Document x5vmbQrka4xwD6jyRz161ZXbm

BACK TO MAIN 3M E ~ O ~ ~ ~ ~ A L L A B O R A T O R Y Author: Kristrm J. Hauscn/Harold 0.Johnson Revision Date: BACK TO MAIN 1.0 scoplGAM)mLIcATIm ~ I.1 Thismethodprovides collection,extrdm, and anal*& pmcdurai for the dekmhationOfPurfluomoctme~sulfbaate(PFOS), PedhmooctaneSulfbnylamida (PFOSA), and Pd-ate POAA) in groundwata; sarfacewater, and drinking water samples. 1.2 This methodwas prepared accding to the EPA document, ''Guidelines and Fonmat fbr Methodsto be Proposedat 40 CFRPart 136 or Part 141" (see Rcfkrcncc 1 8 ~a)nd~is based inpart on thereport Wethodof Analysis fbrtheDetmnhation of P a r f l u o m ~ ~ ~ ~ o sulfbnate(PFOS), PcrfluoroocEanesulfbnylamidc(PFOSA), ami Pcrfhmm-b (POM)inWater"(set Refcrcpcc;18.2). 2.0 2.1 . 3.0 D~pmnrro~s 3.1 33 33 3.4 MS Word 97 m154.0 Dettrminatio~Of PFOS, PMISA, POAA in Wadaby Liquid-W Page 2 of 17 md LCMSIMS BACK TO MAIN 3.5 3.6 3.7 3.8 39 3.10 3.11 3.12 Msword97 BIS-8-154.0 Page3of17 DetfflllintionofPFOS,PFOSA, POAA in Waterby Liquid-SoM ExtraclionandLc/Ms/Ms BACK TO MAIN 3.13 3.14 3.15 3.16 3.17 3.18 4.0 WARNWSANDCAUITONS 4.1 Health and Safety Wvntnga 4.1.1 The acute andchronictoxicity ofthe standards farthismcthodhavenot been precisely ddcrminad;howevm, eachshouldbe treated as apotcntial health hazad 4.13 Unknown samplea may coafaiohigh wncatmh'om ofvolatiletoxiccxmqounds. Sample umtainem &oddbe opcncdin a hoodandhandled with glove8 to . . . 4.13 Tpirmolvaebanrattgatrpyios~rc*spondile firmambmmg a safework eavironmcpt mda . CWTUlt 8- Of ~ ~ O IreglardSiag t h t u Of&8 C h d & usedin thismethod. A refhcwe61e ofmateriald e t y data sheets (MSDS) shouldbe availableto allpersonnel irrvohrodmthcscanalyses. 5.0 ~ C E S BACK TO MAIN No* Brand names, suppliers,and part numbas are forillustrativepurposesonly. Equivalent ~ m m a n cmc y be achicvtdusingapparatusandmatcfials other thanthasespecified hac, but dcmanstratiaatofequivdcatpufommcetbgtmetts thertquiranmcs of tEdsmethzrdia the lrsponsibilityofthe iabaaatory, 6.1 SPmpUneEqafpment. . 6.1.1 Sample collectianbotth-LDPE (e.&, Nalgene`y)mmw-muth bottleswith saww cap* Note: Do not use Tcflm bottles or Teflon lined capti. 6.13 Coole~fsbr sample shipment. 6.13 Icefbr~leshipment. . 6.14 B o t h mustbe lot-certified tobe h e of dfhetsbyrutmingMetbadblanks accardingtothismcthd -. 6.2 .LaborntoyEquipment(Extraction andAnalybkrl) 6.2.1 Balance, analytical(display at least O.OOOlg), Mettk. 6.23 Vacuum pump, BiIcbi. 6.2.3 V i s i p r q p ~ m a n i f b l dS,upelm. 6.2.4 Sep Pak Vac 6cc (lg) cartridges opsrt # WAT 036795),Waters, 6.2.5 5onrLdisposablepolypmpylenecaatrifngetubes,vwR. 63.6 15mLaispOsablcplyppylcnecentrifhgc tubes, VWR. 6.2.7 ~spo~lemicropipctt(e5s0-100crL, 1W200@), Dnumnond. 