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"off AR 226 The Society of the Plastics Industry, Inc. Suite 600K 1801 K Street, N.W. `Washington, D.C. 20006 12IS AlElxeecnutCi.vWe eDiirdecmtoarn Monday, February 03, 2003 Ms. U.S. MEanrvyirFonDmoemnitnailaPkrotection Agency E12P0A0 EPaesntn,sMyalivlanCioadAeve7n4u0e5,MNW Washington, DC 20460 Dear Ms. Dominiak: g z53207 Ss Zz =Z 55A5 =a8 encloseTdhceopSiPeIsoFflu"oDreotpeocltyimnegrasnMdaQnuuafnatcitfuyrienrgsLGorwouLpev(eFlMsGo)fFrleuqoureostpeodlyI mfeorrwPaorldymteoryiozuattihoen `wAaisdsdevAelGoupieddabnycethDeocFuMmGentan.d" TishientGeuniddeadntcoepDroocviudmeenitnf,ocromamtpiloenteodnagnednepruabllgiusihdeedlilansetswfeoerkt,he "badseetedrmoinnatthieoncooflflelcutoirveopeoxpleyrmieerncpeoolfymmereimzbaetirosnoafidtsheininaduvsatrriye,tybouft amraetrnioctesi.ntTehndeegdutiodebleincietshaerre exhaustive or inclusiveofall pertinent requirements. Neither the document nor this cover letter contains CBI Sincerely, Na. cc: Lynne Harris Sewer MOY OBL I Detecting and Quantifying Low Levels of Fluoropolymer Polymerization Aids -- A Guidance Document Fluoropolymer Manufacturers Group (FMG) -- Technical Working Group (TWG) ~ Analytical Working Group (AWG) `The Society of the Plastics Industry, Inc. 1801K Street, NW, Suite 600K Washington, DC 20006-1301 NOTE TO USERS This Guidance Document was developedbythe Fluoropolymer Manufacturers Group ofThe Society of the fPllausotriocspoIlnydmuesrtryp,olIyncm.erainzdatiisonintaeindsdedinato provide variety ionffomramtarticieosn.onTgheenergaulidgeuliidneelsinpersovfiordetdheadreetberamsiendatoinonthoef collective experience of membersofthe industry, but are not intended to be either exhaustive or inclusive of all pertinent requirements. The information providedinthis guide is offered in good faith and believed to be reliable, but is made WITHOUT WARRANTY, EXPRESSED OR IMPLIED, AS TO THE gMaruEeidRteChleiHynAecsNlTparAiomBveIiddLetIodTsaaYnt,distfFhyeIaleTlxNcaEumSrprSleentsFOrineRcqluuiAdreedmPeaAnrtResTonIoftCGUionLtoAednRdLeadUbSotEorba,etoOdriyRrPerAaccNttYitecodesOa.TnyFHoEplalRrotwiMciunAlgTarTtphEerRoG.duuictd,aTnnhcoeer obDfaolscaeubdmoiersansttuobrdjyoeecestqtunoioptcmhgeaunnatgr.ea,ntUwesheeirccshomampealiycaainunctveiaolwinidetadhtetahanantyytrohereguaillnalftooifortnmhaeotricosnotamunmpdeaonrndt,wshsciaofcnehthataihnnidesldGihnuegir,deainnno.cresaDfoecoupmereanttioins TphriodsucGtusiodranpcroeceDsosecsu.meInntdeissignnoitngienxtepnedreidmetnotsparonvdiodpeersapteicnigfiecquaidpvimceen,t,luesgaelrsoofrthotihserGwuiisdea,ncoenpDarotciucmuelnatr should consult with their own legal and technical advisors, their suppliers, and other appropriate sources (including but not limited to product or package labels, technical bulletins, or sales literature) which contain information about known and reasonably foreseeable health and safety risksoftheir proprietary products and processes. SPI, its members and contributors, do not assume any responsibility for the user's compliance `with any applicable laws and regulations, nor for any persons relying on the information contained in this `Guidance Document. ApSloPllIyimdneofreoisrzmanatotitioonennadaiodbrsos,uetretashniensipnrodoripvrpiirdeoutdaaulrcytmsap,nruoofdraucacttnusyroemrra'npsurfopacrceotsdusurecestrsoofcroanuntsyaeirmnaeondfuflheaarbceotirunarteohrraysoribneussetenrrupmorefonvtfislduoeodrrosbupypopltlyihmeoses.re `manufacturers who are solely responsible for the accuracy and completenessofthe data. Copyright 2003 `The Societyofthe Plastics Industry, Inc. All Rights Reserved SPI Literature Catalogue #: BZ-102 DeterminingCoLpoyrwigLhetv2e0l0s3 TofheFiSoucoireotypoofltyhmeePrlaPsotilcysmIenrdiuzsatt,ioInnc,AiAldlsi--ghAtsGRueisderavnecde Document Determining Low Levels of Fluoropolymer Polymerization Aids -- A Guidance Document 10 PUIPOSE...ovvvvvnnsssnssessssssssssssssssssssssssssssssssssssssssssesssssssssssssssssssmsseessnn. | 30 Safe Handling I0formation........oceossvvssssssssssrsssssesssesssssssssssssssssminsesnes 3 40 AnalyticalTechBOIORIES...ceessssssssrrrrssssssssssseesseceesssssssessessssssmsssesesssmnerems 4 S50 Analysis OfPFOA intWALET........ovovvrrssssssneesssssssssssesssssssssssssssssmmmessones 60 Analysis ofAmmoniumPerfluorooctancate (APFO)inAif.............cceoorrrssreeess 7 70 Determination ofAmmonium Perfluorooctanoate (APFO) in Biological Matrices... BO Sli.cevreessesinrsrinsesssssissssssssssesses ssssssssssmsesesnns 9 90 Additional AnalyticalCOBSIAErAtONS.cevssevvvvvvssssssssseseneseeessnrressssssssessssmnees 9 100REEFENCES. ...ovvvrrrsvnnnnressssssssasssssssssssssssssssssssssssssesssssssssssssssssssssnneenss 11 TTAABBLLEE21::GDeneefrailnTierotmfiiQnuooallnoigtsyy AasnsduDreafintcieon(s.Q.A.)..C.r.i.e.r.i..a....c.o...v.c.ev.v.v.r.s.r.e.s.ssososrsrsssssoesssssocrmrssroern,s 2 10 TABLE 3:Physicaland Chemical PRODEIties............cvvverrrrrrrrsssrmesererssossmrs 14 AAPPPPEENNDIDXIBAX.: GEexnaemrpallesPohyfsiFclauloarnodpoClhyemmeircPaollPyrmOeDrETiHziaets.i.o.n..A.i.d.s..............................................cooooonoss 12 13 APPENDIX C: ComparisonofAvailable Analytical Techniques for Fluoropolymers........ 