.026%ofPFOS added in the preceding 600Ctestswas extracted from the PUF in the PFO interim blank. Table 5.4.1.5. PUF Extraction Results for PFOS Combustion Test Temp Exwaction PFOS PFOS ) Gg) (ug) 600 PUF @ 251 0.62 PUF (2 640 16 900 PUF (1 431 oll PUF (2 901 02 5.4.2. FC-1395 Combustion Test pTarbolbee w5.a4s.2w.1eisghhoewdsbneeftoraemaonudntaoftfesratmheplceomgbaussiftiieodnftoerstFs.C-1395 combustion tests. The sample Table 5.4.2.1. Net AmountofGasified Sample for FC-1395 Combustion Test Temperature Usage Loaded Dried Remaining Net Amount of 0) Mass(mg) Mass (mg) Gasified 600 (mg) PUFF 214 0.56 Sample (mg) 0.04 0.52 TB 222 0.58 0.06 052 900 PUF TB 220 223 057 0.58 002 015 0.55 043 "TCoaTlicnuleaGtOedVbaEseadnaolnytshiseawnadtoefgcoantenctosll(e1c4t%i)o.n wing PUF. *OFline GUMS analysis singTedias Bag. Table 5.4.2.2 and 5.4.2.3 showsflowrate profiles usedfor FC-1395 combustion testsat 600 and 900C, respectively. The detailed explanation for each value can be found in section 5.4.1 00L088 18 TimTeaPbelreio5d.4.2.R2e.acFtloroFwlRoawte PrPoyfriolperfoobreFFCl-o1w3R9at5eCombTuosttalioFlnoTweRsatteat 60V0olCume, (se) Rate(mbmin) Air (mimi) Air CH, (m/min) (ml) 600--8650" 905030 00.8050 016 000 1054 0.00 1054 000 18557--115677 995533 0850985463 001166 1051403154432 1220675 167-177 177-197 9.53 820) 463 4s@E' 016 0 "237 422349 `To`tTaolvtaollvuomleumpaespsaesdstehdrtohurgohurgehaPctUoFr ((mmll)) ~~ 3219..8052 SystemopeneddueT1ot0aslamvpolleumineseurstieodnf.oArosffisneuvG0moMuilSenfSlgoOw q*Luainnteiraiinvcereaansal(yssipspr(omxli)za_te_) 21".#35S%wichetdo phaeslisuemdftohrrsowugehepP.U.Tota*lVcarrioerufsll eodwvtoou lcuamleumtlahtae ptaostsaleamtohurnoutgohfSthOe rreeacctoovre.re*dTuostailngcoafrfe-lrifnleoGwCv/oMlSusmyetshtaetm. "TimTeaPbelreio5d.4.2R3e.acFtlorowFlRoawte PrPoyfrioleprfoobreFFCl-ow13R9at5eCombTuostatlioFlnoTweRsatteat 90V0olCume (se) Rate (Amiirimin) (ml/min) Air CH, (mimi) Gal) 0-60 714 60-85 000 063 000 000102 07.0809 708009 18759--117899 771144 0630363463 on 012 7.89 7.891189 1236 165 118999--211999 GL71A4 M 434H63)! 002 1110.6879 315968 Tot`aToltavlovloulmuepmaespsaesdstehdrothurgohugrheaPctUoFr((mmll)) ~~ 2274..4240 SystemopenedGusTo0tsalamvpolleuminesuesrteidon.forAosff-sineuoGomoCu/tilMeStnfSlgOo,w quLainntietratiinvcereaansaly(sspipsr(oxmi)maie. _19.55 Swiich0ed pahselsieudmtfhorrsowuegehpP.UFs*.TolVcaeorulsleodw ovu coallucmuemlahtaee tpotaaslsaemdotuhnrtoougfhtSOe;rreeaccotovrered*uTsoitanlg c of-lia neoGwCv/e oMlSumser ytshtaetm. 54.2.1. In-line GC/MS Analysis pFeigaukraet50..44.2t.o1 1s.h0omwisn.thweatsotnaolticolnecarhlryoimdaetntoigfrieadm. fTorheFCs-e1c3o9n5d pceoamkbuastt1i.o7ntaot26.040coCr.reTsphoenfdisrstto s`muilnfuutredsiowxaisdei.deTnthiefpieedaaksabten7z.1enmien.folwlaosweiddebntyiffileudoarsobceanrzbeonne disulfideandthe at 11.1 min. The lwairdgeestppeeakak at 10 ainpcpleuadreedbeantzo1n0ittroil1e3 amti1n7u.t7esmicno.rarnesdpnoanpdhstthoatleetnreafaltuo2r1o.s1ilmainne.. FTihgeurpee5a.k4s.a2f.i2erstheotrwasfltuhoerotsotiallanieo:n csuhlrfourmadtiooxgirdaemafnodr FthCe-p1e3a9k5acto1m1bumsitni.ownaast 9i0de0ntCi.fieTdhaesfibresntzpeenaek.aTth2e.2shmairn.p pweaaskiatde1n4t.2ifmiiaensdutes and the subsequent wide peak both show a strong 85 signal that is attributed to tetrafluorosilane. 002069 19 "Figure 54.2.1. In-line GMS Ton Chromatogram for FC-1395 at 600C "Figure 54.22. In-line GC/MS Ion Chromatogram for FC-1395 at 900C 5F.i4g.u2r.e2.5O.f4f.-2l3insehGowCs/tMhSe tAotnaalloysnischromatogram for off-line GC/MS analyses for FC-1395 c0o9mbmuisnt.iwoanastid6e0n0tiCf.iedTahse1l,a2r-gieflpueoarkaoetthheenebfeoglilnonwiendg bsyassuslofcuiradtieodxwiidtehaatr3. mTihn.e,nextpeak at dDiifflfuuoorrooddiimmeetthhyyllssiillaanneeaatl4s.o8ismilni.k,elbyepnrzoednuecaetd9d.u9riminng.thaendgafsilfuiocraotbieonnzpernoeceasts.10F.i1gmuirne.5.4.2.4 s90h0owCs.thThteotlaalrgieosntcpheraokmaistaosgsroacmiaftoerdwoifft-hliinre.GCSu/lMfSuradniaolxyisdeesafto3r FmCin-.13w9a5sctohmebounsltyiiodnenattifiable product 002070 2 "Figure 5.423. Off-line GC/MS Ion Chromatogram for FC-1395 at 600C reoooe] | prvered | Figure 5.4.2.4. Off-line GC/MS on Chromatogram for FC-1395 at 900C 5Ta4b.l2e3.5.L4.C2.-4MsShoAwnsaltyhseiasnoaflyEtxictarlacrtessusofthe amountofPFOS was found. reactor/ transfer line extractions. No detectable Table 5.4.2.4. MethaExntorlacEtxitornactPiFOoSn(pRge/uslu)lts fo_rPFFOCS-(u1g3)95 Combustion Test | 1 500 <0.035 2 <5.00 <0.035 5Ta4b.l2e4.5.L4.C2-5MsShoAwnsaltyhseiasnaolfytPiUcaFl results for the PUF sampling cartridges, amount of PFOS was found. No detectable 002071 2 . Table 5.4.2.5,_PUF Extraction Results for FC-1395 Combustion Test Temp Media PFOS PFOS Q Ogu) (8) 60 PUF() <s00 <012 PUF(TM) <500 <0.12 90 PUF(Y) <500 <012 PUE() <500 <0.12 5.43. FC-807A Combustion Test Table 5.4.3.1 shows net amountofsample gasified for FC-807A combustion tests. The sample probe was weighed before and afte the combustion tests. `Table 5.4.3.1. Net Amount of Gasified Sample for FC-807A Combustion Test Temperature Usage Loaded Dried Remaining Net Amount of co M(amgs)s M(amgs)s (mg) Gasified Sample (mg) 600 PUR 268 059 000 0.59 TB" 268 059 000 059 900 PUF 243 053 008 045 TB 255 055 002 053 *1"CnaTlicnuclaGteCd/bMasSeadnoanlytshieswaanldeorfcfo-ngatsecnotlsle7c8t%i)on.using PUF. * OF-lneaGnC/MaSlyswiingsTedla Bag. Tables 5.4.32, 5.4.33, and 5.4.3.4 show the flow rate profiles used for FC-807A combustion tests at 600 and 900C, and the blank test between 600 and 900C, respectively. The detailed explanation for each value can be foiunsenctidon 5.4.1. PUF samples were collected from the blank runs between the 600 and 900C test runs. The unheatedvalve transfer line tubing. downstreamofthe reactor/ransfer line tubing was also extracted after the combustion test at 600C. The purposeofthese analyses was to measure the carryover between the tests on a single fluorocarbon product done at 600 and 900C. `Table 5.4.3.2. Flow Rate Profile for FC-807A Combustion Test at 600C Time(ePce)riod RRaetaect(omrliFmlionw) Pyrop(rmo/bmeiFnl)ow Rate Tot(amlVFmlionw)Rate Vol(umlm)e, 0-60 A9i7r0 0A8ir4 C0H1,5 1069 1069 8650--8155"7 097000 008040 000105 1000.609 102080 115677--116777 99.7700 0844363463 001155 106914481448 224110 177-197 8.89 (He)" 4."5T3ot(alHvoo)lume pas0sedthrough1r3e.ac4t2or (ml) 324.5407" "Total volume passed through PUF (ml) 29.64" Total volume sed foof lineGOMS SO, quaniative snalysis(m) _ 2181 hSelyisutmefoorpsewneeedpG.uTottosalacmaprlreieilnsewrtivoon.luAmeshaspuaBsosmoeudltilhertnoufglghowh?eLrienaectaorr.incTroetaasl (caaprperroxfimlaotwev).oluSwmhiaelche0d passed through PUFs. *Volume used to calculate total amountofSO recovered usiog off-line GEMS system. 002072 2 Table 5.4.3.3. Flow Rate Profile for FC-807A Combustion Test at 900C Time Period ReactorFlow ses) Rate (mimin) Pyro(pmrolb/emFilno)w Rate To(tmall/Fmlionw)Rate _ Vo(lmiu)me Air 0-60 7.25 A0i6r6 0C1H 803 803 60-84" 000 000 000 000 000 187-81-17888 772255 0606.366468 001122 80385013200 1125687 188-198 725 46 012 1200 200 198-218 627 (Hey 4.T5o3ta(lHev)o*lume pas0sed through r1e0a3ct0or (ml) 27.38.86"0 Total volume sed for off-line"GToCta/lMvSolSuOm,eqpausasneditthirvouagnhalPyUsiFs ((mml)) _ 1294..8655* Shysetelmfooirpsewuneeemdpd.u*eTtootsaalmcpalreerinsfelrotwiovn.olAumeshastpuansosmoedutilehnflrgow.oth>Luirengaecthroirn.cr* eTaosal(caapperorximlaotwve).oluSwmtihteacthetdo passedthrough PUFs. * Volumeused ocalculatetotalamountofSO;recovered singoflne GC/MS sysem. `Table 5.4.34. Flow Rate Profile for Blank Analysis between 600 and 900C TimGeeP)eriod RReaatceto(rmF/lmoiwn)_ Pyrop(rmob/emiFlno)w Rate To(umll/FlmoiwnRate Volmlu)me 0-120 A9i7r0 0A8r4 0C0H0 1054 21.08 112300--113400 9.9.7700 084436463 000000 1051445313433 220379 140-160 BSI(H 4S3(HOT 000 Total V1o3l.4u2me (m) 3a0.a01 *Linar crease (spproximate). ** Switched to helium for sweep 5.43.1. In-line GC/MS Analysis Figure 5.4.3.1 shows the total ion chromatogram for FC-807A combustion at 600C. The first peak at 06 to 1.3 min. was not clearly identified. The second peak at 1.9 t0.2.4 min. was identified as sulfur dioxide. Thepeakat 7.1 min. was identified as carbon disulfide. The peak at 8.1 min. whichshowsstrongspectra atm/z = 69 and 51 was not clearly identified.Peaksat 10.3 and 11.1 min. were identified as benzene and fluorobenzene, respectively. The wide peak that appeared at 11.2 t0 12.6 min and the subsequent background correspond to tetrafluorosilane. The two major peaks after tetrafluorosilane were not clearly identified. Figure 5.4.3.2 shows the total ion chromatogram for FC-807A combustion at 900C. The frst peak at 2.0 to 2.8 min. corresponds to sulfur dioxide. The largest peak at 15.4 min.andthe subsequent high background comespond to tetrafluorosilane. 002073 2 = | Jus "Figure 5.43.1. In-line GC/MS Ion Chromatogram for FC-807A at 600C "Figure 5.43.2. In-lineGC/MS fon Chromatogram for FC-807A at 900C 5.43.2. Off-line GC/MS Analysis Figure 5.4.3.3 shows the total ion chromatogrfaomr off-line GC/MS analyses for FC-807A cato3m.b0usmtiino.naantd6t0h0etCh.irdTpheeaklaartge4st.8pemainka.twtehreebiedgeinntniifngiaeisds assuslofcuiradtieodxwiidtehaanidr. Thesecondpeak sdihfotwusortohdeitmoettahlyilosnilcahnr,ormeastpeocgtriavemlyf.or Tofhfe-rleinweeGrCe/nMoSfuarntahelrysiedsenftoirfiFaCbl-e8p0e7aAksc.oFmibguusrteio5.n4.a3t.4 900C. Similar results were obtained. Thelargestpeak a the beginning is associated with air. Tdhifelsueorcoodnidmpetehaylksaitla3n.e0,mries.peacntidvtehleyt.hirdpeakat4.8min. corrtoesulsfurpdiooxidneadnd 002074 2 prod LL LL Figure 5.433. Off-line GC/MS lon Chromatogram for FC-$07A at 600C lzoaaze: ||i . poy "Figure 5.434. Offline GC/MS Ion Chromatogram for FC-807A at 900C 5Ta.b4l3e3.54L.3C.-5MsShoAwnsaltyhseiasnaolfyEtixctarlarctessusofthe reacto/ransfer line extractions. No detectable amount of PFOS was found. `Table 5.43.5. Methanol Extraction Results Extraction PFOS(pg/a) for FC-807A PFOS (ug) Combustion Test S00 0.035 ad <500 <0.035 T5.a4b.l3e.45,.L4.C3.-6MsShoAwnsaltyhseiasnoaflyPtiUcaFl resultsforthe PUF sampling cartridges. No detectable amount ofPFOS was found. 002075 25 | Table 5.4.3.6._PUF Extraction Results for FC-807A Combustion Test Temp co) Media PFOS ~~ PFOS Geb) (ue) 600 PUF5] <500 <0.12 PUF(2) <5.00 <0.12 900 PUF a) <500 <0.12 PUF (2 <500 <0.12 `5A.f5t.er 2* the Heated Blank combustion tests Combustion were complete Analysis d, the heated b lank re a ct or / tr ans fer ine tubing was analyzed again to examine system cross contamination at temperaturesof600 and 900C. In- line GC/MS analysis, off-line GC/MS analysis using Tedlar bags, and PUF cartridge sampling `were conducted. The same process used for the first heated blank analysis before the sample `combustion tests was performed for this second heated blank analysis. The PUF samples were sent to 3M Environmental Laboratory for LC/MS analysis. 5.5.1. In-line GC/MS Analysis `Tables 5.5.1 and 5.5.2 show flow rate profiles and carrier flow volumes used for heated blank analysis at 600 and 900C, respectively. Figures 5.5.1 and 5.5.2 show total ion chromatograms fboarckregarcotuonrdtenmopiesreaatnudrensoatco6n0t0amainndat9i0o0nCw,asresfpoeucntdivfeolry.eitThheretcehmrpoermaattuorger.ams show only TimeTerTiaobdle 5R.5e.a1c.toFrlFolwowRate PPryorfoiplreobfeor HeaTtoetdalBFllaonwkRaAtnealysisTaoti6l00CSampled (sec) 0-120 113200--112300 10-160 Rate (ml/min) 100 1100.00 8S3(H (Fmllo/wmiRant)e 081 0.814634.63" 4.53 (Hor (m/min) 1081 10.8114>6314.63 Toal V1o3l3u6me (m) Vo@lu)me Vo(laum)me? 06 108 220142 21.2975 _d_a_s3063_27a5n7 *Linear increase (approximate). "* Switched to helium for sweep. * Sampled volume for PUF `and Tedlar bag collection. Table 5.5.2. Flow Rate Profile for Heated Blank Analysis at 900C Time Period _ Reactor Flow Pyroprobe Tol Flow Rate Total Sampled 2%) Rate (mUmin) ~~ F(lmoiwfmRiant)e (m/min) Vo@lu)me VoGlmu)me? 0-150 7.11 0.62 173 19.33 16.83 150-160 7.1 0.62 >4.63" 7.733 11.74 1.62 146 160-170 7.11 4.63 11.74 1.96 L179 170-190 6.16 (He)* 4.53 (He) 10.69 3.56 323 Total Volume (ml) 2647 23.30 *aLnidnTceadrlianrcrbeaagseco(lalpecptriooxni.mate). Switched to helium for sweep. Sampled volume for PUF 002076 26 """" Figure 55.1. In-line GC/MS Ion Chromatogram for Heated Blank at 600C "7" Figure 5:52. In-line GC/MS fon Chromatogram for Heated Blank at 900C 5.5.2. Off-line GC/MS Analysis Figures 5.5.3 respectively. and The 5.5.4 large spheoakwstoattatlhieobnecghirnonminagtoagreraamsssofcoirattehde whietatheadirb.laNnok oatt6he0r0paenadks9w0e0reC observed. "Figure 5.53. Off-line GC/MS Ion Chromatogram for Heated Blank at 600C 00Z077 2 | Figure 5.5.4. Off-line GC/MS Ion Chromatogram for Heated Blank at 900C T5a.b5l3e. 5L.5.C3 -MshSoAwnsatlhyesiansaolfytPicUaFl rCesaurlttrsifdogretshe PUF sampling cartridges. No cross contamination was detected. Table 5.5.3. PUF Extraction Results for Heated Blank Analysis Temp PFOS (pg/ul) PFOS (ug) Q 600 <100 900 <100 <025 <025 S5.a6m.plTertarnasnspfoerrtefEfficfiiecniceyntcesytsTewsetrse cfoonrdPucFtOedSto investigate how efficiently PFOS transferred through reactor/ransfer line system. Three typesoftests were conducted would as be described in the Phase III protocol and its addendum. I5.n6t.h1.e f1ir*stTtrraannssfpeorretffEifcfiiecniceyntceystT,ePsFtOS was volatilization in the pyroprobe chamber and the `rpeearcftoorrmaedn.d tTrhainssfteerstlienxeasmwienreeshtehaetterdatnsof2e6r0efCfi.ciPenUcFyocfasrtarmipdlgeessagmapsliifinegdoifntthheeopfyfr-ogparseosbewaasnd ttrraannssfpeorrteefdfitchireoncuyghterste.actToarb.leTa5b.l6.e1.52.6s.1h.o1wsshtohwesflthoew net amount profiles of gasified sample for the 1% Table 56.1.1. `Sample Net ALmooaudnetdof GasifiReedmSaaimnpeldeafftoerr 1" TransNfeetr AEfmfoiucnietncoyf Test --PPrFoOSs Mass (mg) 00553 Gasification (mg) 00005s _Gasified Sample (mg) 0 004488 002078 23 | Time Table 5.6.1.2. Flow Period Reactor Flow Rate Profile Pyroprobe for 1" Transfer Efficiency Test* Total Flow Rate Total Sampled (sec) Rate (mlimin) Flow Rate (ml/min) (ml/min) Vo@l)ume Volmu)me 600--6804 010600 008020 1060802 1060802 1582 18546--115666 116600 0802.382453 1681265822053 0318 12899s 166-186 160 453 Total V2o0l5u3me (ml) 68 __4695 651 4426 "PHUeFlicoulmlewctaisonu.sed for all carrier flow, Linear increase (spproximate).