6.2.8 Chss A pipcttaandvolumetric flasks,Various. 6.29 Hypacarb drapinguard column(4mm) @art ## 844017-400), Keystone. 62.10 Stand-alone dropin guard carhide holder, Keysta~. 6.211 125mLLDPE n8rrow-mouthbottles,Nalgcnc. 6212 Hpu:pump (LCIOAD), slimadm 6.2.13 2mLclearHPW vialkit (cat# 5181-3400), HcwIett Packa;rd. 62.14 Standard lab equipment ($raduatedcylinders,disposable tubes, atc.), vaxiow. 6.2.15 Lc(MsM[s andHpLc systems,asdcscrii in section 10.1. 6.3 EquQmentNotes 63.1 In orderto maidGO- ' `on,the usc of diqosable labware ishim ncommended (tubes, PipcCtGs, &.). 6.33 Teflonor Teflon-linedcontainemor equipment,including Teaan-liasdHPLC vials or caps fbr theHPLC auto sampiermustnot be used 6.33 Type Iwater uwd drning the sample andstandad extmckm should be^ Wugha Kypercarb guardcohmmtlfiinna,HPLCpump. Thir,w a t e o h d d t o as "filteredtypeI w,hereafter in thisq o r t 6.3.4 Itisncccssaqto check fhesolvents (methanol) for thepresence ofumtambW (especially POAA)by Lc(Ms/Ms prior touse. Certainlot numbershavebeapD f;Mtndtobe unsuitablt fix use. 63.5 Use disposablemicropipettesorpipettes to aliquot rtanrfanl solution^ to maka Cah`ibrationstannarAnandmatrixSpikes. BACK TO MAIN NO* Supplias pad crrtafognumbasarc fai I l U s t r a t i v c 7 only. Equivalentpesfarmanoe m r y b achievedusingchemicals obtaiocd from othersupplias.Do notuse a lesser grade of Chemicelthrnthcwrtlistod. 7.1 Chemkab 7.1.1 Methanal (McOH), HPLC grade, JTBaker, catalogNo.rrsK)93-2. 7.1% AmmomumAceta& matgrade, Sigma-AldriCh,CatalogNo.A-7330. 7.1.3 Wata, type I, prepared ia-housc. 7.1.4 Sodimn'Rkt~&@Rerrgant g~&, JTBakar. 7.2 Standud0 7.2.1 PotassiMl pdu-e salfanate (see At- A, F@c 1). 7.23 Pufluomoctane&mylami& (seeA t t a c M A, Figure 2). 7.2.3 AmmoIliumparfluoraactanoate(sceAttachmmtA, Figure 3). 73 Reagent Preparation 7.3.1 250mghL sodium tbioslllbte solution (lve 25g of wdium . thiofml.&3inloomLnagcat~. 73.2 40% methand@ x t r a c t i o n w m 4OOmLmethanol and ad!!& the volume to 1.0Lwith reagentwater. 7 3 3 loomM ammoniumaceta& solution (Andyds)---Weigh 7.71g ofammonium acetate anddissolvem 1.OL of reagent water. Dilute the lOOmM aohrtionby a factbrof 50 to mrrLe the- ammonhn acetate solation used fbrmobilephase A . . Nota: Altcmative~olmesmaybe preparadas long as thtratios of the solventbsoluteratios Bltmsmtpmdd 7.4 spudng stock standard (SSS) Preplurtfon - 7.4.1 l-g/mL each PFOS, PFOSA,andPOAA SSb-WUgh out lolng of analyticalstandard (coxrectedfixpercent salt and @ty---i-a, IOmg c;F,#JC purityW! 