16 H 1.0 Purpose PolymerTihziatsiodnoAciudmsen(tFPAwSil)linfvoacruisouosnmattrhiecedse.teTrhmiisnadtoicounmeonft lisonwotlmeveealnst otofbFelaulolr-ionpcollusyimveer, but and rather data atcoqueimspihtaiosnizoenthtehessteatemaotferkinalosw.ledSgiencaendthteheFdPifAficuclotvyerofaenwsiudreingrarnegleiabolfe sampling chemical s2tsruucsteufruels,faorsauncoctehsesrf.ul Amlestoh,otdhifsordoonceumceonmtpowiulnldddiroeecst ntohte nreecaedsesrartiolyaesnusbusreettohfetmheetahpopdrowpirlilabtee wliittehratthuerettehramtinwiolllogbyeanusdedfeufliinniteisotnasbluissehidnignatnhaelyftiieclad.l protocols. Table 1 will provide the reader " 2.0 Introduction surfactaFntlsu,ordiosppoelrysmaenrt,Poetlcy.meTrhiezamtioosntAciodmsm(oFnPAuss)eaorfeFusPeAd iisnadsivseurrsfeacitnadnutsst.riaFlluaoprpolsiucraftaicotnasnatss are similar in structure hydrophobic part. The to conventional difference lies surfactants in that the inhytdhraotphtohebyichapvaertaohfydtrhoephiflluiocropsaurrtfaacntdanta molecule fluorine contains atoms in ftlhueorisnuraftaecdtacnatrbmonosl.ecuTlhee extent affect of the the fluorination characteristics and the position of the of the fluorosurfactant. Consequently, perfluorinated). thTehesuhryfdarcotapnhtosbemsaoyf be termed either partially fluorinated partially or fully surfactants contain fluorinated both fluorine (aka and hhyyddrroopgheonbaetocmosn.sistUsnolfitkewtohe hydrophobes of mutually phobic hydrocarbon parts which asurrefancottanctos,mptahteibplaer.tialCloynsfelquoureinntaltye,d mpaircteilallely cfolnucoreinntartaetdiosnurf(accmtea)n,ts aenxhdibiint amniocmraolsiceospiinc mpachreonsocmoepniac cahsarawcetlelr.istHicosw,evsuecrh,aspacrrtiitailclayl hfyludorroicnaartebdonsusrefgamcetannttsprhoavviedessesvoelruabliliatdyvainntmaogrese over fully commonly perfluorinated used solvents, surfactants. The lowers the melting cpohienmticoafPltehrseftlasbuuiorlrfiitanyc,attawendth,icrsheudreufanccaetbsalnveotslsattihalreietmy,traoenmbdaerdkueascberledyasinessataptbphlleei,accaithdiaosvntisrnetgnhgattehxwcooefupftlliduoonrbaielnattoteohdesarecmviaedlrse.afnodr cthoenFvenattitoancahledhytdoroCc=aOrboins -nboatsesdtabsluer)facistasnttasb.leTthoeavceidrsy, satlrkoanlgi,Co-xFidbaotinodn,inaandcarrebdounctcihoani,nev(enontea:t rdeeltaetrimvienlaythiiognhoftlemopewralteuvreelsso. fIFtPiAsSsthiussvienrgycostnavbeinlittiyontahaltainsaltyhteircaolottceachunsieqoufetsh.e difficulties in the surfactaFntlsu,orfolsuuorrfoascutrafnatcstaanstsaacrleasesitohfercioomnpicouonrdnsoncioovneicr.a rloannigceosufrcfhacetmainctsalcasnt,ruucntulriekse. nLoinkieonailcl surfactants, negative or dissociate into positive ion. ions in an aqueous medium. The hydrophilic part can belong to 4 oisnaenanainoiFnolinuc;ora2o)nsducraoftniaeocntciaacn,ttiswonhcieacrnegbretohuecpl,haysasdnirdfoipe4hd)ilniniotcnoipofanroitucr.istyapecsa:tio1n);an3i)oanimcp,howtheerrice,twhehihcyhdrhoapvheilaitclpeaarstt aanisounrifcacLfeil-kuaeocrttoihsveueirrffahocyntdarnwotisctahtrhbaatonnboecpaopruontsthieetrenplaeyrgtacst,hiavireognceihdcarfcgloeuu.onrtoIestruiirsofnta.hcetaanInttisoinds iitschsfeolcuisoaurtroefsauicnref-waaacctttaeinrvteasnfdonfsoromf the most important classof fluorinated surfactants. They are classified based on the that are structure of 1 Ss Table 1. General Terminology and Definitions Fiuormated A general, non-specific term used synonymouslywith fuorochemical." Chemical Fluorinated Organic Polymer | Abagckbeonen(epreomlyurasmeiddaie,odlpeoslycersitbeekr,napopoowllnyyuamrseetarhwfalhnueio,crihenhcaat)sedoaal`hkwyyhdlirccohhaciiasnra;bpoapnnended a "fet Alxuaomre ipnlaettor ewddoecusaclmrrdibbboene acahspaionl,uymalesrarocstiufvceh,aaTso-wcm[olCeceuHla;r CHw(eiCg(htO(J1O00C0C)H,E:PC)Hy FOlrugoarniincatSeudrfactant | s`nuobns-tsapnecciefwichibcuth ocfotnetnaiunssefdlsuyornionnaytmedoucsalrybo;nasn; the ters fluorosurfactant example is is Fiuorochemical | F`Ac(ogneCnteFraail2,ni)nginotCnhH-es;eplCeecHmie,fnNiStcHtOf,els"ruomruinsee;dspteocidfeisccarlilbey, tbhreotadelrym ial s ucsheedmimcoaslts Caroemmmosotnolftiyoendeusscerdibfeorsrmeaflrlig(e1r-a8ticoan,rbaosnfilreengstuhp)prfelsusoriionnaatgedenmtoslaencudlaess that Frioropolymer |sAtphgeeecnimaaeljrtoayrlistoeylorvmfencutassr.ebdtoondaetsocmrsibwehiapcholcyommeprrisewhic thehpaoslfylmueorricnheaaitniabcahcekcbotone Ep[1ocelo.y:mvimtnhoyenlsiefdlaeurnoeertofylppuoiolcryailmdleeyr(shPiaVgrheD:Fm)poo,lleyfcltuuelotrariarnfwaletueiodrgoheettthphyyollleeynnmeee-(rpPrsoTupFsyEel)ed,nien(hFiEgRh), performance applications where chemical resistance and thermal stability Frioropolymer Polymerization || aAmreegmeebsnseeerrnastlioatlfe.armcluassesodftocodmesmcerricbieaallsuybasveatiloafblpeerpleurofrlouoarlokayllkaytlceadrsbuobsxtyalnactees; Aid Foorosarfactam | sA`umronfloaencc-tuaslnpatersc,iwfediiicsg,phgeetrns(ae<nr1ta0sl0,0te)etr,cm.subsutsead ntcoedweshcerriebecaarsbuornfsacbeeaarctfilvueo,rilnoewin place `NofHhy,droFg(eCn.FAECxaFm2p)le;sCwHoiulCdHi,NnSHclO"uy,deCCHFyi(CCFH2:)iCSEOs,KC',F:HCCFH2:)N,CHCOSOO,O'etc Perluoro- / Perfluorinated |cDaersbcorinbaetsosmpseacirfeicraelpllyaacesduwbisttahnfcleuowrhienreaetaolml sRyd~rCoFg,en awthomesreatnt=a1ch-e4d.to to describe a surface active, low molecular weight (<T000), PerTuorinaied Surfactant A``SHuutboesrrtomasnuwcreefawdchtearnte iaslllecsasrsbpoencsifbiecarbuftluuosreidnesiynnopnlaycmeooufslhyy;draongeenx;amtphleeteisrm eroroalkylai Substance e d | FaAl(gsCeoFnk2e)nreaolSwOneyraNmsHaad"peesrcfrluirboirnogalskuyblsftuannccteiotnhaalbgeraorusp,aFp(eCrF2u)oir-oRc,arwbhoenreunnli,s or hydrogen. Examples include an Fin(tCeFge2r)ainCdH;RCiHs;nOoHt,a Fh(aCloFg2e)n,sSO:N(CHs)CH:CH;OH, and p-F(CF2)s- CgHIOH 2 their hydrophile, which can be divided into four main categories: a) carboxylates (RCOOM, bR)y