* Sampled volume for Tfarbolmet5h.e6P.1U.3Fscharotwrsidtghee. PTUhiFscraersturlitdignedsicaamtpelsitnhgatretshueltssafmoprlPeFwOaSs.eiNtohersatmheprlmealwlaysdriescsoocviearteedd in tPhyeroppyrroobperlorebaecctohramtrbaenrsfoerrtlhienegtausbiifnige.d sample was completely condensed in the `Table 5.6.13._PUF Extraction Results for 1* Transfer Efficiency Test Sample _PUF PFOS PFOS PFOS Extracts (<eg/0ul) <(0u1g)2 2 <500 <0.12 5.6.2. 2" To investi gTartaentshfeeprosEsfifbiicliteynctyhaTtetshte s a mple c o nd e n se d on th e walls ofthe pyrop robe/reactor straamnpslfeerclairnter,itdhgeesswameprleecwonanseccotleldecttoetdhdeipryecrtolpyrforboemusthiengpytrheopsrhoorbteesutpsptosrseiabmloefttrhaensfreeracltionre. PUF hsehaotwesdtthoe2n6e0taCm.oTunhteopfyrgoaspirfoibeed asnadmptlreanfsofrer2l"interawnesrfeereexftfriacciteendcuystiesntg. meTtahbalneo5l..6.T2.a2blseho5w.6s.2t.h1e flow profiles Table 5.6.2.1. Sample Net Amount of Loaded Gasified Sample for Remained afier 2* Transfer Efficiency Net Amount of Test --PPRFOOSS Mass (mg) _ Gasification (mg) o0d47 o0.w 00 _Gasified Sample (mg) o0.a47 092079 29 | Table 5.6.2T.i2.meFPleoriwodRatePPyrroofpirloebfeoFrl2o"w TransfVeorlEuffmiceiency Test" sec) 0-60 Rate (ml/min) 063 Gm) 063 60-82 82-176 000 063 000909 117866--128166 0634353453 024237 *Helium was used fToocualrrVioerlfulmoew.(ml)Linear in_c_r_4e.a32se (approximate). `reTsaublltes5f.o6r.P23UFshcoawrtsrtihdegeansaalmyptliecsa.l rTehsuilststefsotrsthhoewesxttrhaacttsm.eaTsaubrlaebl5e.6a.m2.o4unsthsowosftPhFeOaSnalsyutrivciavle pHyorwoelvyseirs,cnoonndieotifotnshoefPtFhOeSpysruorpvriovbees,traanndsietnttoerthtehePhUeFatseadmtprlainnsfgecralritnreisdguep. to the reactor. Table 5.6.2.3. MethSaanmoplleExtrEaxcttriaocntsResulPtFsOfSor 2*FTOraSnsfer Efficiency Test --_PROS __ T g89i7 ) (uogl) 2 <100_<04 Table 5.6.2.4. PUF Extraction Results Sample PUF for 2*! PFOS Transfer PFOS Efficiency Test Extracts (pe/ul) (ug) PFOS = <10.0 <025 2100 _<025 5.63. 3" Transfer Efficiency Test tAhr3o"ugthratnhseferreeafcftiocri/ernacnysfteerstlwinaestcuobinndgucatneddstaomepxlaemdibnye PhoUwF mcaurctrhidPgFesOiSftchaensebesatrmapnlsefserwreedre ftuobrimnegdianndth2e) trheaecutonrh.eaTtewdovmaelvtehaannodlaesxstorcaicattsewdetrreanosbftearilniende:tu1b)itnhgeuhpesattreedarmoeafcttohre/tPraUnFsfer line ceaxrpterriidgmeesn.tsTwaeblree 5c.a6r.r3i.e1d sohutowussitnhgebnoetthaamioruanntdofhgealsiiufmiteodcsoammppalreeftohreeraecshulttess.t. The Aftera sample w0apsrpelvaecnetdthine tchoendreenascatotrioannodfthgeassiyfisetdemsawmapslec.loWsehde,nthtehteeGmpCeroavteunreteomfGpeCratouvreenrweaacshiendc2r6ea0seCd, tghaes fcuorlnleacctetioenmpuseirnagtuPrUeFwacasrstertidtgoetshweatseminpietriaatteudrewhsehnowtnheinGTCabolveesn5s.t6a.r3t.e2dahnedat5.i6n.g3..3. Theoff- 002080 | 30 | SaTmapbllee 5.63.Ca1r.riNeert AmoLouandteodfGasiRfeiemdaiSnaemdpalfetefror PUNFetCoAlmloecutnitonof Gas Mass _ (mg) Ga(simfigc)ation ~~ Gasifi(emdgS)ample PFOS Ar 048 --PRPFOOSS HHee 00550 0.00 0.48 oo0044 ~~ 004466 o`Txaybgleens-d5.e6f.i3c.i2enatndco5n.d6i.t3i.o3nasl.so show flow rate profiles PFOS gasification under oxygen-rich and Time PTearbiolde 5.6.3.2.TeFmpleorwatRuarete Profil foCraPreUrFGaCsolUlseecdtion (PF"OToSalGVaosliufmiec.ationSwaimtphleAdiVro)lume" 0(-se4e)5 GCCoOndviteionn (2C25)650 aod FloAw 1Ra0te7(ml/min) 7(8m2)5 499-67 Fumace 103 575 Air107 331 7a0l9)7 3201 963377--999377 GGCC ==226600,, FFuumamcea==c557e755 HAe1s0s7 $836500 7.6500 Sampled volume for PUF collection. Toul (ml) 1570 159.08 Time0PT)earibolde 5.6.3.T3Ce.onmdFpiletiorowant(ReaCt)e Profilea0fdoCFralrPoewUrRFaGtaCeso(lUmlsle/emcditni)on (PFTOoSi(lGaVaosliufmiecationSwuimtplheGHdae)V)ohume' 4010--461105 GFCuOmavceen13400>3256750 615-975 GC =260, Fumace = 575 HHeel1o0s8 He 108 73368900 450 393.748 58.50 Sampled volume for PUF collecion. Toul (ml) 175.50 - 15925 Tables 5.6.3.4 and 5.6.3.5 show the amountofrecovered sample from the extracts and the PUF vmcaoerlatasrtuilrdigazebesld,eirPnesFtpheOicsStitv(ees5lt.yt2.o%tTahhiere,P3U1"F2s.t.8ra%LnsaHfreeg)reercfoafuimlcodiuepnnatcsyssotfefsrtPosmFhOtohSwee(hde5a.qt6uei%dtearierc,alce3ta9or.lry4w%thheHartee)soiatmlwseaos PacFcOuSmualcactuemduilnattheed rienatchteorp/orratnisofneorfltihnees turpasntsfreeramlionfethheeatPedUFtoc2a6rt0riCd,gessu.gTghesetimnajgtohraitttyhoifsthe compounds could condense, or were in a particulate form, at this temperature. Table 5.6.3.4. Reactor/Valve Transfer Line Extraction Results "Sample Gasification Location Extracts PFOS FOS _-- Reactor T (e1u908) (u2g4) Air Vale 2IT 365%4 ods 24 PFOS Reactor 2 1 28 13530 oom 171 He TF Vave a 2 10s 7179 2 102 035 002081 | 31 Table 5.63.5. PUF Extraction Results Sample Carrier Cartridge PFOS POS Gas gu) (up) PFOS He T0330 58 ul 44 Ll Ar 1 or 2 2 <100_<012 5.7. Sulfur Recovery Rate as SO;, SOF, and SO;F; SBaOsFe;downetrheedeitne-catnedd.ofTfh-leinseulGfSur/rMeScoavnearlyysreast,e asuslSfuOr;wuassinfgouinn-dlimnaeiGnlCy/aMsSSsOy.stNemowSaOsFn;otand quantitatively repeatable. This was due primarily to the low SO; peak resolution using the cusriynoggetnhiecoffof-cluisnienGgCm/etMhSodsaytst-e6m0wCerweimthucahhsohladrinpgertitmheaonfSOca;. p4emaikns.obsBeercvaeudseustihengSOin;-lpienaeks GreCc/oMveSr,ywanealdyesciisdeasd StoOsu.seTohfef-dlienteaiGleCd/oMpSeraatniaolnyatlicparlorceesdulutrsestowqeuraentdietsactriviebleydainnaSleyczteiothne5.4sulfur Taambollear5.b7a.s1isa.ndTFhiegufroerm5u.7l.a1osbthaoiwnetdhefcraolmibtrhaitsicoanlirebsrualttiso.n Twahse:sulfur recovery rate is reported on SO; (Mol) [A+r 4949e 80]a / [1.7997x 10") `Table 5.7.1. SO; Calibration Results Using PLOT Column Conc. (ppm) _ Mol. # Areal Area2 Area (Avg) 1000 4.09E-08 7191079 6980771 7085925 700 2.86E-08 4414365 4366705 4390535 400 163E-08 2304594 2295497 2300046 100 409E-00 425431 416699 421065 vLZ082 2 80 |-- 10"- md me vod A TT J 7 5010" o w0r%t -- DZ I I 1 -- 00 10 0 - TT1 110% 210% 310% a10* 510 Figure 5.7.1. SO; Calibration Curve (Molar Number vs. Peak Area) Prior to the sulfur recovery analysis as SO, a third SO; transfer efficiency test was conducted usingtheoff-line analysis approach. Table 5.7.2 shows the results. Air was flowed through the `reactor at 8.85 ml/min fo2r min. 30 sec. while the SO, standard was being injected and the offgas was collected using a Tedlar bag. The average recovery rate was 75.6%. Thisisvery similar to the recovery rates obtained from the in-line analysis, i.e. 83.7 and 76.4%, suggesting that the lack in 100% recovery is due to sample losses in the combustion systemandnotthesampling `Table 5.7.3 shows sulfur recoveryrateas SO, for PFOS, FC-1395 and FC-807A. The last column shows the sulfur recovery rate taking into account a transfer efficiency rate of75.6%. Results for the Cg perfluorosulfonamides were quite reasonable, 10025%. Results for PFOS `werenot as good, with recovery rates ofonly 50-60%. Table 5.7.2. Standard SO; TransferEfficiency Volume (ml) Area Calculated Mol. # # of Mol. Used Transfer Efficiency (%) 002083 33 Compound Temp. Volume`TablAer5e.a7.3.CSoluclufluatredReGcaosvifeireyd RfaotfeMaosl.SoOf; Recovery Recovery Fare Mol# (Mmsg)s GSaasmipfileed Rate(%) aCtoemreEcftfoicnie(n9c)y PFOS G00 900 2207 1962 2169830 327E:07 038 2676600 346E0T 050 7.06807 929E07 463 372 61.2 492 FC-395 600 900 2135 1955 4159651 SS2E07 3402701 423E.07 052 043 TASE07 SSIET 772 716 1021 94.7 FCBO7A -- 600 2181 09000 1199885 6587251 88E-07 6363554455447 775.S55E6007 059 005533 O.05E-07 B8M2E.07T 9338 991199 1240 n1a2l15s 5.8. Extracted Ion Analysis c`Thhreofmoaltloogwrianmgsioofnsth(6e9P-CFFOsS, 1a1n9d-CC;yFpse,rafnludo6r7os-uSlOfFo)nawmeirdee etxesttrsac(tiend-lfinreoamntdheoftfo-tlailneioGnC/MS `aTnhaelypsuersp)otsoeoafnatlhyizseafnoarlytshiespwraessetnoceporofvpiedreflaudodriitnioantaeld iannfdorsmualftoinoantree-gcaorndtiainngitnhgeipnotteernmteidailates. ifdoernmtaitfiioedn ionftvhoelaGtiCl/e MflSuoarpopcraorabcohnsouatnldinveodlaitnitlheefplruoerviinoautsedsoecxtyisounlsf.urTchoemapnoaulynsdesstihnadtiwcaetreedntohatt ithnede6e7d iaocncsoeuxnitsetdinfonregilnitghieblaenaalmyosuisntofstthheutsotianldiicoanticnghrthoamt aaltloggasr-apamhsasseulsfuulrfudricoxoimdpeoaunnddcsarwbeoren tdihseultoftiadle.ioTnhicshraonmalaytsoigsrfaumrst.herMionsdticnaotteadbltheathe6r9e awnads 1t1he9pornessewnecreeopfretsheesnetiinonmsionstthief nGoCt aslilgonfals natotshiodretntrieftieendtiinontthiemaensa,lytshiussofintdhiceattiontgalthiaotn octhhreormvaotloagtirlaemsfl.uorocarbons were present that were: iIonncownatsradsettteoctteesdtfsrroesmultthsefPoFrOotShecromfbluuosrtoicoanrbcohnrcomoamtpoogurnadmss(oYbtaamiandead farnodmTaeyiltoherr,t2h0e02i)n-,linnoe 6or9 iofofn-ilzianteiosnamdeptleicntgorpr(oHcFeIduDr)esa.s wDeulrlinasg mthaessansapleycstirsaolfdtahtea wofefr-elicnoelsleacmtpelde.s,Dhuyedrtoogtehne sfulsapmeect creosmublutsstfiroonm,tthhee eHxFtrIaDctdeadtaiofnorantahleysciosmobfutshteiotnotparloidounctcshorfoamnaottohgerramcsomgepnoeurnatdewdiftrhom PFOS tpheerfHluFoIrDoadlaktyal fmooriePtFieOsShcaovmibnugslteissonthparnoducctasr.boAnnsa,lylsaibseolfedthaessPeFXHSF,IDwdaastaansahloyzweedditnhaeddition to sftorrumcatturiaolnosfimviollaartiitlyoefflPuForXoScarabnodnsP.FOTSh,isthainsalaynsailsysdiisdsnuobtstgainvteiaqtueasnttihfeipaobtleentriesaulltfso,rmbauttidouneotfo the volatile fluorocarbons from the combustion of PFOS. lFiingeuGreC5/.M8.S1 asnhaolwyssitshaett6o0ta0lCio.nAchHrFoImDapteogarkaamppaenadrtshewictohrrseasmpeonrdeitnegntHioFnItDimseigansalthfeor"aPiFr"XpSeaofkfifnoraitrhe(Ntzo,taOlyi,oAnrc,hCroOm)abtougtrdaome.s SrienscpeonthdetHoFflIuDordooceasrbnoonts,reitspisonadpptaortehnetmtohaltecvoullaatirlec:onstituents sfpleucotrroaclairobnosnscoarrreeeslpuotnidnignrgotomvtohleatGilCe fcloulourimnnatseidmculotmapnoeuonudssly, wiintchlutdhiengaiCrFc;onHs-t5i1tu,enStOsF.-6M7a,sCsFi6n9,FiCgFu,rCeF53.H8-.210a1l,onagnwditC;htFsh-e11H9F,IWDerseigenaxl.tTrhaefrcreostumlettshdeindtiotcaalteiotnhact thhre HoFmIaDtpoeaagknradtaaarme shown, retention timeof0.8 min. corresponds to amass spectral signal that contains the following 002084 34 6fl9uaonrodca1r1b9oinoinosnso:cc5u1r,n6e9a,ratnhde p1e19a.kofTthhee51FIiDonosicgcnualr.snLeiakretlhyectaanidlidofatthesetHhaFtIcDansibgenaaltwthriibluettedheto thheex5af1lauonrdoe6t9hianoen.saPreenttraif-alunodrtoeettrhaafnleuoisrodmeettehcatneed.atLiloknegelrycraentdeindtaiotnestfiomrets haend11a9lisooncoanrteapines na toar `swtoruolndg e1l0u1teioeanrltiheart tishannotpepnrteasfelnutiornotehtehuannekdnuoewtno ptesakl.oweItrsbpolialuisnigbploeitnht.atThheuxsa,ftlhueormooestthane tpertorbaafbllueocraonmdeitdhaatneesatnhda/tocrorherxeasfplounordoteothtahnee.HFID signal at 0.8 min.aretri and Figure 5.8.1. Total Ion Chromatogram and Corresponding HFID Signal for Combustion of PFXS at 600C (off-line sample) 002085 35 =| ER EeR EASTERE E Ree ER 2 I. Ge Be ise abe ake 366 3Ee ABs iEeTTT ---- : Figure 5.8.2. Extracted lons (CFH-51, SOF-67, CFy-69, CE;CF;H-101, and C;F-115) and Corresponding HFID Signal for Combustion of PFXS at 600C (off-linesample) Figure 5.8.3 shows the HFID signal for PFOS combustion at 600C, and the integrated HFID peak areas for PFXSand PFOS are shownin Table5.8.3. TheretentiontimeoftheHFID response from PFOS combustion is nearly identical to the HFIDresponse from PFXS combustion (see Fig. 5.8.1), strongly suggesting that the same combustion products areforming from these two different compounds. The HFID signal and integrated HFID peak area for PFOS combustion at 900C are shownin Figure 5.8.4 and Table 5.8.4. The peak is ca. 1% of the 002086 36 | rceosmppoonusendosbiuanidneerd tahte6s0e0coCn,ditthiuosnsi.ndicating nearly complete destructionoffluorinated --1 20000 | | ~~ Figure 5.8.3. HFID Signal for PFOS Combustion at 600C (off-line sample) Figure 5.8.4. HFID Signal for PFOS at 900C (off-line sample) Table 5.83.SaImnptleegratedPeHaFkIADrePaeakNAerteaAmoofuPnEtXoSfGaansdifPieFdOSat 600C PEXS 1150193 Sample (mg) 052 PEOS 3547614 038 TableS5a.m8.p4l.e IntePgreaatkeAdrHeFaIDNPeetaAkmAoruenatooffPGaFsOiSfieadt 900C PFOS 3901 Sample (mg) 050 . VuL08? 6. Discussion `The motivation ofthis study was to determine the incinerabilityofperfluoro-octanyl sulfonate (PFOS) ainfotdher perfluoro-octanyl compounds could be transformteod PFOS during the incineration process. A laboratory-scale study simulating a full-scale hazardous waste incinerator was envisioned in the phase I test protocol. Based on prior experience with halogenated compounds, we initially planned to use relatively modest conditions in the primary combustion zone (ca. 400C) to gasify the materials with more severe high-temperature (600 -- 900C), oxidative conditions applying to the secondary combustion zone. TGASofthe active ingredients indicated that higher temperatures (~ 600C) were necessary to gasify these unique `materials. The sponsor also requested that the experiment be designed to detect low-level (0.1%) concentrations of PFOS in the exhaust gases. These factors necessitthaetuesde of large amounts osfecm)atienraiaslpe(cmiiallllyigdreasmiqgunaendtiptyireso)praonbdehtioghf-ultleympgearsaitfuyrteh,elmoantegrdiuarl.atiTohneesxepcoosnudrietsio(ncsa,. w1h2i5l0eC, 40 representing quite severe conditions in the primary zoneofan incinerator, ..,a rotary kiln, are representativeofthe rangeofconditions that occur in a full-scale system. As such, the approach employed in the laboratory-scale combustion study described in the phase II test protocol is a reasonable extrapolation ofa full-scale incineration studyofPFOS and its potential precursors. `Combustion tests for PFOS and two Cy perfluorosulfonamides, FC-1395 and FC-807A, were `completed as requested by the sponsor. In-line and off-line GC/MS analyses, reactor effluent sample collection using PUF cartridges followed by LC-MS analysis, and chemical extraction of various transfer lines throughout the reactor system including the reactor itself followed LC-MS `analysis were conducted to investigate the following: 1) the extentofconversionofthe active ingredients, 2) the formation of fluorinated intermediate organic products, and 3) the extent of conversionofthe sulfur to sulfur oxides. `There was no indication that PFOS was generated from FC-1395 and FC-807A combustion. No quantifiable amountofPFOS was detectable ata detection limitofca. 