siuslfaonaftleuso(rRiEneS-Oc;onMt"a)in,ing) shulyfdartoesph(oRbOeSOa;ndM"M)*, aannd di)noprhgoasnpihcatoers a(nRIOorPg(a0n)ic0;cMat;i"o)n,. whTehree cparrebdooxmyilniactaecfiodrs m(PusFeOdAa)nadnfdotrhweihriscahs.there isthemostanalyticaldata arethe perfluorinated In cationic fluorinated surfactants, the fluorinated hydrophobe is attached directly or iCnadtiiroencitclystuorfaacptraonttsondaitsesdocaimaitenoingrwoautpe,r,afqouramtienrgnaarysuarmfamcoen-aicutimvegrpoouspi,tioverlay hcehtaerrgoecdycliiocn baansde."a bneygatthievpelHoy fchtahregemdecdouinutmerainond.thLeiekleecatnrioolnyitecs.surTfhacetraentiss,acagteinoenriaclbseulrifeafcttahnatts acraetiuosnuiacllsyuraffafcetcatnetds adsorb oAnmpnheogtateirvieclyfclhuaorrigneadtesdurfsaucrefsa.c"tants are bifunctional compounds having at least one 3 Acamtpihoonitcergircoupf,luoornienaatneidonsiucrfgarcotuapn,tsancdanarfeunecltecitornonbioctalhlyasneuatnriaolniacroaunndd their isoelectric points. as cationic surfactants depending on the pH ofthe medium? They are compatible with other types of surfactants and falrueorbienlaiteevded stuorfaacbtsaonrtbs oanreeituhseredposiintivefloyam snteagbaitliivzeerlsy, cheamrulgseidfiseurrsfacefso.r' manAumfpahcottuerriincg fluoropolymers, spreading agents wetting agents, on hydrocarbon repellants surfaces, for paper and cleaning agents textiles, fire-extinguishing agents, for degreasing metal surfaces, and personal care products. not Nonionic fluorinated dissociate into fons in swuartfearc.tantCsoanrseeqsuoelnutblley,innaonniaocniidc ofrlaunorailnkaatleidnesumrefdacituamnt.s They do arc less sensititvoe pH and electrolyte changes. surfaces. They are not preferentially adsorbed on charged generaAlpppheynsdiicaxlAancdovcehresmiscoamleoprfotpehretsietsr.ucturetypesof these molecules. Appendix B discusses 3.0 Safe Handling Information for Fluoropolymer Polymerization Aids IndustryR,eIandc.sa(fSePtIy) i"nGfuoirdmaetitoonSaprfieorHatnodulsien,gionfclFuldiunogroMpoSlDySme,rsanDidsptheersSioocnise,t"yavoafiltahbelePleaistthiecrs Aonnlyinie(nhftortmpa:t/i/ownw,ww.fhelthueroinranoMpSoDSloyrminetAhPrisFsgOus.iadfeeo,harmnadglyi/ncghngauneigdeew.apssdfr/)esuolrtsdoirfefcutrlythferromstSudPiLe's `become available. A general Consult your supplier or SPIforthe treatment of physical and other most up-to-date information. properties of FPAs may be found in `FbleueonricnoantdeudctSeudrfoacntaanmtsm.o"niTuhme pmearjfolruiotryooocfttahneoattoexi(cAoPlFoOg)y.datAaPaFnOd hiesaaltphersitluudoireisnaotnedFcPheAmihcaavl;e aitbsisorebxetdrebmyeltyhestbaobldey, adnegdrmadaeysbselodweltye,ctaendditnhtehreefbolroeopdersstirsetsaminfotlhleoewnivnigrionngmeesnttio.n,AiPnhFaOlatciaonn boer Hskyigniecnoinsttasct.(AACGPIFHO)haass abneeannicmlaaslsicfairecdibnyogtehne, AbmuetraivcaainlaCbolenfeevriednecneceofdGooevsenrontmesnutggaelstIntdhuasttrtiahle agenti likely exposure. to cause cancer in humans except under uncommon or unlikely routes or levels of (PPE) Use of engineering controls, good are critical in reducing exposure hygienic practices and personal protection equipment to FPAs. Avoid contact when handling materials containing FPAs. FPAS may be released when dispersions are heated or dried. Although solids, 3 TT -- some FPA have high vapor pressures. It is important to clean up spills before they dry and allow the FPA to sublime. Handle all chemicals with caution, including fluorosurfactants. It is the responsibility of tphreecianudtiivoindsuatlosfhoalnldolwibnagsneedatonmaatveariilaalbsl,esitnafnodramradtsi,oan.nd samples to determine the most appropriate 4.0 Analytical Technologies | | The application logical approach to is to define the need, ddeetteerrmmiinnienwghwihcihcahnaanlyatliyctailctaelcmhentolhoogdietsomiugshetfboer abalpearttoicsuollavre [ the problem, determine if these resources are available in a timely fashion, and if so, proceed. | Odifftfeincultthe process is not as simple as it might seem, especially if the analyte of interest is A useful tool to define the need is "Fitness for Purpose." Fitness for Purpose is the propertyofdata produced by measurement that enables the userofthe data to make technically correct decisions for a stated purpose.' Fitness for Purpose refers to the magnitude of the uncertainty associated with the measurement in relation to the needsofthe application area. For many applications of perfluorinated fluoropolymer polymerization aids, it might be sufficient to simply determine the total fluorideafter combustion with a fluorine ion-selective electrode. For | `measurements required in an industrial, regulated environment, it would be necessary to have more exacting quantitative and qualitative tools with defensible quality assurance as an integral partofeach step. | `The following checklist might also be a useful tool inselecting the analytical method. Whatis the purposeofthe measurement? WHhoawtwiclolnctehnetrmaattieornioalfabneaildyetnetiifsieedx?pected? What quality assurance procedures are required? How will sampling and transport be accomplished? WWhhaattasretthheemesthooduospfrepciocftiecenittiys?al cross contamination? Should screening be used to expedite the measurement process? * What is the linearity and range ofthe measurement? WhWhaatitsstthheedsettaebciltiitoyonflitmhiet (sbaomtphlmeeitnhtohde acaodntaiinnsetrrsumaenndt)c?onditions from sampling to analysis? Whattype of error analysis is appropriate? Whatcriteria are needed to reject data? (R?, `blank less than the method detection limit (MDL), nonzero blanks) VTailmieda,tmioonney, resources Have you obtained? carefully considered the next steps ("What if" planning) after the data are InneeedvaelduatotiinmgptrhoevoevetrhealalcFciutrnaecsys, fporrecPiusripoons,ea,ncdonqsuaildietraattiivoennsahtouurleodbfetgheivaenanlytsoits.he resources Generally, the more precise, accurate, and certthehaigihenrt,he cost andgreaterthe time needed. 3 "The most common fluoropolymer polymerization aid is ammonium perfluorooctanoate, APFO. Since itisthemostcommonmaterialinuse,itisalsothemoststudiedandreported upon. Inwater, APFO dissociates into its anion, perfluorooctanoate, and its cation, ammonium. For analytical measurementtsh,e concentrations are usually expressaesd the original ammonium vsaalrti(ouAsPaFsOp)ecotrs iitns vpoalrvenetd,ipnetrhfelusoarmopolcitnagn,oiscamacpilde (pPreFpOaAr)a.tioTnh,eanfaollylsoisw,inagndsedcattiaonrsewdiulcltihoinghfloirght PFOA. 5.0 Analysis of PFOA in Water 5.1 Sampling and Preservation Care must be used in sampling to avoid later problems in analysis, especially when determining perfluorooctanoic acid (PFOA) and its salts at part per billion (ppb) levels or less. It is important that multiple blanks and standards are run. If blanks show measurable quantities of PFOA, results should be considered suspect. To avoid contamination from sampling equipment and containers, fluoropolymers should be avoided, since PFOA is often used in fluoropolymer `manufacture. Field blanks can help to identify problems in this area. It is important to ensure the sampling equipment being used is not subject to adsorption, absorption, or volatilization | losses, and does not compromise the sample. Sample history should be well documented and contain details of sample collection and transport. It is important to verify hold times for analysesofthis type. Ifnot analyzed promptly, samples should be stored at temperatures at or near zero degrees Celsius. 52 Preparation Different types of water have different sample preparation issues associated with them. If the PFOA salts dissolve more readily than the free acid, it may be necessary to adjust solution conditions through the addition of appropriate bases, such as ammonium hydroxide (see Appendix B). Since PFOA and its salts are surfactants, they tend to spread and coat sample containers and apparatus. Thus unnecessary changing of the test sample container should be aanvaoliydteed,maanyd bsepilkoestredcuoevetroy tahnisalpyhseesnosmheonuolnd.beFpiletrrfaotiromnedoftothaessseasmsplthee mdaeygrebee tnoecwehsiscahrythteo rtoemaobvseorupntdiiosnsoolnvteod sotlhieds.filTtehri.s shPooullydprboepdyolneeneonlfiylitefr nemceedsisaarym,asiyncbeeanaplreyfteermready fboer locsetrtdauien perfluorinated surfactants, In the caseofvery dsiilnucteeasbasmoprlpteisoint imsagyenbeeranlelcyelsessasrtyhtaonpfroercootnhceerntmartaetreiatlhse.sample. This can be accomplished using preconditioned cartridges such as C18, Porapak Q, or Tenax. Recovery of spiked blanks and samples should be assessed to determine the efficiency ofanalyte recovery from such cartridges. Additional sample preparation may be necessary depending on the analytical method chosen for the determination. 53 Typesof Water "Clean" water, such as drinking water, usually should not require filtration. Since the concentration of PFOA is likely to be very low, however, it is especially important to avoid contamination during sampling and handling. Preconcentration and pH adjustment may be necessary. Interference from inorganic fluoride may cause problems with a non-specific analytical method, such as total fluorine content. re 1 Groundwater and river water may of may not require filtration, depending on the source. Mostofthe comments pertaining to "clean" water also apply.Theremay be additional problems created by the presence of biological organisms and other interfering compounds, especially in river water. Process water, such as that found in fluoropolymer manufacturing facilities or in plants that use fluoropolymers in their manufacturing processes, may contain relatively high concentrations of PFOA or its salts. It is important that the time and place of sampling is carefully noted, since concentrations of PFOA may fluctuate substantially with time. Filtration may be necessary to remove undissolved solids, but it will probably be necessary to analyze any Solids removed, since they may contain sizeable quantities of PFOA asa result of sorption. Interference from other components in the process stream should be considered when choosing an analytical technique. Each typeofwater mentioned above should be considered as unique, and has its own set of sampling and analytical problems. Seasonal variations might be significant. Again, it is important o verify hold times for analyses ofthis type. 54 Analytical Methods There are many methods that may be appltioethde analysis of PFOA and its salts. Factors to be considered when choosing a method include cost and availability of equipment, analytical skill level required for analysts, time requirements for sample preparation and analysis, and any trade-offs required between sensitivity, accuracy, and precision of measurement. These considerations are summarized in Appendix C. Total fluorine content is non-specific to PFOA, but may be adequate for relatively high concentrations in samples where it is known that there are no other sources of fluorine