10 ng/ml. During PFOS combustion, small amounts of PFOS were detected in the reactor/transfer line system and the PUF sample cartridges, specifically, 0.04%ofgasified sample in the reactor/ransfer line system, less than 0.4% in the PUF cartridges at 600C, and 0.05% in the PUF cartridges at 900C. High levelsofPFOS destruction were thus achieved at temperaturesof900C. "To validate the experimental results pertaining to the sampling and analysisofPFOS where in `many instances the analytical results were below the levelofquantitation, a seriesoftransfer efficiency tests were conducted. The goals of the transport (or transfer) efficiency tests were: 1) 10 seeifPFOS could pass through the combustion system under nondestructive conditions and reach the PUF cartridges and, 2) to determine recovery efficiencies and analytical detection lPiFmiOtSsw. aIsnatshsee1ssetrda,nsafnearlyesfifsiocfietnhcey tPeUstFwhcaerrteritdhgeesabiinldiitcyoatfetdhtehecloamcbkuosftiaonnysdyestteecmtatboletrmaantseprioarlt. `This result indicated that PFOS was either thermally destroyed in the pyroprobe chamber (1250C) or the gasified sample condensedinthe pyroprobe/reactor transfer lines and never rtreaancshfeerd etfhfeicPcieiUnecFyncystatemessptlweacsarctorinddguec.tBeadts1oe0dionvnestthieinvestga graetseultthse olfat1te"rtproasnssifbeirltieyf.ficIinentchyesteestte,sas,2% (00 38 esxutbrsatcatnst.ialHoawmeovuenrt,s,o3nc.e4%aogafinP,FaOnSalygsaisisofifetd,hewePrUeFincdareterdifdgoeusnpdoisnittihoenpeydrdoporwonbset/rtreaanmsofferthliene pPyFrOopSrosbuer/vtirvaenspfyerorllyitniecwceornedinteigoantsiivne tfhoer pPyFrOoSp.roTbheea2nd* ttheesthsehatoewde(d2t6h0atCm)eatsraunrsafbelrelianmeso.uTnhtes of tuunbainnsgwaenrdedsaqumepslteidonbywaPsUhFocwarmtruicdhgePsiFftOhSiswamastetrrianaslfwerarsedftohrrmoeudghintthheerceaocmtbour/sttriaonnsfcehralmibneer. A p3l"actreadnsifnetrheefcfiocmibeunsctyitoenstcwhaasmbtheursacnodndnuotctiendtotothaeddpryersosprtohbies.quTeshteiotne.mpIenrtahtisurteeostf,tPhFeOS was ocfotmhbeusttrianosnfecrhlaimnbeserwiatnhdintrtahnesfoevrelnindeursiynsgtetmhewaacstutahlecnohmebautsetditoon2t6e0stsC..ATthtihsisstetmhpeetreamtpuerrea,ture t`hTrGoAusghintdhiecastyesdttehmer(ethweoTulGdAbewneroePcFoOnSduvcotleadtialtizUatDiRonI, sdourtihnegrethweouPlhadsbeeIpnrooPtoFcOoSl movement rdeevmealionpemdenats)2.60ThCe. cWomhbeunsttihoencocmhbaumsbteironwacshathmebnerhewaatsedhetoat6e0d,0sComwheoifltehtheePtrFaOnsSfewralsinelsi.kely seunbtsrtaainnteidalinptoorttihoengoafstshterePaFm,OaSnwdaasltarragnesrpporrotpeodrtthiroonwugahstphreobtraabnlsfyerdelsitnersoyteodt.hNeePveUrFtshewlhesesr,eait mweaassudertaebclteedP.FPOFSOS(3w.a8s% aailrs,o1f1o%unHdei)n ptahessterdanfsrfeormltihneesc.oSmpbecuisftiicaolnlyc,haremsbueltrstsohtohweePdUtFhastampling acacrcturmidugleast.eRdesinultthsearlesaoctsohr/otwreandsftehratlisnliegshutplystlraergaemor afmtohuenPtsUFofcPaFrtOrSidg(es4..4T%heaisre, 3re0s%ultHse) PdUeFmso.nstTrhearteefdorteha,twifhePnFOnSo PwFasOSfowramsedobisnetrhveecdoimnbtuhsetitroannscfhearmlbienres,oitrwPoUuFlsddboewdnesttercteeadmoifn tthhee lciotmleb,uisftainoyn,cPhFaOmSbefroirnmtehdedcuormibnugsctoimobnustetsitos,n.one could conclude that there must have been very wAosuulldfubremoaxsisdibzaeldantcoeSwOza,sSaOttFe,mpatnedd bSaOsFed;ounndteher phrieghm-itseemtpheartatalulroeftohxiedastuilvfeurcionndtihteiosnasm.pTlhese GReCc/oMveSryanraaltyessewseirnedivcaartieadblteh.atNtehaersluylf1u0rw0a%ssurlefucrovreerceodvearsySwOa;s oNboaiSnOeFd;ofrroSmOFFC-;13w9a5s.dTetheected. rfeorcoPvFeOrSy.ratTeheobrteaairneedtwforopmotFenCt-i8al07soAurwcaessoafpperrorxoirmiantethleys1u2lf0u%r.mRaescsobvaelrayncrea.tesTwheermeo5s0t-l6i0ke%ly is pthyerocpornodbeensaantdiotnhoefptyhreoparcotbiev/ereiancgtreodriternatnssfaenrdltihneesi.r pTrhiemasruylfduergmraasdastbiaolnapnrcoedudcotessinnotthteake into a`ancacloyuznetdthfiosrpsoutlenftriaclomsopuorucnedso.f sAulnfoutrhienrtphoetesnytsitaelmsoasurtcheeosfe leirnreosr wisetrheelnoatckexotfraccotmepdlaentde 7qu8a.n6t2i4ta%t.iveThteraSnsOp,orttorafntsphoertSeOf.ficTiherneceywSaOs; atrcacnosupnotretdeffofriicnientchyetseusltfuyrimealdsesdbaanlaenfcfei.ciTehnecyhoifgh proetpeenattiaablilciotynodfetnhseatsieonroefcotvheeryactteisvtse siunggrgeedsitesntthsaatntdhitshseoirurpcreiomfareryrdoergrisadsamtailolncpormopdaucrtesditnocluding 0; on the wallsofthe reactor and transfer lines. iGnCte/rMmeSdiaantaelsy,siis..o,ftphroedurcetasctoofrienfcfolmuepnltewtaescocmobnudsutcitoend.toThasesemsosstthaebfuonrdmaanttiocnoomfbucsotmibouns.tion F`blyuporroodbuecntzweanse wbeanszeanles.o oBbesnezrevneedwfarsomobtsheercvoemdbufosrtithoenaolfl FofCt-h1e39s5amapnldesFeCxc8e0p7tA.PFFOoSr.PFOS, the intermediate in highest concentration at 600C was a C; or C; fluorocarbon alkane, most 002089 39 lciokmelpyoturin-dorwatestmraufclhuolroowmeetrhiannecoomrphaerxiasfolnuowriotehthtahnee6.0A0tC90re0suClf,s.theThceonncaetnutrreaotfitohnoifstbhyipsroduct athnadt isths otwhetrhmaatlpsetrafbliuloirtyiniastceodnasilsktaennetswairtehosttahbelretiensttesrmweedihaatvese acnonddruecqtueidreotnemfplueorraitnuarteesdisnatmhpeles `sCehceomnidcaarlys cCoomrpb.u,st2i0o02n).zoSnmeailnleaxmcoeussntosfof910,01-Cdfiofrluhoirgoheltehveenleso(fPdFeOsStrouncltyi)onan(dCi1b,a2-Special d`ainfdfuaolrkoeentehsewneas(FnCo-t1u3n9e5xpoenclty)edwaenrde aislscoonosbissetrevntedwiatth60t0heCm.olTehceulfaorrmstartuicotnuorfeopfertfhleuosrtaoratliknagnes `material, where that fluorinated aCg saturated fluorocarbon chain acids were significant combustion s present. products. There was no evidencteo suggest Fluorinated acids have been oSpbesceiravletdybCyheGmCic/aMlSs Caonraply.s,i2s0i0n2)c,ombbuutswteiroennsottudoibessoerfvoetdheinrtfhliusosrtiundayt.edTmhaeteproitaelnsti(aClifboarmation o`fTfhlerueorwiansatneod esvuildfoennicceafcoirdsthceoufolrdmnaottiobneoafsmceorrteaihniegdhulsyifnlgugoraisncatherdomaartoomagtriacphciocmtpeocuhnndiqsu,esi..., doir-dtihorxoiungshchoeuxladfhlauvoerofboernmzeedneunndoerrwtahsestehecroendeivtiidoensn.ce to suggest that polyfluorinated biphenyls pFruerctuhresroarnsaltyotPicFaOlSt,eswteinrgewnaost cfoonrdmuecdtdeudrtiongvetrhiefycothmabtutshteiofnoltleostwsi:nPgOcoSmFpaonudndCsy,Fp1o7tSenOt;iNalH. `eTxhaemrienwaatisonnoofetvhiedetnoctealtihaotn tchhersoemparteocgurrsaomrssffoorrtmheedSdOuFriinognPaFlOsoSicndoimcbautsetditohne.lFaucrkothferformation ocfosmebcuosntdiaornoyfamPiFnOeS,preFcCu-r8s0or7sA,,.a.n,dNF-CM-1e3F9O5S.EAaslmcaolhlola(mCoyuFn1to7Sf0u2nNd(eCsHt;r)oyCe;dH,POFHO)S, dwuarsing the oprbosceersvsedduien tthoetLheCp/rMeSsenancaeloyfsleasr.gIetaismounulnitkseolfy mtheatthPaFnOeSasretfheorfmueeldfdourrtihnegctohembcuosmtbiuosntiporoncess TcohnecepnrtersaetnicoenosoffexHceastsommestthhaatneefffuiecliernetllaytisvceatvoenfgleuoFroacthoemmsicaaslHprFodauncdtprreesvuelntt itnhesirgenfiofrimcaanttion ohfiglhoenrgupnedrefrluaocrtouaallkiynlccihnaeirnast.iTonhceonhdiytdirooncsa,rfbuornthfeurellitmoitfilnugotrhoechreenfiocramlatriatoinoo fwiplelrlfilkueolryobaelkeyvlen wcheariensl.imPietrefdltuoorCi,naatnedd Cal;kcanoemsp,onuencdess,safruyrtbhueirldiindnigcbaltoincgksthtaottrheefofromramtaitoinonooffPpFrOecSu,rsreoqrusirtionPgFCOy , perfluoroalkyl chains, did not occur in the combustion system. 002090 40 7. Conclusions r`TehleeadsaetPaFprOeSsetnottehdeheerneviinrocnlmeeanrtly.sThhoiws tchoantcilnucsiinoenraitsiboanosefdFmCa-i1n3ly95onantdheFLCC-8/0M7SAmdeoaessurneomtents, bneugtlwiagisblseubasmtoauntnitastoefdvboylatthieleexsturlafcotneadtieo-ncoanntaaliynsiinsgtdheagtrsahdoatwieodnnpergoldiugcitbsl.e 6S7ul-fSuOrFreicoonveirnideiscawteirneg: `aplesrofqluuiotreingaoteodd,al1ky0l0s:u2l5f%on.aTteheprdeocumrisnoarnstisnidnikcaftoerdsutlhfaturswucahspSrOec;u.rsGorCs/wMeSreannaoltyspirsesoefat in the rtheaatcttohreeCf-flSuebnto.nTdhwiassfcionmdipnlgetieslcyondseissttreonytedwi(tahndthdeiLdCno/tMrSefmoerams)urinemtehnetcso,mbaunsdtsitornontgelstys.suggests cHoingchlulseivoelnswoafscobnavseerdsoionnoLCft/hMeSPmFeOasSuwreermeenotbssoefrtvheedrferaocmtotrheeffinlcuiennetraantdionattehsotsr.ouTghhisanalysis of t6h0e%t,radnesppeonrtdoifngthoenmtahteerreiaaclttohrrtoeumgphertahteurceo.mbTuhsetidoonmisnyastnetms.inSkulffourrsurlefcuorvewraisesSvOa.rieGdCf/rMoSm 50 to apnraelsyesnitsoinfthpeerrfelaucotroirneaftfeldueanltk.ylTshuilsffoinnadtienpgreiscucrosnosirsstienndtiwciatthedtthheatLCsu/cMhSprmeecausrusroresmewnetrse, naontd s`tcroomnbgulsytisounggteesstts.s that the C-S bond was completely destroyed (and did not reform) in the Flilmuiotreidnattoefdlourograonbiecnziennteer(mFedCi-a1t3e9s5waenrde FobCs-e8r0v7edAionnltyh)e,rCe;acotrorCe;ffflluueonrto.aTlkhaenseesc(olimkpeloyupnrdosduwcetrse a1r3e9c5itohnelry)C.HHFi,ghCeFr4,moolreCcuolFa)r,waenidgh1t,1f-lduiofrliunoartoeedtphoelnyec(ycPlFiOcSaroonmlayt)iacnhdyd1r,o2-cdairfbuoonrsoewtehreeneno(tFCobserved. `iTnhceindeartaatifornosmysthtiesmlsabcoarnataodreyq-usactaelleyidnicsinpeorsaetoiofnPsFtOudSyainnddictahteeCs thpaetrpflruoopreorsluylofpoenraamtiidnegs.full-scale tIhneciennevriatrioonnmoefntth.esFeurfltuhoerirnmatoertdhece,omfpinoduinndg sthiastntohte lCi-keSlybotondbewaa ssicgonmifpilceatnetlsyoduerscteroofyePdFiOnSdiciantteos t(hfaltuorreifnoartmedatoirognaonficPcFoOmSpoiunntdhse,aStOmso)spihsehrieghflryomuntlhikeeelmyi.ttWeidtchotmhbeuesxtcieopntiboynporfodsutcatbsle C, and Cz ffalcuiolriotceasrdbuonrsi,ngfltuhoeriinncaitneedroartgiaonnoifctihnetserememdaiteartieaslsa.re also unlikely to be emitted from these 002091 a . 8. References CWaarsrotlel,MaGn.Ja,g,eT.hAusmsaouc,,R1.9C9,3,L4e2e,, J1.43W0.., Waterland, L.R., Dellinger, B.,and Taylor, PH.J, Air Ciba Specialty Chemicals Corporation, Final Report, 2002. Clark, W., Heap, M,, Richter, W. and Seeker, R., The PredictionofLiquid Injection Hazardous `Waste Incinerator Performance, ASME/AIChE 22* National Heat Transfer Conference, 1984. DMealtleirng,er1,98B4,,, T1o,r1r3e7s., ., Rubey, W., Hall, D., Graham, 1., and Carnes, R., Hazard. Waste Hazard. Dellinger, B., Rubey, W., Hall, D., and Graham, I, Hazard. Waste Hazard. Mater., 1986, 3, 139. Dellinger, B., Graham, M., and Tirey, D.A., Hazard. Waste Hazard. Mater., 1986, 3,293. Dellinger, B,, Taylor, P.H., and Tirey, D.A., Minimization and Control ofHazardous Combustion By-Products, Final Report and Project Summary, EPA/600/52.90/039, 1991. Dellinger, B, Taylor, P.H., and Lee, C.C.J,. Air Waste Manage. Assoc. 1993, 43,203. Giesy, J. P. and Kannan, K.,, Environ. Sci. Technol., 2001, 35, 1339. Graham, 1, Hall, D., and Dellinger, B., Environ. Sci. Technol., 1986, 20,703. Kannan, K., Koistinen, J Beckmen, K., Evans, T., Gorzelany, 1F., Hansen, K.J., Jones, P.D., Helle, E., Nyman, M,, and Giesy, J.P., Environ. Sci. Technol., 2001, 35, 1593. Rubey, W.A., and Cames, R.A., Rev. Sci. Instrum., 1985, 56, 1795. Rubey, W.A., and Grant, RA., Re. Sci. Instrum. 1988, 59, 265. Sidhu, S., Graham, J., and Striebich, R., Chemosphere, 2001, 42, 681. `Taylor, P.H. and Dellinger, B., Environ. Sci. Technol, 1988, 22, 438. Taylor, PH, Dellinger, B, and Lee, C. C., Environ. Sci. Technol, 1990, 24, 316. Taylor, P.H, Dellinger, B., and Tirey, D. A, Int. J. Chem. Kinet, 1991, 23, 1051. `Taylor, P.H. and Lenoir, D., Sci. Total Environ., 2001, 269, 1. Be bheuooalSo FlRepm ortparedm oSCoe .ODRTR. 2002-00153. Trenholm, A., Gorman, P., and Jungelaus, G., Performance Evaluationof Full-Scale Incineration, MRI Report under EPA Contract 68-02-3177, 1984. 