besides PFOA. The organic fluorine must be converted to soluble fluoride ion for many of the more common techniques, and this will require some type of combustion. It should be noted that sptearnfdlaurordisnaantedd scpoimkepdosuanmdpsl,essaurche iasmpPorFtOaAnt, taoreensdiufrfeictuhlatt tcoomcboumsbtuisotn cisomcpolmeptleeltye.." Analysis of Ges chromatography with flame ionization (FID), electron capture (ECD), or mass spectroscopic (MSD) detection can be used to determine PFOA. These methods have been reported for the determination of PFOA. in blood plasma and urine**"", and may be adapted to water analysis. Since the acid form cannot be chromatographed, it is necessary to first convert the carboxylic acid to an ester. Various procedures can be used for the esterification, and it is importatnot ensurethatthe esterification is complete by using spiked samples. These techniques are semi-specifi, since the retention timesofknown standardscanserve to identify the materials being analyzed. The lower limit of detection for these techniques isofthe order of one to five parts per million by weight. They have the advantageofusing relatively inexpensive and widely available equipment. Nuclear magnetic resonance (''F-NMR) has been reported to be applicable to PFOA analysis in water with a detection limit of 10 ug/L. It is also semi-specific, but perfluorinated surfactants other than PFOA can interfere with the determination. The presence of branched surfactants can lead to erroneous quantitation; care must be taken to account for the amount of branching. _Pre-concentration of samples may be necessary, but derivatization is not. The equipment is expensive and may be available only in larger laboratories. High performance liquid chromatography (HPLC) has been reported to be applicable to tahnaelyasniasl.ysiSsipnecreflPuForOoAcarabnodxylitiscsaacltisdslaicnkbicohlroogmiocpalhosraemsp,leist''i,s aalnsdo mnaecyesbsearaydatpotadbelreivfaotrizweatteher sample before analysis when using fluorescence detection. As with gas chromatography, it is semi-specific in that retention time of standards can be used to identify the analyte. HPLC 5 \0 equipmentis only moderatelyexpensiveandisreportedto be moresensitive than gas chromatLogiraspihyc.l'y"omgtogaghsjanders sas ester (LOMSIMS) bs been used i dreeqtueirrmeidneerPivFatOiAzatiinornoivfetrhwaeter'sampalnedprhiuormtaon saenraulmy.s"is. IItt iiss csomuppouentdrosLipeCco/iMfriScianntdhdaoteist pnrootvides an additional dimension, which helps to avoid false positives. A detection limit of 1 pg was reported for water and 10 ng/mL for serum.'? It s likely tobethemost generally applicable technique, especiallyfor tracelevels, but the equipment is expensive and likely to be available only in larger laboratories. 55 BeAfnoarleytgiecnaelraMteintghaondalVyatilciadlatdaitoan on unknown samples with anyofthe methods mentioned above, it is important to ensure that the method is validated. This is especially importantif a method developed for one type of medium, e.g. human serum, is to be adapted to another `medium, e.g. water. Lab spiking should be performed to address matrix effects. Blanks are very important for low-level quantitation and minimizing sampling artifacts. Good guidelines for `method validactainboen found in reference 13. 6.0 Analysis of Ammonium Perfluorooctanoate (APFO) in Air includAeppmleitcahtoidonvsaloifdaatiironsacmriptleirniag caonnsdisatneanltysweisthmeatphporodpsritaotethreegmuelaastourryemgeuindtanocfeA. PFDuOesthooutlhde pmoetdeintaiails bcirpihtiacsailc. naMtuertehoofdAdPeFveOloapnmdeontthesrhaoirublodrnienclfuldueoro"zcehreom"icaailrs mceonassiudreermaetinotnsofassawmeplllinags asdhsoourlpdtiboen aabnlde dteosdoirspctriiomnineafftiecibeentciweese,nanandalhyotledionng tpairmteicmleesasvuerresmuesntansa.lytPereifnertahbelyvatphoermpehtahsoe.d Tcohnedrietisohnosuelxdcebpet "froerahl"avbilnagnktsh,e aiinrclpuudmipngedfitehldrobulgahntkhsemt.akeDnemtoonstthreatfiieolndofanldabexcpapoasbeidlittyo vailal analysisofspiked samples and replicates and all associated quality control requirements should be documented. This documentation should include instrumental calibrations and written Standard Operating Procedures (SOPs) or written lab procedures for each step from materials `preparation, sampling, analysis, documentation, reporting and deliverables, and data retention. Third party validation or review is desired. Established quality criteria including method ppreercfiosrimona,ncsepecsihfoiuciltdy,becaldiobcrautmieonntcerdite(rLiai,mibtlaonfk Qcuriatnetriita,atimoantri- xLoOrQ,labunccoenrttraoilntisepsi,keacccruirtaerciya,, replicates, retention-time window criteria, tuning criteria). Reports of analyses of semivolatile or non-volatile fluorochemicals in air have been limited. "!9 A recent analytical air method exists for the analysis of APFO in workplace atmospheres. This method involves LC/MS/MS analysis of acetone extracts from OSHA VmeertshaotidleapSpalmipesletro (thOeVSan)altyusbiess o(fOc"cculpeaatni"onaamlbiSeanftetwyoarnkdplHaecaeltahir.AdmAipnpilsitcraattiioonno,ftOhSHeAm)e.t"hoTdhitso espnevciirfoincmveanltiadaltimoann.ufOaVctSurtiunbgesewmeirsseiuosnesdstaomspilmiunlgtaonreooutshleyr tariarp mfalturoircoecshewmoiucalldparretqiuciurleatseosuarncde vapors from workplace air. Analytical methods were developed for air samples collected on. OVS tubes to quantitatively analyze for both total fluorine, using oxygen bomb combustion/ion selective electrode, and for nineteen analyte specific organofluorochemicals using LC/MS, GC/MS, and IC (ion chromatography).'* A method validation study was conducted according to 4 1} the National Institute of Occupational Safety and Health (NIOSH) with minor revisions of the epxeprefroirmmeanntcael fodresAiPgnFOdaunealytsois swpaecsifsiucfsficoifentthiinstepramrstiocfulaanralystaimcpallirnegcovaeprpyl,icsaatimopnl.e'r caMpeatcihtoyd, msteotrhaogde sctoabmibliitnye,sdeOtVerSmitnuabteiosnamopflliinmgitwsiotfhdLetCe/ctMiSon,anaanldyspirseacinsdioins aapnpdlibciaabsolefftohreqsuaanmtpilteast.ioTnhoef 0.06 - 6 jigs APFO in an OVS tube sample. This method range corresponds to quantitation of PFO in ambient air in the concentration rangeof 0.001 - 0.1 mg/m' with a 60-liter air sample. 7.0 Determination of Ammonium Perfluorooctanoate (APFO) in Biological Matrices `Analyte specific detection ofAPFO in biological matricesattrace levels (parts per billion by we`Tihgehftir)sctatnecbheniaqcuceocmopmlbiisnheeds cushienmgictawlodperriivmaatriyzaatniaolnyttieccahlnideqtueecstcioonuptleecdhnwiitqhuegsa.s 174 vito) chromatography/mass spectrometry detection. Thesecond technique combines biological matrix extraction with liquid chromatography/mass spectrometry detection. Biological matrices are highly variable and impact analytical method performance with tuhneprseadimcetaabnlaleyrteiscualltsm.etShigondifwihcaennt idtifisfearpepnlcieesditnombeitohloogdicpaelrfmaotrrmiaxncvearciraittieorinas coafnbtiessuoebsteyrpvee(d.fgo.r, vliavreiratvioenrs(ues.gs,erraa)b,bittisvsueersufsrarcatt)i.onsF/ocoomdpoannedntDsru(eg.gA.,dmwihnioslterabtliooond(vFeDrAsu)sbsieoarnuaml)y,tiacnadl msepetchioeds validation guidance has been recently published to ensure analytical method performance criteria are defi`nSeodmaenrdecaernetcpounbsliisctaetnitownistohnretghueldaettoerrymmienatthioodn goufidAePliFnOesifnobridoaltoagirceaplormtaitnrgi.ces show low rseppiokretirnegcotvoerrye.gulLaotowry(iacg.e,n<ci7e0s%.) spike recovery percentages may not be appropriate for Analytical method validation successfully met all requirements plans of a for full "partial" validation validation will differ of a method based on the tshpaetciaflirceamdeythhoads vaclhiadnagteionth"aatreregqiuviernesasvaallisdtaitinotnh.e FEDxaAmgpuliedsanocfe dsopcecuimfeinct.method changes requiring "partial 1. 2. CTrhaannsgfeerisnbaentawlyeteincallabmoertahtoordioelsoogryb(eet.wge.ednetaencatliyosntssystem) 43.. CChhaannggeeiinnmaanttircioxagwuiltahnitn isnpehcairevses(t.ign.g, hbiuomloagnicpallafslmuaidto human urine) 5. Changeinsample processing procedures | 76.. CChhaannggeeiinn rsepleecviaenstwciotnhciennmtartatriioxn(er.agn.,gerat plasma to mouse plasma) 98.. CLhiamnigteedisnaminpslteruvmoelnutmsean(ed./go.,rpseodfitawtarriec psltautdfy)orms 10. 11. Rare matrices Selectivity in t(hce.g,prelsiemnicteeod fncuomnbceormoiftianndtivmiedduiaclatsiaomnpsles-endangered species) 12. Selectivity in the presenceof specific metabolites x ! \& 8.0 Solids The determination of perfluorinated carboxylic acids or their salts in solids can be accomplished directly or indirectly. An indirect method such as the combustionofthe material with a Wickbold" torch for total organic fluoride, followed by determination with fluoride ion- selective electrode measurement, is used to seeif a fluorinated compound is present in the solid. Of course the indirect method cannot definitively confirm the presence of any specific fluorinated material. A direct method would probably employ either thermal desorption, derivatization, gas chromatography mass spectrometry (GC/MS) or solvent extraction followed by liquid chromatography tandem mass spectrometry (LC/MS/MS). The mass spectrometric g methods are specific and definitive since they provide both qualitativeand quanitatdaitva.e The massspectrumand retention time are the minimumdataneeded 10identifythe presence of a i| `materialOfintaenswoliitdh. a complex matrix, such as a solid, it is necessary to also characterize the solid since the extraction efficiencyofthe analyte from its matrix will depend on the composition of the solid and also perhaps how long the solid has been exposed to the analyte of interest. It might also be necessary to perform an aging and sequestration study to determine the effect of aging and other components of the matrix. The EPA document "Preparation of Soil Sampling Protocols: Sampling Techniquesand StrategiesTM"*notes that mostofthe variance involved in soil analysis comes from the sampling and not from the laboratory analysis. With solids from a manufacturing process, however, more information on the composition of the solid would be known so that defining the analytical task should be somewhat less complex. If the solids matrix contains other fluorinated species, a determination of the concentration and source (decomposition or reaction with the analyte of interest) might also have to be performed to ascertain the "real" concentration. 