002092 2 D`eTtsaonxgi,fiWc.atainondoSfhHaauzba,rWd.o,uCsheWamsitceasl, PJ.roEcxensesre,siEdn.t,hAenInncAirnbeorart,io1n9o82f,H4a1z.ardous Materials, 002093 a Appendix 1 Timeline and DatesofTesting 002094 Project Time Line [Phasel TMarch2001- October200l | [Phasell-- TFebrary2002| (Phase IT March2002 --September2002] Date 21,24, 2/70/15, 218,2/19, 224 319-729 30 82 818,819 819,820 823,826 827 8028 830 93-915 96 9/18-9120 Combustion Test Schedule - 2002 Description Standard sample calibration CPoFmObSusetxitroanctteisotnsystem and method development Heated blank extraction before combustion test FC-1395 combustion test FC-807A combustion test PFOS combustion test Heated blank extraction after combustion test PFOS transfer efficiency test PFOS transfer efficiency test Off-line GC/MS SO; calibration Non-heated blank extraction PFOS transfer efficiency test 002095 | Appendix 2 Sample descriptions and Certificate of Analysis (Cof A) for PFOS sample) 002096 Appendix Sample descriptions and Certificate of Analysis (C of A) for PFOS sample 3M chemical container descriptions as presented on sample container labels: For PFOS 4xdx] 1.5 em (w.xd.xh.) square column shape with 2.2x3.0 cm idx0.d) circular top madeofclear glass with black screw plastic cap Labeled as: CBF17S03-K+ 98-0211-3916-1 Lot 217 For FC-807A 7.5 em 0.4. x 13.5 emheight circular column shape with 5.26.0 cm id.x0.d Jeircular top madeofclear glass with metal screw cap. Labeled as: Material FC-807A 8681 BCAS Time 11:10 Lot No. 30177 Drum T1 Step 4 Date 1222:2K Sampled By C. Senior For FC-1395 7.5 em o.d. x 17.5 cm height circular column shape with 1.9x2.5 cm(idx0.d) circular top madeofamber glass with black screw plastic cap. Labeled as: Name: FC-1395 Lot #90086 Date: 11/7/00 002097 Reference Standard Descriptions: `The following was retrieved from 3M Environmental Laboratory's sample tracking systems. The original shipmtoeUnnitvofDayton during April of`01 was the following: 20.1 PPM Perfluoro octane sulfonyl fluoride, serial # CC79754 4950 PPM Thionyl fluoride, serial # CC43285 10,049 PPM Sulfuryl fluoride, seria#l FF17680 99.94% Sulfur dioxide, lecture bottle, 3M barcode E0000002106 002098 T G Ceno trewAnR alye ticw al a Labc orSaan tteorD Coileegesw .,PAIIGe Bn0cT.. Phone: (514) 2918002 Fax: (814) 231o-(8114)22315-15380 INTERIM CERTIFICATE OF ANALYSIS Revision 1(9/7/00) Centre Analytical Laboratories COA Reference #: 023-018A 3M Product: PFOS, Lot 217 [Teams pe Referen#ce: SD-018 PurSitpy:ef86a.t9e% w [Rew lr sen] Thentfcaation Metal21s.. (MCIaaClgPcn/iMeuSsm)ium 3. Sodium 4. Potassium 5. Nickel 6. Iron 7. Manganese CgaiaY l Fe eT Fer sali i pid [roe| 2 0c00o1 nwisme% 3. L439wtms% 4 6849wim 5. <0.001 wi/wt% 6. 0.005wtiwt% 7. <0.001 wt/wt.% Len Tard oes (GC/MS) BRAS ni [[PRPeOsuiAdyuAablySoDlvSenCts_(_TG_A)||c _o ragF eifwm les dvio--mie | | No0N.no3te3hDpweptlt/iewccattb.el%ed Taorganic Anions To meee 21.. FChlluoorriiddee: - 2#551,5 S2AREREEVS. 21. <0005195wwtw/wet% 3. Bromide i 5 Wo 45.. NNitiraete +E 54E S1 RA 0 3 <0040 wit 54.. <<000.00096wwiiAnnk% PromTsH & D007 ma Orga7n. iScuAlcfiadtseT! CSEPX ZF Tan SO I twos 2. PFPA. TALE 3. HFBAL "0% Elem4e.ntalNFAPmAa"l 1. Carbon ii" 32.. NHiytdorgoegne"|n 4 1. Theoretical Value = 17.8% 32.. TThheeoorreettiiccaallVVaalluee==00%% 7. 8.76 wtiwt% 2. <0.1wt/wi% 3 0.10 wtin% 4. 0.28 wt/wt% 1. 1248 wt/wt % 32. 012474w6imii% 45.. FSullufourrine 4.5. `TThehoreetoicralVeVaaltluuiee=c=65a.09%l5% 54.. s8.a84lwwt/twmts% cononsosa 002089 Petors Centre Analytical Laboratories, Inc 3048 Research Drive Siate College, PA 16801 Phone: (814) 231-8032 Fax: (814) 231-1253 or (814) 231-158 INTERIM CERTIFICATE OF ANALYSIS Centre Analytical Laboratories COA Reference #: 023-018A Dateof Last Analysis: 08/31/00 Expiration Date: 08/31/01 Storage Conditions: Frozen <-10C Re-assessment Date: 08/31/01 "Purity = 100% - (sumof metal impurities, 1.45% +LC/MS impurities, 841%+norganic Fluoride, 0.59%+NMR impurities, 1.93% organic acid impurities, 0.38%+POAA, 033%) Totalimpurfriomtaylltests = 13.09% Purity = 100%- 13.09% = 86.9% Potassium is expected in this saltform and is therefore not consideredan impurity. oPbusreirtvyebdyfoDrStChisissagemnpelrea.lly not applicable to materialsoflow purity. No endotherm was "iSnuolrfguarniicn atnhieosnammpeltehoadppceoanrdsittioonbse.coTnhveeratneidontoreSsOul,tanagdrheeesncweelldewtietchtetdheussiunlfgutrhe determination in the elemental analysis, lending confidence to this interpretation. Based on the results, the SO is not considered an impurity. TFA HFBA NFPA PFPA Trifluoroacetic acid Heptafluorobutyric acid Nonofluoropentanoic acid Pentafluoropropanoic acid "Theoretical value calculations based on the empirical formula, CFi7SO5K" (MW=538) "This work was conducted under EPA Good Laboratory Practice Standards (40 CFR 160). cormionsa 002100 vwwzots Centre Analytical Laboratories, Inc P3h0o4n8e:Re(s8e1a4r)c2h3D1i8v0e32 Fax: (814) 231S-ta1t2e5oCr3ol(g81e4.) P20A11-6185081 INTERIM CERTIFICATE OF ANALYSIS Centre Analytical Laboratories COA Reference #: 023-0184 LC/MS Purity Profile: Tapurity EWE a 11323 a117d wat Note: The C4 and C6 values were calculated using the C4and C6 standard calibration curves, respectively. The CS value was calculated using the average response factors from the C4and C6 standard curves. Likewise, the C7 value was calculated using the average response factors from the C6 and C8 standard curves. Prepared By: Z2% gLgill 2/op0 10id S. Bell Date Reviewed: (ScOieLnfist9, C1ent0re 1 ical Laboratories 2 John Flaherty Date Laboratory Manager, Centre Analytical Laboratories cornsoisn 002101 Pree dof Appendix 3 Phase II Final Report and Raw Data 002102 | Aug 1,2002 3M Phase II Final Report: Laboratory-Scale Thermal Degradation of Perfluoro-octanylsulfonate and Cs Perfluoroalkyl Sulfonamides Prepared by: Environmental Sciences and Engineering Group University of Dayton Research Institute Summary Calibration curves and detection (hexafluoropropene (HFP)) have limits for SO,, SOF, SOF, POSF, and CsF been established. The transport efficiency through the UDRI thermal instrumentation system for each compound was also examined. This report describes eplxoptesr,ilmiennetaarlfisteetquupa,toipoenrs,atdientgecptrioocnedluimriet,s,aannaldyttricaanlspmoerttheofdfsicainednctyheairrerpersuolvtisd.edThine tchailsirberpaotrito.n Verification that Cs perfluoroalkyl sulfonates can be gasified and transported through the system o`wnitllhebepopteernftoiramlecdonftoalmlionwaitngiotnhoeftcohmeplseytsitoenmofhtahdethpehtarsaensIpITorttesttse.stsTbheisendedcoinseiporniowratso`mtahdeephbaasseed III combustion study. HFP was selected as the surrogate volatile fluorocarbon due to the lack of availability of CF, and CF;H from gas suppliers. Experimental Setup Six standards (SO, SOF2, SO,F2, POSFand HFP) were injected through the STDS reactor configuration that will beused for the Phase II combustion test. The same samples were also tirnajnescptoerdtdeirfefcitcliyenicnytofotrheeaGcCh/mMatSersiyals.teFmiagnurdec1omsphaorwesdawsicthhetmhaetieacrdliieargtreasmtosftroedaecrtivoertahned in-line `GC/MS system thatwasused for the Phase IT study. wr] ow Dus cut --= Sabine I. Jay tnEr| ne Rape ee PEO) _.| [=] F=2 y Figure 1. Schematic Diagram of Experimental Setup for the Phase II Study. 002103 | Aug 1, 2002 `The system consistsof transfer lineat 260C two GCs, thefirst GC (GC1 in Figure to transport samples efficientlyand the 1) was second us tomae intd ain reactor and GC (GC?2 in Figure 1) was used for sample analysis. The furnace in GC was also maintainedat atemperatureof 260C. Helium (He) was usedascarrier flow andflowwassetas 21 + 1 ml/min usinag differential flow controller (Porter Instruments). A flow splitter was installed between reactor and GC column to ventexcess gas. A 21 mUmin flowratewas us tode efid ne aresidencetimeof 1 secinthe tceosmt)buiss t4imonmrexac6tmori.mT(hie.d.cxo0.mdb.u)swtiitohn arneaecftfoerctuisveedlienngthtihsost5fudcym(.anWdhtihleePthhaesseaImIpI lceowmabussbteiionng collected, valve was the switching valve then switched to (2) was open position ed to toward exhaust line (( pressurize GC column 1) position in when sample Figure 1. analysis The was started. The pressure was maintained at approximately 6 psi during:sample analysisandthe `pwraesssaurHeewwlaesttmoPnaictkoarredd5u8s9i0ngA/a5p9r7es0sBuriencgoarupgoer.atTinhgeaGDCB/-M5SMsSysctapeimlluasreydcionlPuhmanse1(310amnalleynsgitsh, 0.25 mm i.d., Agilent Technologies, Inc.). All samples were diluted in helium (Research Grade, Air Products, Inc.) to establish calibration curves and detection limits. The amountofsampleinjectedwas 1 ml for gas-phase samples (SO;, SOF, SOzF2, POSF, and HFP). Measurementswereperformedin duplicate for each sample and concentration. Operating Procedure Calibration Prior to sample injection, the switching valve was set to (1) position to vent excess gas and the second GC oven approximately 1 (GC2) min. to was held at 60C. After sample injection, the flow purge the sample from the reactor/transport system. was vented for The system was then pressurized by turning the switching valve to the (2) position, and the GC oven temperature programmiwansg started. The GCovenwas initially held at ~60C for 1 min., heatedto 50C at 10C/min. and held for 1 min. The GC was heated to 250C for 10 minaftereachanalysis to flush out any tributylamine residual material from the (PFTBA) and operated at column. The MS EMV (2000V) in was auto-tuned withperfluoro- the scanning mode sweeping from 45 0 550 AMU. Direct Injection All conditions, GC oven temperature programming, total flow, split rato, injection port temperature, and column pressure, were set at the same condition that was used for the calibration study. The temperature programming was started immediately after sample injection. 00.104 | 2 August 1,2002 Results Calibration `ITnhemdoesttecctaiseosn,lciamliitbwraatsiodnestweerrmeinmeadduesbiansgeadsoinmifloaurraepvpernoacinhtetrovEalPAco'nscednettreacttiioonnslifmoirtecarcihtersiaampfloer. aidbeunntdiafnytinigoanns cuonmkpnroiswend(tMheetrheofder8e2nc6e0Bmapsasgesp2e3ctra.24)W.eInthoeunrcahpopsreotahche,mothsetmaabsusnedsaonfttihoenmost d(etatregcettioinonl)imaintdwmaasjtohreinosnpsewcihfoiseed iansttehnseiltioewsesatrecgornecaetnetrratthiaonnctah.a2t 0ha%sotfhtehteartgaertgeitonisona.ndThalel of the major ions whose relative intensity agrees with the reference spectra within ca, + 20%. FspoercterxaamfpolreS,OFZiFg;ur(e101,904a9ndpp2m0).inTthheemA/ppze=nd8i3xiiolnluisstrtahtee mthoesttoatabluniodnancthrioonma(ttaorggretamioann)adnmda.ss 6`m7/,za=nd484,86c7o,rarnedsp1o0n2datroeStOhZeF;m,ajSoOrFio,nsSO(Fw,/zawnidllSnOo,trbeespsehctoiwvneltyhearnedafitteirs).reTahsoeniaobnlse otfo c1h02o,os8e3, cthhersoeimoantsotgoraqmuaanntdifmyasSsOsFpe.ctFriagfuorreas2co4nacnendtr2a5tiionntohfe 2A0p.p1epnpdmi.x sThhoewmtahsestostpaelcitorna still contain the target (Fig. 20). ion and the Figures 26 3 major ions and 27 show and the their total iroenlacthivreoambautnodgarnacmeaangdremeasswsistphectthrearfeofreraence spectra dceotneccetnitornatliiomniotffo4r.S0 pOpFm.waTshede1t0e2rmiionneids nasot20p.r1espepnmt.at Stihimsilcoanrcaennatlryastiisonw.asThceornedfuocrte,edthfeor al of standards and the results are briefly discussed below. `FTihgeulriensea2rftiot7esquhaotwiocnaslifborrateiaocnhpsloatmsplfeor, SthOesi,rSliOnFea,r cSoOrFrel,atPioOnScFo,efPfBicSiFe,ntsan(dR)HFaPn,d rdeestpeeccttiiovnely. limits are tabulated in Table 1. i `Table 1 Linear Fit Equations and Detection Limits _Sa--mple Name Linear Fit R Detection Limit 50; (Y: peak area, X: concentration (ppm) Y= S8813E3* X - 3.8541ES 09971 (ppm) 785 SOF SOAF: YY==8L3O3S3ISEE34**XX-7+.108226773E846 0.99941 0.99708 303 201 -- YP- HOESPL F 49TYY==S11..4B 90754EA 42*X-3' - E828452X 05*433EX- S6 208 9019909992 77 5331349.9B1 6 `cTohnecelnitnreaatrifoitnsfocroueladchbecamliebarsautiroendsahboowvsertehaesdoentaebclteiohniglhimciotrrfeolraPtiOoSn ,coetfhfeiRcievnatls.ueBiesc1a.u0.seBoansleyd2 oannaltyhseilsidneeasrcrfiitbeeqduaatbioovne, itnhdeicdaetteesctaiomnuclihmistmfaolrleHrFvPalius e1(839.9pppmp.m).HoTwheivseris,dtuhee tdoetneocnt-iloinnelairmit GC/MS response throughout the concentration range examined. d`Tehteecctoinocnenlitmriattiwoansrdaentgeerumsiendedtoasob7t8a.i5npthpe.SOF;igcuarliebr1a0itinotnchuerAvpepweansdi1x5s70hotwos1t5h7epmpams.s sTpheectra 002105 | 3 J froerspSeOct;iv(e1l5y.70Tphpem)i.onoTfhe64iownasosfno4t8 wasthusdetermined as 78.5 ppm. e(vSiOd)enatnadt a6c4on(cSeOn;t)rwaetrioencohofs1e5n.7aspptamr.gTethieondeatnedctmiaojnorliimoint, - ERT Bl LTiT t I" TTT A1TT LAT A bL d en T , Figure 2. Calibration Plot for80; `The concentration range used to obtain the SOF; calibration was 3034to 303.4 ppm. Figure 9 in the Appendix showsthemassspectra for SOF,. The ion of 67 (SOF) was chosen as target ion and the ionsof86 (SOF)and48 (SO) were chosenasmajor ions. All ions existata concentrationof 30.3 ppm. At 6.1 ppm,therewas no GC/MS response to the sample. Therefore, the detection limit was determinaesd 30.3ppm. 002106 | . T : August 1, 2002 - w" s HA Fa H wl |LAT] eS l AT we d LT dflT d] , Figure 3. Calibration Plot for SOF; `Theconcentration range used to obtain SO;F; calibration was 7034.3 to 100.5 ppm. The detection limit was determined as 20.1ppmas discussed above. i S TTETTTIeTT fT T E PT TT T m Pa Tm T 2g Figure 4. CalibratCoinoc.n(sPolm)ot for SO:F; " The concentrations used to obtain the most accurate POSFcalibrationwere 20.1 and 14.1 ppm. d`eThtiesctliiomnitleidmirtacnrgieteirsiad.ueFtiogturhee2l9o w concentrationo in the Appendix fshtohwesstathnedamradspsrospveicdterda by for P3OMSaFnd(t2h0.e1t ight ppm). | The 69 ion (CF) was chosenastarget ion and 67. (SOF), 100, 119 (CzFs), 131 (CsFs),and 169 , 002107 | ne o(Cf8sFyp)pwme( re F choi seng anads.tthh3 eedme3 atejco)trii, oonns.limTihtewa1s00deatnedrm1i3n1edioanss w14e.r1epnpomt.present at a concentration Jo A eeA=] I ipcort 4 JI Figure 5. Calibration Plot for POSF The concentration range used to obtain theHFP calibration was 10,000 to 1,000 ppm. Figure 44 inthe Appendix shows mass spectrafor HFP (10,000 ppm). The 69 ion (CFs) was chosen as otfa8rg1etwiaosn and not 50 (CF), presentat 8a1co(nCcaeFn)tr,a1t0i0o,n 131 (C5Fs), of 1.9 ppm (aFnidg1.5510)w. erTehecdheotseecntiaosn `major ions. The limit was thus ion determined as 3.9 ppm. 002108 6 August 1,2002 210 wep wo 4 / a ) J ea wa] n ewe a Ge. gon) Figure 7. Calibration Plot for HFP Transport Efficiency a`Trheea torbatnasipnoerdt wefhfeinctiehnecyosafmepalcehwasstanidnajredctwedasinetsotiinmjaetcetdiobnypocrotmipnarGiCnIg tahnedmpeaasssuerdetdhrsoaumgphle peak `icnojemcbtuesdtidoirnercetlayctionrtoantdhetirnajnescfteirolninpe (osoyfsrtGeCtm2tra(ndsipreocrtt)inwjietcthiotnh)a.t obtained when the sample was `Table 2. Transport Efficiency Fe PekAma [SampTTl"e 20d] | [AVG | T |pe2k*Am[AVe| [iiopm]| S[OSF0:,|" 259214340335322 [SO,F; [86850304| 