9.0 Additional Analytical Considerations Fluoropolymer polymerization aids are unique in their physicochemical properties; therefore special care must be taken in sample preparation and analysis. Common predictive models may lead to significantly erroneous results for physicochemical properties. Since these compounds "look" like hydrocarbons, the temptation is to assume similar characteristics for measuresofvolatility, solubility, etc. This temptation must be resisted and thought given to cach step in the method with a full slateofquality assurance (QA) components incorporated into the process from sampling through analysis and data acceptance and reduction. Method validation studies need to be conducted to ensure the method is sufficient in terms of analytical recovery, sampler capacity, storage stability, determination of limits of | dtheattecttihoen,woarnkd pbreecriesviionewaendd fboirasquoaflitthye asanmdplreigso.r.' ABegfooorde arnesyoudractea airse"rGeupoirdtaendc,eitfiosr iImnpdoursttarny,t Bioanalytical Method Validation." This document is especially useful when GC or LC `methods are employed, and is especially helpful for asingle laboratory initiated validation. Table 2 contains some suggested QA components that will add to the defensibilityofthe data. Fe 13 Table 2. Definitionsof Quality Assurance (QA) Criteria -- Blank rr | sample subjected totheusual analytical or measurement process o establish a zero or baseline value. Calibration fusiments. A comparison ofa measurement standard, instrument, or item with ha standardor instrumentof higheraccuracy to detect and quantify finacuracies andtoreportoreliminatethoseinaccuraciesby CheckStandard Duplicate Samples `standard prepared independentloyf thecalibration standardsand fanalyzed exactly like the samples. [Two samples taken from, and representative of, the same population and carried through all stepsofsampling and analytical procedures n an identical manner. Field Blank `blank used to provide information about contaminants that may b fintroducedduring sample collection, storage, and transport. Taboratory Control Spike [Determinesthedesorption efficiencyofthe target analytes from the sampling media. Samples are prepared by spiking blank sampling media, preferablyfromthe same lot ofmedia used in sample collection, with quantities oftarget analytes commensurate with the ge determined in samples. Laboratory Split Samples[Twoor more representative portions takenfromthe same sample land analyzed by different laboratories to estimate interlaboratory precision or variability and the data comparability. "sampleprepared byadding aknownmassof atargetanalyte (0a. specified amountofmatrix sample for which an independent estimate of thetarget analyte concentration is available. Method Blank `Blank prepared to represent the sample matrixasclosely as possible and analyzed exactly like the calibration standards, amples, and quality control (QC) samples. Resultsof method blanks provide an estimate of within batch variability ofthe blank persopocnesedurea:ndan indicationofthe bias introduced bytheanalytical Split Samples "WO or more representative portions taken from one sample in the {hfaibelodraantodrioersin the laboratoryandanalyzed by different analysts or Validation onfirmation by examination and provisionof objective evidence atthe particular requirements for a specific intended use have been| ffulfilled. `Hh 10.0 References ! EE.d.KiVssoal,u"mFelu9o7r,iMnaatrecdelSuDrefakcktaarn,tsInac.n,dNReepwelYloernkts,,2"0S0u1r.factant Science Series, A. T. Hubbard, ? B.R. Bluestein and C.L. Hilton, eds, "Amphoteric Surfactants," Surfactant Science Ser. Vol. 12,Marcel Dekker, New York (1982). * Guide to the Safe Handling of Fluoropolymer Dispersions. Fluoropolymer Manufacturers Group, The Societyofthe Plastics Industry, Inc., Washington, DC, October 2001. * ACGIH Threshold Limit Values for Chemical Substances and Physical Agents and Biological Exposure Indexes (current edition). ACGIH, 1330 Kemper Meadow Drive, Cincinnati, OH 45240-1634. | 5M. Thompsonand M. Ramsey, Analyst, 120, 261 (1995). J. Belisle, D. F. Hagen, Analytical Biochemistry, 1980, 101, 369-376. 7 R. Wickbold, "Quantitative Combustion of Fluorine Containing Organic Substances," Angew. Chem., 1954, 66; 173-174. * C.A 2001, Moody, W. C. 73, 2200-206. Kwan, J. W. Martin, D. C. Muir, S. A. Mabury, Analytical Chemistry, M. Ylinen, H. 14,713-717, Hanhijrvi, P. Peura, O. Ramd, Arch. Environ. Contam. and Toxicol., 1985, 1 J. Belisle, D. F. Hagen, Analytical Biochemistry, 1978, 87, 545-555. ''" T. OhyaN,. Kudo, E. Suzuki, Y. Kawashima, J. Chromatogr. B, 1998, 720, 1-7. 12. C. Sottani, C. Minoia, Rapid Commun. Mass Spectrom., 2002, 16, 650-654. Guidance for Industry, Bioanalytical Method Validation, U. S. Department of Health and Human Services, Food and Drug Administration, Center for Drug Evaluation and Research (CDER), Center for Veterinary Medicine (CVM), May 2001. 4 oWfKS.eleRcetaegdenS,emeit.-Vaol,l,at"iAlnealayntdicNaolnT-eVcohlantiiqlueesOrAgnadnoMfeltuohroodchVeamliicdaatlisonInFAoirrT,"heAMIeHaAsuJroeurmneanlt, `manuscript in preparation. 'S JW. Martin, et. al., "Collection of Airborne Fluorinated Organics and Analysis by Gas Chromatography/Chemical Ionization Mass Spectrometry," Anal. Chem. 2002, 74, 584-590. "Gu`iTdecehlniicnaelsRfeoprorAtir(MSaaym,pl1i99n5g).and Analytical Method Development and Evaluation, NIOSH "7 KQu.anJt.itHaatnisveen,ChLa.raAc.teCrilzeamteino,n Mo.f E.OrgElalneifcson,FlaunodrocHh.emOi.caJloshnsionn;Bi"oCloomgpiocuanld-SMpaterciicfeisc,," Environmental Science & Technology; 2001; 35(4); 76-770. '8 6"P0r0e/pRaYr/a1t2io8n(1o9f92)S.oil Sampling Protocols: Sampling Techniques and Strategies", EPA ' (T.1J9.50)B.rice, in "Fluorine Chemistry," JH. Simons, ed., Vol. I, Academic Press, New York D. Lines and H. Sutcliffe, J. Fluorine Chem, 25, 505 (1984). 