25[2890830778107||252920545052656|| 85572809 11952302| 24862639| 84435720| 11762267] 2749777338638136|| 11857285 2842801887106118||1T0o5.60]] [POS| E 1280370| 1228718 | 1254544|1064431| 1067947] 1066189 117.7 [HEP 148679354 | 145606343| 147142849 | 148372504| 142271896| 14532[22010 013] u`Tnhceerttraainnstpyorot feff1i0ci%enciisesrefaosroSnaObFl,e fSoOr2tFhsi,styapnedoHfFaPnawleyrsiesw.itThhiantfanoarlyPtOicSaFlwerarsor.liAgnhtly higher, abuttwios-ncoonmepthoenleensts maicxcteputraeblwei.thThSaOtFf.orSSinOc;ewtahseatrroaunsnpdor7t6e%f.ficTihenecySOfo;rsSOtF;awawnsansdeaanraalylry1z0ed0d%,as Sth0e2reissuelxtpseicntdeidcattoebseoomneeosafmtphleemlaosjsoerscfoomrbSuOs;titohnrobuygphrotdhuectresa,cwtoerwainldl trreapnesafterthleineefsf.icBieecnacyusteest 002109 7 August 1,2002 atsepst raesourlfttsthteo cPhoamspeenIsllatsteudfyo.r tWsemewaisllureesdticmoantceeantSraOtiocnordruerctiinogntfhaecPtohrasbeasIeTTdsotnudSy.O; efficiency 5 002110 | 8 August 1, 2002 Appendix (Raw Data for Phase II Report) Thprehexesaeftnolttuaeoldriobopenrlocopwhe.rnoeMmaa(tHsoFsgPsr)pa)emcastnordafttahheeems6hasostwansnpdfeaocrrtdrtsah(cSohOrisgr,heesSspOto,Fndd,eitnSegeOttFios,ntalPniOmdiaStr,Fdapanendadkbselaorwe detection limit concentrations for each standard. =| [Pe Svar "Figure 8. Total Ion Chromatogram for SOF; (3034 ppm and SO, (1570 ppm) | peoions sean 0am crnoran 0 | on T ooo || T : foe | luo " ~~ Figure 9. Mass Spectra for SOF; (3034 ppm) 002111 | 1 ) = : `August1, 2002 -=Riri Spee rE: -- | August 1,202 Figures. Total Ion Chromatogram for SOF; (303.4 ppm) and SO; (157 ppm) To: cLsorr2n wool | ac00 | <o00 2000 00. /400.600.801.001.201.401.601.802.002.202.402.602.803.003 20 5Figure 14. Total Ion TO] Chromatogram for SOF; (151.7 ppm) and SO; (78.5 ppm) = | ==] || pod! = Figure 15. Mass Spectra for SO; (78.5 ppm) 002113 3 Avunaanes or :EE 2 Co] : --| r-- ouRaLs | | August 1,202 -- Figure 19. Total Ion Chromatogram for SOF; (10049 ppm) prises |T J Figure 20. Mass Spectra for SOF; (10049 ppm) ho "Figure 21. Total Ion Chromatogram for SO;E; (7034 ppm) . 002115 5 || me me | | I svg "Figure 2.Total lon ChromfaorStOFo,(p12r0papmm) wl) == | E= ! 77 Figure 2.Toa onChromatogr or SO A003poy pBvootd y|| \ "Figure4. Tota LonChromatogrfoarmSO(S20.1Fppsmy 6 002116 ; : Avg 1,2002 Tl .. Figure25 Mass Spectra for SOSF; (20.1 ppm) = "7 Figure26.Total lon ChromaftoroSgOLrE:am (L0ppm) ~ Rt crane 2 2 | || | =| | TTT Figure sam SpontorSO 0pom 7 002117 = re ee rr , 002118 August 1, 2002 J senza unos mp OuG Je | ee | 2000 ow || wT a "00 rn Figure 31. Mass Spectra for POSF (14.1 ppm) 20! 1 "Figure 32. Total Ion Chromatogram for POSF (8.0 ppm) | on 022 902m9a0 OT wl | we Figure 33. Mass Spectra for POSF (8.0 ppm) 5 T wuL1is =| "acoces August 1, 2002 Figure 34. Total Ion Chromatogram for Hexafluoropropene (HFP) (10,000 ppm) haonooscoonot|| Scan30 @.414 mi Pr. so0000 == = T Cr Figure 35. Mass Spectra for HFP (10,000 ppm) Teens bSoite || "Figure36. Total Ion Chromatogram for HFP (7,000 ppm) 10 002120 August 1, 2002 m= errr "Figure 37. Total Ion Chromatogram forHFP (4,200ppm) "Figure 38. Total Ion Chromatogram for HFP (1,050 ppm) "Figure 39. Total Ion Chromatogram for HFP (3.9 ppm) | 002121 1 ' August 1, 2002 . a. N wr J Figure 40. Mass Spectra for HFP (3.9 ppm) TT Figure 41. Total lon Chromatogram for HFP (19 ppm) 270 T oom Figure 42. Mass SpectraforH(F19pP pm) 12 } cue | Appendix 4 Phase III Test Protocol and Addendum | v0i123 | July 30,2002 Phase III Protocol: Laboratory-Scale Thermal Degradation of Perfluoro-octanylsulfonate and Cs Perfluoroalkyl Sulfonamides Prepared by: Environmental Sciences and Engineering Group University of Dayton Research Institute Summary `thTihse spthuadsye iIsIthsetusdiymuwlialtlicoononfsitsht eoif6ncsienpearraattioentoefstss eavsesnhfolwunorioncaFribgounr-eb1.aseTdhesammapilnesobpjreocvtiidveedobfy o3fMt.hesSepemcaitfeirciaaltst.entIino-nliinsebaenindgogfifv-leinnteoGCth/eMpSoteanntailaylsifso,rPmaUtFio(npooflyPuFreOtShadnuerfionagmt)hesaimncpilneeration cPoUllFecctairotnriadngdescaonnddetnhseeedxtprhaacstse wsialmlpbleedeexltirvaecrteidontowi3llMbfeorcoanndaulcytseids.ofIPnFthOeSlabtyteLrCt/wMoSt.estsP,rtihoer tloatbhoreatsoarmypslpeikceomabnuaslytsiiosnfaonraPlyFsOisS, twhielltbraenspfeerrfoefrfmiecdi.enAcyhfeoartSeOd;blwainlkbleinreeaenxaalymsiinsewdilalndbethe performed at the onsetofthe sample combustion tests. After the combustion tests, another p`heeraftoedrmbeldanakt ltihneecaonnacllyussiisowniolfl tbheepeprhfaosremIeId.stTurdayn.sfer efficiency tests for CsF1;SOyK* will be 3. Heated Blank Combustion Test 4. CombustionanTdesCtsiFfoyrSFOC,-K13'95, FC-807A, 5. Heated Blank Combustion Test (repeat) 6. Transfer Efficiency Test for CsF17SOyK" Figure 1. Chronological summary of tests to be conducted during Phase IIL, 002124 1. SO; Transfer Efficiency Tests I7n6.th4e%.phaTsheeISOtr;ansstfaenrdeafrfdiwciaesncayntaelsyt,zesdulafsuradtiwoox-idceom(pSoOn)ensthmoiwxetdurreecwoivtehrySOeFff:ic(itehnicoynyolf fluoride)andthe SOF; recovery rate was nearly 100%. Therefore, it is quite conceivable that SO,wasabsorbed on the surfaceofreactor and transfer line. We `will conduct another analysis to confirm this result and to estimate the recovery coefficient for the calculation of SO; `concentration from the combustion tests. 2. Laboratory Spike Analysis for PFOS A 1pgsample will be used for the PFOS spike analysis. This is the amountof PFOS that would `bweerfeorcomnevdeifr0te.d1t%ooPfFtOhSe ipnertfhleuroeraocatlokry.lApnoarltyisoinosfotfhtheefelxutorraoccthsefmricoamltphreosdeuscptiskeudsed in thisstudy `reactor/transport systems will showifthis amount ofPFOS can be extracted and detected accurately. 10 mg of PFOS willbedissolved with 10 ml methanol (Aldrich, HPLC grade) and 1 ul ofsolution (containing 1gofPFOS) willbeplaced into a reactor (4 mm (i.d.) x 6 mm (od) `xwo7n'ctmblleonwgtdhr)opalnedtsd outrtbhyeibolte hoewrid nengd.hiAgfhtpeurrtihtey dnrityrionggenp,roocresbso,tttlheeddtrryanasiferrovleinreiwtilalt a rate be that `assembled and extraction will be performed using the same lotofmethanol used to dissolve the samples. The total volumeofentirereactorand transfer line is 1.1 mlas shown in detail below. Reactor volume `Total volumeoftransfer line ==00.2mmil:: aass cmaelacsuularteedd(02 em x 02 em x 3.14 x7cm) Total =Llml `The concentration of PFOS in the spike that is extracted with five times volume of `ersetaicmtaotr/etdradnestfeecrtliionne l(iumsiitnfgomrePtFhaOnSol(caa.s t1h0ensgo/lmvle)n.t) will be 180 ng/ml. This is 18 times 3M's. Figure 2 shows a schematicofthe PFOS laboratory control spike extraction system. The esxutbrsaecqtuieonntptrooctehdeuhrieg will h-te be based mperature on the perspective combustion stage that on would ly be the ind iccaotinvedoeflniskeoalyftPPiFFoOOnSS rel ease otontthhee ehnivgihr-otenmmpeenrtfatruormearcetaucatlori(ndcoinwenrsattrioenamsoyfsttehmes.hiTghhuess,t ttheempeexrtartaucrtieopnopinrto)ceadnudrethweilrleafcotciuosn pforloldouwcitntgrapnasrfaegrrlaipnhesdbesectrwiebeens tthhee raenaaclyttoircaalndextthreacvtairoinoupsroscaemdpulree.collection systems. The. 002125 | The endof 2 1/16" tee will be capped prior to extraction. The total amount`ofmethanol used will be 5.5 ml, five times the volume ofthe reactor/transfer line. The `methanol will bestoredin 40 `ml vials (Wheaton CLEAN-PAK, clear certified with pre-cleaned lined cap) and the vials will be connectedtothe endof 1/16" tubing using 1/16" stainless tubing. Theotherendofreactor will `lbiencedoncnaepc)tuesditnog a1n/o8t"hsetrai4n0lemsls tvuibailn(gW.heMaetthoannCoClLwEilAlNb-ePAsKlo,wlcyleianrjceecrtteidfiiendtowtihtehspyrset-ecmleabnyed pressurizing a methanol reservoir by helium gas flow (2.7m/min) until all methanol isinjected into the system. The initial methanol (5.5 ml) level will be marked onthe40ml vialpriorto i 2 collection and will be used for confirming that allof sample introduced is collected. The extraction will be performed twice for each sample. The collected samples will be secured, labeled, and appropriately packaged for overnight delivery to 3M Environmental Laboratory `with one blank vial (40 ml) containing 5.5 ml methanol. He Line {OS J Flow controller Vent Reservas | 116Tubing 8Tubing PaFa afg 26m a1} Tom) net i CVoilallection Figure 2. Experimental set up for PFOS laboratory control spike tests. 3. Heated Blank Combustion Analysis Before and after the sample combustion tests, a heated blank combustion test will be conducted forareactor temperature at 600 and 900C to examine system contamination. The sample collection will be performed twice for each temperature (one for the sample collection using polyurethane foam (PUF, (Supelco ORBO PUF Cartridge) and one for the sample collection using Tedlar sampling bags (0.5L, SKC Inc.). Two GC-MS analyses with different GC columns will be conducted for the heated blank exhaust gas analysis (one with in-line GC-MS analysis. and one with off-line GC-MS analysis). After the gas-phase collection and analysis,thereactor will be cut inhalfand condensed phase product extraction will be performed using the method previously outlined in Section 2. Figure 3 shows the schematic diagramofthe experimental setup to conduct in-line GC/MS analysis and PUF sample collection for the heated blank combustion test. It also shows the detailed dimensionsofthe reactor/transfer line system. For off-line GC/MS analysis, the PUF shown in Figure 3 will be replaced by a Tedlar bag. Compressed air will be delivered both to the pyroprobe chaanmdthbereeactror. The total airflowratewillbe 10.3 and 7.6 ml/min (with 0.8 and 0.7 ml/min to the pyroprobe chamber)forreactor temperaturesof600and900C, respectively. The residence timeinthe reactor (4 mm i.dX.6 mm o.d. X 14 cm length with cm effective length) will be ca. 2.05. The determinationofthe effective lengthofthe reactor is discussed in Section 4. The flow rate wil be controlled within 10 % error. A majorityofthe 002126 3 effluent will pass through the PUF cartridge for sample collection and 1 m/min will be directed . into the GC column for in-line analysis. In-lineGC-MSAnalysis: A HPS890A/S970B series GC-MS with DB-5 MS capillary column (30 m length, 0.25mmi.d., Agilent Technologies, Inc.) will be usedforthe phase III study. The inital temperature of GC2 will be held at -60C and sample will be concentrated at the head of the column for2 and 2.5 (5%) min for reactor temperatureof600 and 900C, respectively. `During this time period, PUF combustion effluent sample collection will also take place. Two. 'PUF cartridges will be placed in series as showninFigur3e. After the sample collection, switching valve 1 will be tured to (1) position in Figure 3topressurizetheGC column. As Soon as pressurization begins, the temperature programing ofGC2 will be started. The initial temperature will be held for 1 minute and the temperature will be raised at 10C/min up to 260C. `The final temperature will be held for 5 minutes. Alsoafterthe switching valve 1 is tumtoe(d1) position fortheGC column pressurization, the PUF cartridges willbe removed from the system. `The PUF cartridges will be secured, labeled, and appropriately packaged for next business day delivery to 3M Environmental Laboratory with one blank PUF. Off-lineGC-MSAnalysis: After the PUF sampling collection, identical sample collection will be performed using a Tedlar sampling bag. The collectedoffgas will be sampled within 15 min. of collection and analyzed using HPS890A/S970B series GC-MS with SPEL-Q PLOT (Porous Layer Open Tubular) column (30 m length, 0.53 mm id, SUPELCO). The Tedlar bags will be heated to ca. 50 -- 60C to ensure that allofthe sulfur compounds that are soluble in the condensed water vapor present in the bag are partitioned into the gas-phase. This column will capture the light compounds (<C) that the DB-5 MS capillary column may not effectively retain during in-line gas sampling. The initial temperature will be held at 35C and 1 mlof sample will be injected using a 1 ml gas-tight syringe. The initial temperaturewillbe held for |minuteand the temperature will be raised at 15C/minupto 245C. The final temperature willbe held for minutes Allofreactortransfer line systems including pyroprobe chamber and sample insert probes used in the Phase ITT analyses will be appropriately packaged and stored for the future analysis. 002127 4 VSeotanton )- [yo-- r = Pow Q Ed rmoawetr oLO oCTL7Ge YBa 0 | = eeJ r, =Eo car ete 22cm PCyhraomprbaebre (7 x9.5mm x Sem) 1/16 Tubing 1/8 Tubing 7] (4 xRe6amctmorx 14cm) 38cm 16Tee emg Tee DFiigmuernesi3.onEsxpoefrtihmeernetaacltosretaunpdftorrahnesafetredlibnleasnakresaamlspoleshaonawlnysiinslaonwdercodlrlaewctiinogn.. 4. Combustion Tests of Seven Selected Compounds `Combustion tests for the seven selected compounds will be performed after the heated blank tanhaelryesiasc.torStiemmipelratarotutrheeohfea6t0e0dabnldan9k0a0naCl,ysains,d tthhee ssaammppllee ccoolmlbeucsttioinonwitlelstbsewpilelrfboercmoenddtuwcitceed ffoorr 5 002128 eTahcehstaemmepearnaatluyrteic(aoltneestfsorwiPlUlFbesacmopnldeucctoeldleacstifoonratnhde ohenaetfeodrbtlhaenTkeadnlaalrysbeas.g sAafmteprlethceolglaesctpihona)s.e analysis and collection, the reactor will be cut inhalfand extractionofcondensed phase products will be performed using themethodpreviously outlined in Section 2 an3d. Figure 4 shows the schematic diagramofthe experimental setup to conduct effluent in-line GC/MS analysis and PUF sample collection for the combustion testofthe selected compounds. For off-line GC-MS analysis, the PUF cartridges in Figure 3 will be replaced by a Tedlar bag. ASiimrualnatdemientchianenrea(tiifonnoefcetshsearsya)mpwlielsl.beThientfrloodwucreadteionftoHteheapnydroaiprrowiblel cbheacmobnetrroalnleddtbhye raefalctoowr to ccoanltirborlalteerds(yProirntgere pFluomwpIn(sKtDrSu1me0n1t,s,kdDSFcCie1n4ti0f0i)c)a.ndBemceatuhsaentehewimleltbheanientrfoldouwcreadtuesiisnvgeray low, it isnecessartyo use syringe putomobtpain accurateflowrates. Thesolidand liquid phase samples will be gasified using a pyroprobe (Chemical Data Systems, Model 120) and mixed with aofiirgannidtimoentwhialnle(rainfngeecfersosmar1y0)0i0n ttohe12py5r0opCraonbde2c0hatmobe4r0.sTechoendtse,mpreersaptecutrievaelnyd,tdheepdeunrdaitnigonontimteh.e `actual sample being gasified. The gasified mixture will be mixed with the air stream and undergo itnhceiGneCr-atMioSn fionrtphreofduuscetdasnialliycsairseaacntdorr.esAtofpeofrftliuoneonfttwhilelebfeflpuaesntse(d1 tmhlr/omuignh)twwiollPbUeFdeclairvterrieddgetso for detection ofPFOS using LC/MS analysis at 3M environmental laboratories. Further details are provided below. -- us [] He Ioi . i] CT omer" Na i we] = Ge @ ot Er ED Fneateime@ oLPT, EBre I FE JE we (O)O | - | | [Ree =of2iz -- = Figure 4. Experimental setup for the combustion tests. 002129 6 1. Stoichiometric Reaction Mechanisms of Seven Samples Basedon the elemental formulaofthe seven samples providedby 3M, fourof which are `normalized by carbon, stoichiometric equations were developed and the amountofnecessary oxygen was calculated. The results are tabulated in Table 1. In the developmentofthe stoichiometric equations, it is assumed that C is converted to CO, F is converted to HF, N is converted to Ny, and is converttedoSO; Phosphorous and potassium were excluded from the equation since the contributionofthese elements is very small and their effects on the overall stoichiometry are small enoughtobe safely ignored. Methane is also introduced for hydrogen deficient samples to supply hydrogen to convertF to HF. In that case, additional oxygen was supplied to convert C in methane to CO. [ rTabo le 1. Com efficiec nts of Sc toichio[ m metric0 SCm ioormhbiouns] etto iiconofSs elepctoedm sSasmple es| [ssmpe[clu[ [xToleTs xo]om|comolme[son] bros [od ofvl of of d [fwd of of of od Jf d From the table above, stoichiometric equations can be derived for allofthe samples. 2. Calculati ary Amount of vs PEOS) "The amount of sample that will be incinerated was calculated to conserve the same amount of fluorineforeach sample and is tabulatedinTable 2. All samples have the equivalent amount of fluorine that is contained in 0.50 mgof PFOS. To facilitate calculations, we define a "pseudomolecular weight" to be the sumofthe massesofthe elements in the empirical formulation of each producast given in Table 1. The amountofair necessary for stoichiometric incineration for each sample was also calculated and is included in Table 2. 002130 7 Table 2. Amount of Sample That Contains Equivalent AmountofFluorine in 0.5 mg of PFOS (Pseudo) Fluorine MassofSample to Amount ofAir for Molecular Fractionby be incinerated Stoichiometric Sample Name _ Weight (z) weight (mg) Incineration (ml) FC1395 4362 0.527 0572.19) 1.50 FC-807A" 51.567 0519 0.58 (2.63) 137 PFOS 538 0.600 050 138 * Values in parenthesis will be used for the actual combustion test. See sample amount adjustments. For example, the amountof FC-1395 that contains equivalent amountoffluorine in 0.5 mg of PFOS can be calculated as: 0.5 (mg) x 0.600/527 = 0.57 mg and the amountofai for stoichiometric incineration can be calculated as: 0.57 (mg) x 0.001 (g/mg) / 43.62 (g/mol) x 0.98 (stoichiometric O:) x 0.0821 (atm Li(mol K) x 298 (K)/ 1 (atm) x 1000 (ml/L) /0.209 (Oy fraction in air=) 1.50 ml `The necessary amountof sample and air for other six compounds can be calculated in asimilar manner. 3. SampleAmountAdjustments Since FC-1395 and FC-807A were provided in aqueous solution (water contents of 74 and 78 % by weight, respectively), the amountofsample to be loaded wil be 2.19 and 2.63 mg, respectively. 4. Sample Loading Method FC-1395 and FC-807A, bothofwhich are in aqueous solution, will be placed into a slightly larger sample probe (2 x 4mm (id. x 0.4) x 1.5 cm length)anddried with He and moderate heat (less than 100C) before being mounted into the pyroprobe. (The slightly larger sample probe: will be used to enhance the drying process.) This process will aid the gasification process by requiring lesenergyto gasify the active ingredientsofthe sample. Thermal gravimetric analysis show that significant amountsofmass are lost for booftthehse samplesattemperatures of ca. 150to 160C (see Figure 5 and 6). The ratioofthemass at ca. 160C to the original mass is an indicationofthe mass lost due to water evaporation. The mass ofFC-1395 and 807A before and afte this drying process will be measured to confirm that the active ingredientsofthe sample are not vaporized prior o insertion in the pyroprobe. CsFy7SOyK., which is a solid `powder, will be placed into the sampleprobe (1 x 2mim (id. x 0.d) x 2 cm length) with small `amountof quartz wool support (0.5 cm in length) in the bottomofthe sample probe. The quartz wool is necessary to hold the materials in place prior to the combustion test. 002131 s : Fos oo HE i bw me Tampeani,&am me Figure 5. Thermal Gravimetric Analysis (TGA) of FC-1395 roan I. 5Poe wm om Tumwpeennen,&we wm em Figure 6. Thermal Gravimetric Analysis (TGA) of FC-807A S. Experimental Flow Rate Setting and Calculations Table 3 and 4 summarize the experimental flow settings at temperaturesof 600 and 900C, respectively. The flow rates for He and Air can be controlled within + 10 %, and the methane afilrocwornadtieticoannrbaengcionntgrfolrloemdcwai.th1i0n0to54%5.%0Eaecxhcecsosmapio.und will be incinerated under high excess The concentration profileofthe gasified sample s not measured directly and assumed to be an caovnedriatgieonvsalmuaeyionctchuereixncetshsearieraccatlocruldautriionngstdheesgcarsiibfeidcaatbioovnep.roOcxeyssgefonrasnodmmeeotfhatnhee-dseafmipclieesntwhile 002132 9 thepyroprobies heattoheigdh temperatures (1000 to 1250C)andthevoluofmthee gas expands by a factorofup to 2.5. In other words,duringthe gasification process, the flow rate of the gasified sample to the reactor may be faster than the calculation shown in Tables 3 and 4. `The calculations shown in Table 3 and 4 are described below with FC-807A as an example. The calculation can be conducted in a similar manner for the other two compounds. The numbers in `Table 3and 4 arecalculatedusing aspreadsheetprogramandthe numarberoeunrdedsto the appropriate number ofsignificant digits. Therefore, the calculation may not exactly reproduce the numbers shown in Table 3 and 4. In Table 3, the necessary amount of CH for FC-807A can be calculated as: 0.58 (mg) x 0.001 (g/mg) / 51.6 (g/mol) x 0.106 (stoichiometric CH requirement, see Table 1) x 0.0821 (aLt/(mmol K) x 298 (K)/ 1 (atm) x 1000 (mU/L) = 0.03 ml `The necessary amountof CH, was then doubled to provide an excessof hydrogen atoms to scavenge fluorineatomsas HF. `The CH, flow rateand sweeping time through the pyroprobe were calculatedas shown below: 0.06 (ml)/ 1.00 (min) = 0.06 (m/min) `The air flow rate to pyroprobe was added to sweep the sample out ofthe volume in 1 min. The `tovoslwuemeepoftphyersoapmrpolbeeoiusto1.f5thmel (v0o.l3u5mex3a.t1246(0cmC?)is:x 4.5 em -- 0.2 (cm). The necessary flow rate 1.5 (ml)/ 1 (min) x 298 (K)/ (260 + 273) (K) =0.84 mUmin Smli/nmcien.0.06 ml/minof0.84 ml/min is provided by CH, the air flow ratewillbe 0.84~ 0.06 = 0.78 `The necessary air low rate to the reactor for sample combustion can be calculated by the stoichiometric amount ofair for sample and sweeping time: 1.37 (au/1(lmin))= 1.37 m/min r`TehaectsotroifocrhiCoHme,trciocmcboumsbtuisotnicoannrbaeticooalfcumleattheadnaes:to air is 1:9.57. Therefore the air flow rate to 0.06 mUmin x 9.57 = 0.57 m/min `With the m/min. additional air flow rate shown in Table 3, the total gas flow rate is calculated as 10.28 The residence time for 0.4 cm i.d. x cmeffective length quartz tubing at 600C is calculated as: 10 002133 0.22 x 3.14 x 8 (ml) / [10.28 (ml/min) / 60 (s/min) x (6+02703) (K) /298 (K) = 2.00 5. `The excess air ratio is the ratioof additional air to stoichiometric air. For FC-807A, 7.5 ml/min acdodmibtuisontailonai(rsfalmopwlewi+llCbHe)i.ntrTohdeuceexdcewshsilaeir1r.a9t4omils/cmailnciusltahetaaeisdr:flow rate for stoichiometric 7.5 (ml/min/) 1.94 (ml/min) x 100 = 387 % 6. Effective Lengthof Reactor "The effective length ofthe reactor was determined based on measured temperature profiles at 600 and 900C. The temperatures ofreactor wall (outside) were measured by thermocouples (Chromel-Alumel Type K, 304 SS Sheath, OMEGA)wrapped withquartz tape to prevent radiation effects from the heater. For the reactor temperatureof600C, the temperature was set at613C. The effective length of8 cm wasobtainedby allowinag deviationfromthe desired temperature (600C)by +20C, which is 3.3 %ofdesired temperature. The measured temperaturesatthe cenotfethre rea andcatatdio stanrce of1, 2, 3,4, and 5 cm from the center are shown in Figure 7. Forthereactor temperatureof900C, temperature was set at 928C. "The 8 cm effective length was obtained by allowing a deviation from the desired temperature (900C) by + 30C, which isalso + 3.3 % ofdesired temperature. The measured temperatures at `the cenotfethre reactor and at adistance of 1,2, 3, 4, and 5 cm from thecenterare also shown in Figure 7. oe 10 Temperature Praie wo Sm | mo. a 0 7 : 3 : 5 Dito omCee (cm) Figure 7. Reactor Temperature Profile for 600 and 900C. The profiles are roughly symmetrical about the center of the reactor. u 002134 7. Experimental Procedure(Gas Phase Sample Analysis andCollection) `rHeaecltiourm/twrialnlsfbeerulsineed. iTnihteialelxypteoripmuerngtesbsottarhtawiritahnsdemtteitnhgatnhee lfilnoews traotteohfeapiyrroapnrdobmeetahnadne and the temperaturesof GCI (260C), furnace (600 or 900C), and the GC2 (-60C). After the tpyermopperroabteu,reainsdaapiprrwoiplrliabteeliyntserto,dauicreadnidntmoetthheanreea,citfonre.ceTshseareyx,hawuisltl bgeasiwnitlrlobduecveednitnetdo wtihethout pmroeusnsutreidzaitniiotinalblyy sinettthiengstyhsetesmw,iticnhstienagdvtahleveto1potof(p2y)rpoopsirtoiboen.chTahmebepryrwoipllrobbeecwaiplplendo.t Tbehe sample will be carefully loaded into capillary quartz tubing, Imm (id) x 2mm (0.4) x 2.0 cm (tlheentgutbhi)nogrc2armemful(liydi)nsxer4tmedmin(t0o.t4h)expy1r.o5pcrombe(l.enAgftth)e,r tthhee nfeltowweriagtehtaonfdstaemmppelreamteuaresuarreedp,roapnedrly tsoetsatanbdilsizaem.plTehpercepaaprfaotriotnheispcyormopplreotbeedc,htahmebseyrstweilmlwtihlelnbbeeherledmofovre1d mainndutthees ptyoraolplroowbethqeufilckolwy isnasmeprltee.d iAnfttoetrsthcehaampbperorp.riIamtmeeadmioautneltyofatfitemrewatrodss,wteheepptyhreogparsoibfeiewdilslambpeliegnfirtoemd ttohegapsyirfoyptrhoebe chamber (1.2 timesofsweeping time shown in Table 3 and 4), the ir flow for the pyroprobe will `be maximized (5 ml/min at room temperature, 8.9 ml/min at 260andChel)d for 10's. The sawpiptrcohxiinmgatveallyve20fosrebc,otshwitthcehpiynrgovparlovbee 1anwidllrebaecttorumweildlttohe(1n)bpeossiwtiitocnhteodptroehsesluiruimz.e thAeftGeCr column. As soon as the column pressurization is started, GC temperature programming and MS analysis willbestarted. The temperature programmingwillbe identical to that described in Section 3 (Heated Blank Combustion Test). The PUF cartridges will be also removed from the system. The PUF cartridges will be secured, labeled, and appropriately packaged for next beuxspienreismsendtaywidlellbiveerreypteoat3eMd fEonrvtihreonsmaemnptlaelcLolalbeocrtaitoonruysiwnigthaoTneedlbalrabnakg.PUFT.heTshaempslaimneg method aSinndcoefft-hleinseaGmeC-reMacStoarnawliylslibsewirlelpebaeteiddlenytuicsaeldtfoorthtewhoeactoemdbubsltainoknantaelmypseirsatduersecsr,ibtehde ibnlaSnekction 3. analysis will be performed between each analysis to examine any carryover from the previous analysis. The exhaust gas will be ventedto a laboratory hood followingeachtest (as shown in Figure 5) to minimize any cross contamination during Phase ITI study. 8. Experimental Procedure (Condensed Phase Sample Extraction) Afer gas-phase and PUF sample collection and analysis are completed, condensed phase sample extraction will be performed. This process will be identical to Section 2- Laboratory Spike Analysis, as illustrated in Figure 2. The collected sampleswillbe secured, labeled, and appropriately packaged for next business day delivery to 3M Environmental Laboratory with one blank vial (40 ml) containing 5.5 mi methanol. The sample probe (capillary quartstubing)used for sample loading will be weighed after the combustion test to determine the net amount of sample gasified. 002135 12 i 5. Transfer Efficiency Test for CF180;K" `Fmiagtuerreia8lsswhiollwsbescchoelmleacttiecdduisaignrgatmwooftPrUanFsfcearrterfifdigceiseinncythteesstafmoreCmsaFn1n7eSrO;aKs'd.escTrhiebesdtaeratrilniger for the combustion tests, helium flow rate will however, in be set as 20 mthle/smeintesatns,dtthheeftuermnpaecreattuermepienratthuerGeCwiolvl ebenhweilldlabtes2e6t0aCs. The c2o6l0lecCt.ionT.heTshaemspwlietpcrheipnagrvaatlivoen,awnhdilcohadisinogripgrioncalelsysessetatroe (t2h)epsoasmiteioansitheFicgoumrbeus8,tiwoilnlobfef-gas fsowrittcwhoedmitnou(t1e)spaofstietrigoansjiufsitcabteifoonrebetghiensp.yrTohperocboell/escatmepdlseaimnpsleretsiowni.llTbheessecaumrpelde, wlialblelbeed,coalnldected appropriately packaged for next business day delivery to 3M Environmental Laboratory with one blank PUF. Veatinton He shoonyme | N\nCovet GrCurig wVamle]|p \ 22 0 |10dSample: <D= RI | Furnace Me -- R0 es] co Figure 8. Transfer Efficiency Test for CiFnSOsK". 