2 2 J.D. LaZerte, L.J. Hals, HG. Kicin, JN. Meuss T.S. Reid and G.H. Smith, J. doerffaenrd, H. Niederprtim, Am. Chem. Soc. Metalloberflache 75, 29, 4525 559 (1953). (1975). 2. Glockner, K. LunkwiatndzD,.Prescher, Tenside 26, 376 (1989). | 2 N.0. BraceJ,. Org. Chem. 27, 4491 (1962). 5 P. Mukerjee and K. J. Mysels, Pap. Symp., 1974 ACS Symp. Ser. 9, 239 (1975). * J. H. Hildebrand, J. M. Prausnitz, and R. L. Scott, "Regular and Related Solutions," p. 204, Van Nostrand Reinhold, New York (1970). " E. A. Kauck and A. R. Diesslin, Ind. Eng. Chem. 43,2332 (1951). we Is j APPENDIX A: Examples of Fluoropolymer Polymerization Aids i | [rotasiom penadecuoocinosis | CoKwt | 2500 |CFsCok | | | | \e | Appendix B: General Physical and Chemical Properties a. Thermal Stability Pecflucrinated surfactants are remarkably stable; enabling them to withstand conditions `whichwouldbe too severe known, thus providing the fflourohroysdurrofcaacrtabnotnsstuarbiflaicttyanetvse."na"thiTghhe Cte-mFpberoantduries oinn etohfetphreessetnrcoengoefst acids, alkali, oxidation and reduction. It has been found that perfluoroalkanecarboxylic acids and perfluoroalkanesulfonic acids are the most stable fluorinated surfactants, while their salts dnefcolmpoocserm8eore readily with the cation andRychain length apparentlyofprofound b. Chemical Stability Perfluorinated alkanoic and alkanesulfonic acids have excellent chemical stability `towards acids, oxidants and alkali."'*"* Perfluorinated alkanecarboxylic acids are strong acids, similar instrengthto mineral acids. c. Melting Points `The perfluorinated carbon chains of surfactant molecules, as compared to their hydrocarbon analogs, arestiffand inflexible duteo the rigidity ofthe C-F bond." It is believed that this contributes totheirhighermelting points, a high Krafft point with reduced solubility in solvents. The Rechain length and branchingoftheterminal units have been found to have a p`omianrtk.edTefhfeecmtelotnintghepomienlttsionfgppeorifnltu"o!roTohacetsainzoeaotfetshweitchatiinoonrgaalnsiochcaastaionnesfdfeoctnootnitnhceremaesletilinngearly `with increasing sizeofionic radii'". stabilityofthe salt with increasing siTzheoifs tphheenioonmiecnroandiis believed to be due to the reduce d. Solubility `The unusual propertiesofthe fluorine atomandthe C-F bond also affect the solubilities ofthe fluorinated surfactants. Perfluoroalkanes are more hydrophobic than their hydrocarbon analogs as shown by their solubility data." The Rychain and the hydrophile haveaneffect on the solubilityofthe fluorinated surfactant.' with increasingchain length. At25 C, C1 The solubilityofperfluoroalkanoic acids decreases to C6 perfluorinated alkanoic acids are miscible in water in all proportions whereas the C8 and C10 perfluorinated alkanoic acids are only slightly sionluwbaltee.r -- iTch.eitsdaemcereiasstersuewiftorh tihnecrseoalsuibnilgictyhoafianllkeanlgithm.etal saltsofperfluorinated alkanoic acids Pre "n Table 3: Physical and Chemical Properties Molecular [[[ rre ey ][Te or] Smeus e Ee R e e S Ton TNeeEn)] Undecafluorohexanoic acid (a) 307-244 Boiling 157C 12-14CH a| | Pentadecafluoroocatcaindo(igc)| 335-67-1 Ammonium Pentadecafluorooctanoate (a) SET Perfluoro-N-deacciadn(oa,i8c) 335-76-2 mer[emo C8HF1502 41407 oe CIOHF190: 514.09 Ie [Semen at 742 mm (d) 278396 mm NA 55-56C TS7165C 2724180 mm Perfluorododecanaocidc (a,g) 307-55-T CI2HF2302 1410 274450Cmm 107-109C | * BHeeinlnset;eiFnoIx;nJ. s Azmuetrr.FioCeht redmeu.rut Snogcd,e7r3C,h2e3m2i3sc(h1e95n3)W.issenschaften. Copyright 1988-2001 | Benefice-Malouet, S, Blancou, H., Itier, J., Commeyras, A; Synthesis, 647-648 (1991). 4 E.A Kauck and A.R. Diesslin, Ind. Eng. Chem. 43, 2332 (1951). Brice, etal; J. Amer. Chem.Soc. 75, 2698-2702(1953). `RuDbaitao,frSo.m, MBlSanDcSous,heHe.t,sCommeyras, A; J. Fluorine Chem. 99(2), 171-176 (1999). " D.Linesand H. Sutcliffe, J. Fluorine Chem.., 25, 505-512 (1984). N/A ~ not available 18 [OCAFSH [De2 wi | |5 FRefr9 ecive|| sVavpocr || sWaotemr [meee |et[renee] | Rae| at20C at 589 nm (e) Cre Perfluoroheptanoicacid at 589nm 375-859 | 1.792g/em' (d)| 13119at27C NA NA rr ememte ||| m | W]T e T | O om meemm |ie e[|V| @ E Peniadecafluoroosanoste (8) 75 mm tig) B 9 APPENDIX C: Comparison of Available Analytical Techniques for Fluoropolymers hia een bs Technique Strengths Costof "Timing Aller || Instrumentation| SaamnpdleInPsrterpuamreanttion Calibration "Total Fluorine| Low ppm | Non-matrix| Non-specific | <S20,000 USD | Onesampleperhour || spVeecrsiaftiicle _| Odpeepreantdoernt | Towppm | Specificity | Field strength | > S100,000 USD |Onesample ever8y GCFID Towppm | Read `MNuolnt-is-psetceifpic |U$s20D,000 50,000| Dthaatna a1 chqouuisrition less (derivatization) OMS Towppm | Specificity | Multi-step 0,000 `Dafa acquisition less GOECD | Low ppm | Sensitvily | (Mduelriivsattiezpation) | $10200,,000000US50D,000|| than Data 1 hour acquisition ess N(daerrrivoawtirzaantigoeno)f| USD than 1 hour | linearity {| Radiation (*Ni source) | Ic Towppm | Sensitivity | Detector 20,000 -- 50,000| Data acquisiion Tess | TOMS' Specificity |dePpoessnidbelentmatrix | u$s50d,000 t3h0amnin1 uhtoeusrper | sMaimnpilmeal | interference | 100000 USD | sample | preparation | TC/MSIMSTM |Sub-ppb | Specificity | Possible matix|> $100,000 USD| 30minutes per Minimal | interference sample sparmeppalreation **ATneaclyhtniicqauletwehcihncihqrueeqsusihreosulgdrbaetevaolridsaitgendiffoirceanatclhy girnedaitveirdoupaelrlatoorrokpiollytmhearn botehienrgsalniastleydzheedref.or 1 20