6. Cross Contamination Prevention and Examination rEexlteeansseiovfethperesceauetnivoinrsonwmielntbaellaypppleiresdisttoemntinmiamteirziealasniynPtoFtOhSe icmrmoesds-icaotnetalmaibonraattioornydeunevtiorothnem:ent 13 002136 | following each combustion test. The effluent exhaustline has been connected to a laboratory . hood in KL 112 following the results ofthe phase ITstudyto mitigate the release of PFOS into the immediate laboratory environment associated with the off-line PUF sample collection. Prior to Phase IIT study, the laboratory tabletop and STDS combustion apparatuswillbe completely cleaned using reagent grade methanol and acetone and only the cleaned tabletop will be used for sample preparation and system assembly and disassembly. After the first cleanupofthe desktop, the surface will be wiped using 3M Scotch-Brite High Performance Cloths with HPLC grade `methanol that is used for sample extraction. The cloth will be soaked with methanol and squeezed before each wipe test. The wiping methods will follow 3M' instruction given at previous laboratory wipe test. Thewipedcloth will be stoirnethde I-CHEM 40 mi vial provided by 3M. The vial will be stored outsideofthe KL 112 where thePhaseIII studywillbe: conducted. The cleaning and wipe tests will be conducted following the completionof each subsection task and between each sampleifthe section involved multiple sample analysis. 7. Samples to be sent to 3M `The following samples will besentto 3M Environmental Laboratory for each test shown in Figure 1 excluding test 1. Blanks for PU, solvent, and wipe testwilbe includiend cach shipment whenever these analyses/collection are performed. Next business day delivery will be used for al shipments. Eleven total shipmentsare scheduled. The contents for each shipment to be delivered are as follows: Test2 -- Two extracts (5.5 mi) for each test compound, one solvent blank (5.5 mi), one: wipe test, and one wipe test blank Test3 -- Two sampled PUF cartriodnegbelasn,k PUF cartridge, twoextracts (5.5 ml), one solvent blank (5.5m), two wipe test, and one wipe test blank Test4 Test ---- Four sampled PUF cartridges [two for 600C (1* and 2* collections) and two for 850C (1* and 2 `one solvent blank (c5o.l5lemcit)i,ontsw)o),woinpeeblteasntsk,aPnUdFo,ntewowiepxettreacsttsb(l5a.n5kml) (1 and 2, Two sampled PUF cartridges, one blank PUF cartridge, two extracts (5.5 ml), one solvent blank (5.5m), two wipe test, and one wipe test blank. Test6 ---- Tcawrtorisdagem,pltewdo PwiUpFectaersttsr,idagnedso(n1e*awnidpe2t)estfobrlaenackh test compound, one blank PUF 8. Changes in Original Protocol `Three significant changes have been made as the experimental approach has evolved after the original proposed protocol was approved by EPA. They are outlined below. 002137 14 1. Significant changes were made to the sampleinletand gasification system. To satisfy the analytical requirementsfor PFOS detection by LC/MSanalysisby 3M, we determined that relatively large amountsofsample, 0.5 to several mg,hadtobe gasified in the actual experiments. This amount of sample is much larger than initially estimated (ca. 10 to 100 ig) aSnydstceomul(dAnToPtRbSe).gasPirfeileidmiwniatrhytehexpienrleitmeanvatislaibnlpehwaisteIh thaelsAoddveamnocnesdtrTahteerdmatlh/aPthhoitgohleyrtic Reactor gasification temperatures (> 400C) were necessary to rapidly gasify the fluorocarbon-based samples. As such, the System for Thermal Diagnostic Studies (STDS), equipped with a hightemperature pyroprobe that can gasify milligram quantities ofmaterial,i proposed for the phase IanIalcyotmibcaulstciapoanbtielsitts.esTahnedSisTaDSsatiissvfeacrtyorsyimsiulbasrtittouttehefoArTtPheRASTwPiRtSh.regard to its incineration/ 2. In the approved protocol, we had originally planned sample combustion with hydrocarbon `fnueeelds (bee.cga,usne-otchteanlei)qufiodrhayldlroofcsaarmbpolnesf.ueSlusbosreiqguiennaltllyy,pritopwoassedderteeqrumiirenemdutchhatlaarsguebrstaimtoutuenwtaosf oofxy2gseenco(anid)s tion otbhtearienacsttooricuhnidoemertsrtiociocxhiidoamteitroincaonrdeixtciessismapiorsesnivbilreotnommeanitnst.aiMnetthheanreesihdaesntcheetime lowest chemical oxygen demandofany hydrocarbon fuel and is a satisfactory replacement. We PsoruorpcoesteotcoounsveermtetFhtaoneHFa,s aotfhueerlwiifstehfeuselamwpillleniosthbyedriongternodduecfeidciteontthaenrdearcetqouri.res hydrogen 3. In the approved protocol, we also proposed to conduct combustion testsa threetemperatures (600, 750, and 900C). Preliminary combustion tests with several samples indicates that many combustion byproducts were formed at 600C, but those combustion byproducts were not othbesseervheidghaetrhtiegmhpeerrtaetmupreersawteurree v(7e5r0y asinmdil9ar0.0TCh)eraenfdotrheeitGiCs-pMroSpotsoteadltihoantcthwrootmeamtpoegrraatmursefsorare sufficient to analyze the combustion phenomena ofthe selected samples (600 and 900C). 002138 | 15 November 4,2002 `Addenda for Phase III Protocol 9. 2TM Transfer Efficiency Test for CgF1;SOsK* (PFOS) In addition to the transfer efficiency tests specified in phase IIl protocol, direct transfer efficiency tests where the gasified samples are collected without passing through the combustion reactor will also be performed. Samples will be collected using two PUF cartridges. Extraction ofthe entire system (pyroprobe chamber and transfer tubing) will be performed using methanol as the solvent. This additional study will provide information concerning how much PFOS is transportedfromthepyroprobethroughthe transfer lines to the reactor entrance. The transfer efficiency testsinthephase III protocol address sample transport from the pyroprobe to the combustion reactor exit. Figure 9 shows a schematic diagramofthe direct transfer efficiency test for PFOS. The gasified samples willbecollected usingtwo PUF cartridgesinthesimilarmannerasdescribed in Section 5ofthe phase Il protocol. The PUF cartridges willbedirectly connected to the pyroprobe chamber by 19.5 cm long, 1/8" 0.d. Silcosteel tubing (Silcosteel, Restec, Inc.). The GC oven temperature will be held at 260C through theentireanalysis. Thedetailed flow profiles are shown in Table 3. Heliumwill beusedas acarriergas. Theflowwill be set a5 0.63 ml/min and held for one minute before the sample is inserted and gasified.Afterthe sample isplacedin the pyroprobe, the flow will remain at 0.63 ml/min for 94 seconds while the sample is gasified at 1250C for 40 seconds. The flow rate willthenbe maximizedto 4.53 m/min and held for 30 seconds to purge the sample from the pyroprobe chamber andtransferline. The conditionsand operational procedures were determined to simulate gas-phase combustion of PFOS at 600C. `The calculated entire volume is 3.79 ml as shown the detail below: TPryarnospfreorbelinceh:amber: ((01.0358))??(c(me?m)?)x x3.31.414x x8 (19c.m5)(em) ==30..7018mmll Total: 379ml "The system will be extracted with methanol using five times the volumeofte pyroprobe and heated transfer lines (19.0 ml). Prior to the extraction, the sample probe and pyroprobe will be removed fromthesystem. The collected samples will be secured, labeled, and appropriately packaged for the delivery to 3M Environmental Laboratory with a methanol solvent blank 002139 1 November 4, 2002 Table 3. Flow Rate Profile for Direct Transfer Efficiency Test Tim(esePee)riod PyRartoepro(mble/Fmilno)w Vo(l@u)me. 600--6805 o0o63r 006030 1395--117899 063063345 004939 189-219 Total V4ol5u3me ml) 2_4732 TLoinTeaorwindcurea1seo(paepnprsoyxsitmeamtteo)insert Be sample. VSepatmiadon ne DBehA Flow \ \ =9 AN we =) [IFi Seer Figure 9. Direct Transfer Efficiency Test for PFOS. 002140 2 November 4, 2002 10. Additional Extraction AnalysisofUnheated Sample Transport Lines In addition to the extractions specified in the phase II protocol, the unheated sample transport lines downstreamofthe combustion furnace (switching valve and the transfer line between switching valve and PUF cartridge) will be extracted using methanol. This analysis will be performed for FC-807A and PFOS after the combustion tests at 600C. This analysis will determineifPFOS condensation occurs while the effluent is being collected using ambient temperature PUF sampling cartridges. `The method will be similar to other extraction analysis. The measured volumeofthe unheated transport line is 0.55 ml. The line will be extracted with methanol using a volume equal to 5 times the transport line volume (2.75 ml).Thecollected samples willbe secured, labeled, and appropriately packaged for the delivery to 3M Environmental Laboratory with a methanol solvent blank. 11. Blank Combustion Analysis Using Single PUF between 600 and 900C Combustion Test. After combustion testsofthe first three samples were completed, we decided to perform another blank combustion analysis using a single PUF after the combustion test at 600C but before the combustion test at 900C for the estofthe samples (FC-S07A and PFOS). The temperature of the GC oven andreactorwill be set at 260and600C, respectively. Tabl4e shows the flow profile that will be performed for this analysis. "Table 4. Flow Rate Profile for PUF Collection (Blank Analysisbetween600and 900C) Tim(esePce)riod RRaetaect(omrl/Fmlionw) _Pyro(pmrlo/bemiFnl)ow Rate To(taml/Fmlionw)Rate VoGlmum)e. Air Air 102-0-112300 99..7700 084084463 1051405514433 2210.078 113400--116400 8899.7(0He) 45436(3Hf 1134.3032 424379 Total Volume (m) 30.01 *Lincar increase (approximate). * Switched to helium for sweep Air and helium will be used for the sample collection. The flow rateforthe reactorandthe pyroprobe will be sameastheactual combustion test at 600C. Air will low for 120 seconds and then increased to the maximum flow rate and held for 10 seconds.Airwill bereplacedby helium to purge all the air from the system for 20 seconds. The collected samples will be secured, labeled, and appropriately packaged for the delivery to 3M Environmental Laboratory with the other PUFs and methanol extractions. 002141 3 | : November 4, 2002 12. 3% Transfer Efficiency Test for PFOS (Sample in Reactor) Another transfer efficiency test where PFOS is directly placedinthe reactor and gasified will alsobe conducted. This analysis will demonstrate the PFOS transport efficiencyofthe overall system downstreamofthe combustion reactor. It will also demonstrate how efficiently the PUFs capture the PFOSthatexits thereactorin the vapor/aerosol phase. Figure 10 shows a schematic: diagram of3" transfer efficiency test. GC/MS in-line analysis, sample collection using PUF, off-line GC/MS analysis using Tedlar bag, and reactor/transfer line, valve extraction using `methanol will be performed in this study using air and helium as carrier gases. A detailed analytical procedure follows. 1. PUF collection and in-line GC/MS analysis for PFOS gasification with air. 2. Tedlar Bag Colleacndtofif-olinne GC/MS analysis for PFOS gasification with air. 3. Methanol extraction for PFOS gasification with air. 4. PUF collection and in-line GC/MS analysis for PFOS gasification with He. 5. Tedlar Bag Collection and off-line GC/MS analysis for PFOS gasification with He. 6. Methanol extraction for PFOS gasification with He. "The sample will be loaded into a sample probe and placed in the middleofthe reactor. The gasification temperature will be determined based on the TGAs conducted in the development of the Phase Itest protocol. Thetransferlines will beheated to 260C andthenthe reactor will be heated to the appropriate temperature. The reactor temperature will be between 525 and 575C dependingon the sample and carrier gas. The temperature willbeheld for 5 minutes for sample collection and in-line GC/MS analysis. The PUF collection, in-line GC/MS analysis and off-line GC/MS analysis will be performed in the similar manner as described in Section 5ofthe phase III protocol. The flow rate will beset as 10.8 m/min to maintain the sampleretentiontime in the reactor at approximately 2 seconds. The calculated reactor volume and measured valve/transfer line volume are 1.82 and 0.21 ml, respectively, yielding a total volumeof2.03 ml. The reactor/transfer line, valve system will be extracted by methanol using a volume equal to 5 times the volumeofthe reactor/transfer line, and valve (10.2 ml). Prior to the extraction, sample probe will be removed from the system. The collected samples will be secured, labeled, and appropriately packaged for the delivery to 3M Environmental Laboratory with a methanol solvent blank. 002142 4 Yatton November 4, 2002 ene 1 n~|DIG=a i tg `VSwiitvcheins| 0 o<x |=o nCom=rtOer] oie |L_T_VJ Simp Probe cat Figure 10. Schematic Diagramof 3 Transfer Efficiency Test 002143 5 November 4,2002 13. Sulfur Recovery Analysis Sulfur recovery rate as SO; using the in-line GC/MS system was not quantitatively repeatable. `Thiswasdueprimarily to the low SO; peak resolution using the cryogenic focusingmethodat -60C with a holding timeof ca. 4 min. Because the SO; peaksusing the off-line GC/MS system `were much sharper analyticalresultsto than those obs quantitatively erved using in-line GC/MS, analyze thesulfur recovery we decided analysis as to use off- SO. This line GC/ section MS describes the overall protocol for these tests. 13.1 Calibration Curve Pure sulfur dioxide (Aldrich 99.9+ %) willbe dilutetod 100, 400, 700, 1000 ppm using the `oTpeedrlaatribnaggco(nSdKitCioInncs.w,i0l.l5bLe)staomceonassturuscetd tfhoer coaflfi-blrianetiGonCc/uMrvSe.anTalhyesicsoofltumhneaancdtutahlecGomCb/uMsStion tests. Each concentration will be performed twice and the average will be taken. 13.2 SO, Transfer Efficiency Analysis Known amountofSO, standard will be injected into reactor and collected along with carriergas (air) flow by 0.5 L Tedlar bag. 1 mlofcollected sample will be injected to off-line GC/MS system and recovery rate will be calculated using the calibration established above. Figure 11 shows the schematic diagram of SO; transfer efficiency test. The reactor/transfer line `system will be heated at 260C throughout the SO; transfer efficiency test. Dry air will be used as a carrier flow. Theflowrateforthereactorandpyroprobewill be 8.0 and0.75 ml/min, respectively. After the switching valve is turned to (1) position, 1 mlof4.0% concentration SO; `will will be be tiunmjeedcttteood(2t)heporseiatcitoonr.anTdhtehesabmapglweilwlilblebeclcoosleld.ectTehdefsoarmp2.l5 emdinb,atghweinllthbee`bswriotucghhitngtovaolfvf-e line GC/MS system and 1 mlofsample willbe injected. The total amount of molar number in the Tedlar bag will be calculated based on the calibration curve and the total volume collected. "The recovery rate will be estimated based on the total amountofmolar number collected over the total amountofmolar number injected. The test will be conducted twice and the average will be taken. cod | HH | 6 Noveaber, 2002 fran i TED he ne Eo) Vaverr sm 4 rw Eom. &' = = Bn Figure 11. Schematic Diagram of SO; Transfer Efficiency Test , 002145 Appendix 5 `The 3M Analytical Report 002146 Analytical Report Analytical Results for the University of Dayton Research Institute Study Titled "Laboratory-Scale Thermal Degradation of Perfluoro-Octanyl Sulfonate and Related Precursors" Combined Laboratory Report for E02-0820, E02-0821, 02.0840, E02-0867, E02.0895, E02.0899, E02-0916 02.0817,02.0026, E02-0968, E02.0969, and E02-0971 Testing Laboratory 3M Enviro3nMmeEnntvailrToenmcehnntoallogLyab&orSaatfoertyy Services 935Bu2s3h0Av0enue, St Paul, MN 55106 Laboratory Contact WilaBmldKg..R2e3ag6e0n9, Ph SL PaPu.l0,.MBNox5531333133331 PhFoAnXe::(6(5615)1)7777886-1875865 Requester 3M EnvironmentalETreicAhcnoRleoingeyr& Safety Services PB.lOd.g.B2ox3303301 St Paul, MN 55133-3331 002147 er | 3MEnvironmental Lbortory University of DayonIncinerSsxidoyn 1 Introduction P`wSUoalsFveSrnaotmesxpitlereac)twsaehrneedsspauobglmyiiuertseetdgheanneatfrhoseatdm(EaPntUvhFie)rUcmnaoritnvrteirdagsleLs(aoSbfuDpaeydletctooen,rROmeRisBneOaTMar.tc-wh1hI0a0nt0to,2voe2,lsmUmPROFDOID,S andiRngotltoosdtPurdcyturesdr'".abSaomrptle rSecsluesTphraomsnet!eDdohgerraodwaetroongofenPoerrfsuaadrao-3OctaunsinSguLraMtS instrumentationtodetectand quantitatethePFOSanion (CoF S05). ICnodnitvaiidnusalbsotuhdtyhesammepalseusreadnadniqounactoynccaennrtoallsoanmspalnedstahreocporncoesnetnattaodnionfApPpFeOnSdunAc,aewhciscdh {`oCropuarltsypaenrcdentthreeccoonvtreirbiuetsi.oTnhoef itnhterpporteatastsiionumofcraetisounsfobehyeomnadshse ucsoepdeaolfoiwnsgfoUpRrDtIantdo nalbreepcoormt.pleta byURDIsyporsonnlandte3Mrequesteraepresented ntho URDI 2' SamplReceipt Repourstte2d0saanmplSeesptweembreerr2ec3e,iv2e002atntdhael3yMzeEndvbiectrwmeeenntSaelpLtaebmobraetror3yfaondmOUcRDIbe,tw2e00e2n. Tfhoeosatmepmlpeesrscuornssst1asdoamfpmleethcahneoclkeixnacnttslaannadlPysUiFs.cAarfidrgosa,saAmpslamepwleesawaenreasbozresdtdah,et {oefmaihisanmgieexsaarcotdo saomplmewaensshtraorretadwdadtar.figeatoe atapproximately#C. Deofirocsot `iSnasmpalmeps EcGh2e.c0k6i0n5.-T4h3e0s1e4asnadmEeOs2w0eB6r9o-a4s3s0o1d2twaedrwoirhthkooecxatoadcwtiotnhbtahenaksasnodcifalsedesxatmopclieosn {orthsocond esied arkcombusian.Therearooul oporidforhese amps. veesamplecontainers, Chemvials, wero receivednotlabled. 1sassuamteesda WG`siRamplh4ee3sc7c1oi4m,rea sFpCo-En10d32t9.o50ts0h4ae0mb4lp2al7n1ek5,.)fTrfhsoteaihnadcFsCaec.lo1n3dF9e8Cxhtnrecamncativroianlisscaansmsnpoklc,eisast(ieEncd02w-ti0he8hy4wh0-eo4sr2e7s1ra6em,pEcl0oe2ns-e `wnedrroecpoonsne.quentlylabeled 25 EOZ.0B40A,B, an Candwere denied0 suchinth rowdota The iposamplesthtave wih eachseofsampleswerenotanalyzedbutaeresined or possiblefutureanalysis. All studysamplescollectedbut notanalyzedwilbe retaineduntil permissionisprovidedby the requester todiscard them in an appropriate manner. 3 HoldingTimes HSGooalrtdeaisngagenctdoimnaendsaifloyonsrisasndaaaltytsohiesawlareorareslnoGorotycaWsmeseikng!tnecaddopnrivtoretro1swamGpnalteaar.eeceCioapgtro.aStdaesmtpoxlni,npegsedaotcesasl,tsraesecmeipidlpeet {Snattythsoamprloecshweemriocsatsjmeecaesdureod haosthaerlmealndemgarhaadnedilonosvleurcycoinmdaoprersi.oHdiofsBs50ueyxp.aci(e)d024.48 Page2030 --_---- 3M Environmental Laboratory UniveorfsDaiyttoyn Incineraion Study 4 Methods - AnalayndtPriepacraatolry Pqrueaplatryactoonrtyraonlsdpaknealsytaincadl mbleatnhkostdsowaesrsesnsomtevatlhioddapteedrffoorrtmhainscpreo.jFecotrbuthtiasrporpojreoccte,smseetdhawniotlh mettrahcatnsoalenxdtrpaocltysudriedthnaontarfeoquairme(aPnUyFf)ucrathretridprgeepsawreartiooanpnrailoyrzteodavniaalyLsiMsS.H.owMeovesrt,osfotmhee eixtsroacntss )dwderreeqauliirqeuoatseidmnptloesdaimuptloenivinalmseatnhadnaonlaplryizoerdt.oanalysis.Thesesamples (xcsand TIhnseuPmUmFasraym,ptlheesP,UFabwcaonsterxoalbcltaekdsb,yarnedmaovbicnongttrhoellsaprigkeesplraesqtuiicreenddecxtarpacattitohne wpriidceteonandaolyfstihse. c`aaprpirdoigmeaatanldy hpaulsfhwianygdothwenPthUeFcawritihdgea.dTehaenn tdwiesnptoysmaibllteegrlsaosfsmpeatthaineolnwtalsathdedteodptwo tahse f`oPsraUamFpitlnlotewhaasectsaafrilttrooiwodengsed.etTcohosenildasfroagronfpidltateshetniecmnieninundtveoesartpawdoafailsvlreoewptflioamcreesddtesaoonredpnttsihuoernceoapfrrttrohipedeagrneawmliayxstievnsga.ofTxhinemtniertxehseted ``Aafntearfddoionnamlifnoutuerst,itmheessfaomrplateowtaalsodfrafiivneedwaanshdewsa.shAefdeargtahienwiitthhtwhaessha,mtheetmweetnthyamnidlltwearss colectedand aliquoted into a sampleval oranalysisviaLCMS. AExntarlaycstissoofrsOatmhpelreSsywsatsecmosnduUscitnegdbHasPedLonCE-TS-E8-l18e5.1c"tAnarSlpyoesicstsorfopmWerarsyta.e"ySTthr/iesaMmme,atWhasotdesirs inotkerweisttevnisapeLcCi/fiMcSa.llTyhoertmehteehxotdrawcatisonmoofdiPfUieFdcar(tdroicdugmeesn,jtuesd faosrdtehveiaantailoynssi)toofsthtereanngatlhyetnestohfe tdbhaeetgsraeaqamutpaelirtetysfh,oaCrntC0h.Ve9s9ae0r,aenCaiClnVjyesscetsmebudsyatttblheeeafwsohtlteovweirny2gt5:e%snt,satanhmdepaslryedscstu,ertmvheseusciaotraebefiilfctoyibnmetuiosnfjtdeebctete<erd5moi.nn0la%ytiproocnartiitvtooe s`hsotuanlddarbddeevwiiatthiionn(2R5S%D()ofowrearreamciotuonftsqauanndti<t2at.i5o%nR(SLDLOfQo)rr2e3fe0nt%i)onotfmtehsei,ratnudethvealsutasn.daArndsy Geviatonsfrom thismethodare iscussedinsection 5ofthisepart. A`gSparmopliemsatweeirnestarnualmyeznetdcoondnitaionnAsagrieenptres1e1n0t0eSdbeerlieosw.LAcUtMuaSlDcoinnditthioennseagraetdiovceuimoennmtoeddei.n rawdota. LCCONDITIONS: Column Flow: 0300mimin InjectionVolume: 354. `Column Temperature: 30C Column: Betasi C18 Column Size: 260mm, 51 SolvenAt: SohentB: Gradient: 2mMAmmoriumAcetate Methanol Time %A %8 [EC 050 8 15 300 0 100 55% 0 100 600 8 15 800 8 15 002149 Page3of30 3M Enviroameatl Labora MMSodCeO:NDITIOSNMS: VPoolawrt:y. ~~ 4No0g0atviv POSSion: 490 Univesity ofDayion Incineration Study 5 Analysis 5.4 Calibration cCCaoalebibfrracairtoitonsncsoucrfuvdreevsteewsrewmreionraweicotnhsiwtnerur2c5te%rd,eussheionrLgaOitaGlnwea0is9tfn9i0v2aen3cd0on%oc.fenCtcaralalbttriraoantsoownnisstanhndqdauaarrdddrasstoviucoftisdtiidnge.ttihAsol aofnagmrentcoamtiowrovrefecatrehavxtncp1hoo0eisndsaa.rpCosdoo.nciuAmneignCtceOadVbrriaetcthooovnervriaaewcsdawateiaroonkwostniannwdia1rhd2ls5o%(chCrC5iScs)apwasecrteodaabnnayztfhoxod aos. 52 SuytsotfteomtSauniatalbltliatyuns a systemsufi passedfoPFOSexeptforon 1042. TChalestryasitnecmsauviteasbailnitdywCaCsV5s.f2%a,esxsceedefdoirnBgitshean5a.e0s%,RSheDdcraiatewriaosntycpeipcatlelyda.llowed.Sinceal 5.3 wBsoleaennxkctesptbioanrsk.s(wOenrSo 0ss2thaanmaentohhanaollbhaenakrceocisuirnsedosfptphrolsonwaeteiliyt4ofpqoulaln.aotfoPnFwOiSh. lTo3hivseomnssbootmoawottohcbasauLrnLekOnwcGaads(<fe5o0lc0lpoawiefdlbc.ythSEo0c2d.oa0tt8.h9e5n4e2x6t7s3a(mPFeOfSoBlLowKi.nPgUtRh)a,wahrckhvhaasd<LPLF0OGS. SAhbloawnk PoUs FhcaratindgohwlashexaraecaocdunwtihofefahchoswterofIsampflQesaantdaanarze6d0,hTahinsa,nahysss acing he scooptance aonforbarksamp ess. 5.4 L1a0Lb,aobrotrwearyteoGprrtyoprCeornStpiwrkoielshaLSpCciShk)ecsosnosifstPeUdoFsfaPmpUlFecsa.rEtaecshsLpCeSdwaasksnpoiwknadebvyersoofm1pagnahned SIkoeninendpsosbsiotiroasnndcwuaaapsbeoaxovwhaecwihioed3seuaeicncodeosocffbttahedocPsUaFa.tiTenha4anLdChSowjeaocstpnagrl.tohwoedaptproopyrifaotreaamloausrto0f fTohrePaOveSr,agSePaUmFpLCrSesruescaorvoenrostfcoretch t1pfgarnids10cgovsepykeslaormea8t2o%n.anSudm6m2a%riresspoofcetaicehy analysisoftheLCSS roposertd nAppend. 002150 Page dof30 3MEnvironmental Labosry UniofDvayteonIscieiriotnStyuy 5.5 `SSaammppolCealCcaaltcounl:ations Fina Result (og) = IsramenRes (67x Dilton Factor Exton Volume0) Soto EO2096(T8ES4EX3-P3FO6SR2S) Fina Rel0)= 270 x5000101238L05 PolyurethaneFoam(PUF) Cartridgespike recoveries: InstResrultu(/Lm)xe00n2Lt "Recovery `SpikedAmount (ug) 1 Sofor 020023051 (PROS): FeaReso 030828-x0701 6% 6 DataSummary IEnednsiivprieodcunaimleosnLatmMlpSLlueamrbebsauelnrtsa.anSrdaemphprrecsoeednsettehdstiawnraapsgpivesensndoaicxepAt.aedE.awic(hohrtsnhaoomsnpa.lmeopipsauirpdteosnpntiaofivieadlwloita)hlaintds in ug (i applicable)for each analyteofinterest. Samplesthat werenotdetected abovethe lower bleiimintogfthqeuaLntLiOtGatfioorn (LLOaQna)layreroefpoarttepdraisculelsrsstahalne.quantities("<') withthenumericalvalue pLJaeobrvocreeanotftotcrhyeaLCroayntbisogSiprvCiekniae.AsrtvoaerorSoapgprieresyssae,nnndtsditiannudaaprspdaedmonpvldietsownaesranordooaortnocyoocrpaetlcoeoadtfeoidrn peorocglalchansdptkhieg 7 Data/ SampleRetention Topheoraftiinnagl prerpoocretdaunrder.aw datawi beretainedaccordingfo SM EnvionmontlLabstandard 002151 Pagesor30 eee 3M Environmental Laboratory UniversityofDayton Incineration Study. hs -- per `AppendiAx: Individual Sample Results. `AppendiBx: Labaratory Control Spikes. `AppendiCx: Example Chromatograms 002152 Pageof30 SM EnvironLimboer nt Universi of ayion caer Sly 9 Signatures HaraRosPgh.oronayvid HarogWeirlliam k. - SlapRoKeslerudes ha S23 clin htt Grams odaleufr 002153 Fuge 0130 ---------------------------------------- 3M Eavi L err. `University ofDayton Incineration Study Appendix A: Individual Sample Results 002154 Page 020 rrr ----" SO SRS----------y wt rewn iT nt o 5Tn m2os DEeopenTer omsooe,r2mLSEBNCS 2 && B SineslirmeeohlN 2H # rmLioenirme aE rmmmems E roSdhe =ok 23 A CBi ohn pa rem awo = = mmmD oaermeaasnse r mofemmemn cSm hoooIIa 2 on mmEaaorsnaynn oawZmri, IzSmahoNodohmSm sdI2sEm I l eEacr o: Ai eodI mEEBoeaoesrn eemAm0ma 2orwno smD2o2oon mTEBeeoPeenGn a ommoom 2Dmo Z8am #2 B[Bmoaeosfesdiw A T2 momme B2sm Boan ==on H[ moeneiw i EoaoR, 2= vao m = = EPBmoihmiesen emt pamnexmxnndo5 om %o=m Pi aEn on ST 4 E nmosrssa p mnEIn sEn % m8 | 4 002155 -- 3MEnvicamenlLaborsy Univer ofDeynlcariSoony sane w os moT s Coomse mTHiommeeos mmmesemne:sm wdWewm eS 3m oa3m iSTiimpoaagwomnn mTmeoeamanamnni wwamw 4oBx0 neokn TTTmoeammna Hmmhammaeavn: amhe om 5m Tom 0[o08bmrm tee ro tepeaeltdom t nybtsyie paioy n n Thet rm v meta s eet atm---- 002156 Pel00130 | --_-- 3M Eovioamentl Laboratory Univesity ofDayion Incineration Study Appendix B: Laboratory Control Spikes 002157 Page 11 of30 3MEaviroomentalLaborsiory `UsoifDavytoneIocrinersatiotnStyudy Table1:1, tory FCOSontrpoe5rlcent Sumple (gal) recovery RPD QoWIwBLsCS?1 4d3s4s 9E1M% 4S QmWeBBLLCcSST2 44546 O91%% 40% ooooLLCCcSsl2 M38D2 E76N% 14% oomosLLccSsl2 M313 9M0%% 19% ooomssLLCcSs12 338635 MT%M 33% QoUuOoIiCcSsT2 H38T4 6T%H 10% oowwesaLnCcSsty A@s3 s8s%n 20% SunAdavredrDaegveision a4207 885%% TorroRvSeDoFOS 0L1S0m%ir sR0P0Dp-R0eAuLiv1e0P0e0e)tDil Table2:10, 0C8ontpreorlcent Sumple (py/al) ressvery RED DomIsBBLLCCSS34 44A 99%% 68% QmELcS3 49 ok so oImCBLScSIs 4S1I49 180%% 46% omLCs4 43 gm LowCLcIs4 4443 ao1T% 43% LCI 4S 8% Ae oooueLLCCSS34 HAsSs 8o%% AT owLCSA 46 95% Sund`aArvdeDnogveiston 3H 16 o 63% RSD TM Sar00apewLof(70050 00LS ir : 002158 Page120630 ------------------------------------------------------------------S------------------ 3M BavioamenlLaborsry UaiofDveyneIncisertiion Sytudy Appendix C: Example Chromatograms 002159 Page 130f30 FE, iI]i | | 3; I i FETT | i AE ' [8 By | i to: pd: ioE . bPolobiy iEimsohne PE E[A ruIiHEE iHt ] 2 m fad m 1 a : 002460 | : bl iPo I I : : : :; : : T } FEVETCETETYYYY -- hg Po, HI PliiEp on fii i ie i i iI Hil i Poa i i & tt > 1 | C0 REamy vozdes i i : . | ; ; 3 ! ; nd DI olI i iPopo Pligg {jE Ii! k iro ii os JF Rilke | 164 Ea J |hl vong;e a | - ! : i i k ivy | yyreryyy yy|v -- r Poi sob om ii 8 Pon HEEEE J i i! i i] pl 8 wd Es i Bogue i | ii8I iy oimaHaaind | vaztes i 2 bls : : } } | crrrveryrerss || fF i 2 2 i i ai Pil1i8s6my ly ow Eliyig bo EI it i pil i Boal k LL] ir [B| ER8 LdlEN F # Haugy h d | Z 00-134 iPo : !I i EYEE EEYeeYyY ' -- 3 i : 11 geil Polly PlioEyn 2 oi ih if i ji i i] PEpEirdBigke Hod Pd dd fo! 5 anal | 002165 | 1|] : ! : | :il $ Hl 7 | a: vrrerververysy |mmm Polly he i 1 - 2 1.1 it P Plh atigll low, i it f il i i il I He : PoE hike | d daE li E : 002166 ii ] i: i i ny | :: F| reres ery j -- --- } i Toad aE i a hi PPHpicEEp Ia Lilo P[8E aRikla [| en z |: i x | : i IEEE 'i J EE PPod,f. : me | i dg: fi Pilate LNiHe [| F mikey | FI | | i 00%aes a i I : :] } : i ; i" : i | i TT, -- Foy PPooE gedHa Pic om ity 3 } ils i it i il! pil ok " |BE 0 mRilkN # & 3 14 1 1 00216 8 Z 1P| :: ! {| 8 i [ zo Erk E t Pody i. owt i i Hi fi Flamm Pig bo P pil l dboidh} [8# aHigloyd ii #0 fail Nl a { EE : I : | | i ITER F--=, i smn |GPoy { JipihgIs dw EEO RENEE A } in Lil, k HH IER BE oEiE.S ] gi gudpity] | a ;i 002191 I; 3 . ] . 3 | i FEE H srr |e PPoyof i, uire || ki Iii iEy | : 002178 I :; : : | i SRNR } |-- iPPooploi lm PtliEc D i jiod it Lil bh J |bEomRed 4 moro i ] i Em . 0017 II] ; :2: |i YETTEYYyyeeyTy -- | srs piel i Ty i33o0igli louyi ili J pil k nd i sll PEE Bik EB fe i i siti iy | i om] ost 2 I bls } f ! 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