8.35mg C,F,,S03-) and dilute to loomtwith methanol in a lOOmL volumelric aask.Traasfbrto a I25mL LDPEbottle. ]preparca sep'St8 80lutian foreach anal*. Storesaluticmt~in 8 refiigeraforat 4OeoCfor amaximum periodof 6 monthsfrom thc dateofpreparation. 7.43 1pplmL miredSSS-Add 1.0mL eachofthe loO@mL SSSs ( h m7.4.1) to a lOOmLvolumctziuflsskandbringupto~l~witbme?hanol. 7.43 O.ICce/mL miredSSS-Adti 1 0 . M of the l . O p ~ m i x o dution (hm 7.44 to a loomLvolumetric flask andbringup tovolume withmethanol. 7.4.4 O . O l j a g h ~ Lmfu?dsss-Add 10.omL of the O.lp@mL-mixcd solution (&om 7.4.3) to a 10QmL volumetric flask andbring up to volumewith matbanol. 7.45 StorageCondtffollkstoreall SSSs in a &gerabr in 125mLLDPEbottlm at 4*&2OCfor amoudmumperiod of 3 moILfhsfhm the date ofprcpadOZL MSWd97 BTS-8-154.0 Pago 6 of 17 Dc' * tionof PFOS, PFOSA, POAAinWater by Liqnid-SoiidExtraction and LCMSMS BACK TO MAIN 7 5 Calibration Standrurds 7.5.1 lOOpg/mL each PeOS, PFOSA, and POAA stock standard solutions-Wei@ oat lomg of analyticalstandard (corractadfmpercmt salt andpurity) snd dilute to lOOmL with methlllpof in a loomCvolumetric flask.Transfa to a 125mL LDPEbottle,Preparea separate solutionfor eachm e . Stom solutions in a r&igerat0rat4~~f~oCr amaximumpcriodof 6 monthsfrom the dateof P=P-iO= 7.5.2 lpg/mL Working Standard-Add 1.Meach of tbe 1 0 i ) p S~S solutiom (hm7.5.1) to a -1 volumetricflaskandbring up tovolumowith mahanol. 7.53 O.lpg/mLWorking Standard-Add 1 O . W ofthe 1.OpS/mLmixedsolution (from 7.5.2)to a 1OoniL volumetricflask andbring up tovolume with methanol. 73.4 O.Olpg/mL Working Standard -Add 10.- of the O.l&mL mixedsolution (&om 7.53)to a -1 vohunetric flask and bring up tovolumewith msthaool. 7.55 StorageConditions-Store all WSI inarcfkigcmtcx (ii125mLLDPB bottles) at 4OaoCfir ammimumperiodof3 months from the date ofInaparation. 75.6 Calibration Standard-Prepan axin.hutnof five calibretionsolutionsin filtaedtype1water accord@* thc fbllowingtable: Concenhtb ofWS,CrgEmC 0.0 0.010 0.010 0.010 0.10 Volume of WSsIrL 0 100 200 400 100 Fhul CalibrationStaadard volamc, mL 40 40 40 40 40 ___ ppnol Concentrationof CrrltbrotionstUdud,Pg;lmL 0 25 50 100 250 Nota: The absolutcvolurncsof the rtandrwlsmybe varied by the analyst as long as the u n m t plaportiaasof solutetosolvent am maimina 7.5.7 Thastmdmis am processedthroughthe extractonproced.laa (Section 9.0), identical to the laborstorysamples. The extrpcted conax&&'onofthe c a l i i o n standard is -to 8 ~ t h e i n .coin~ccntrition,dueto the-oc *onof tb staadard during thecxlmctionprocess. 73.8 Storage Conditiom-Ston all extractedcalibratcm standards m 15mL potypropylmetubes at 4OaoC, fixamaximumperiod oftwo we& fiam the date of preparatioa Ms Word97 Elrs-8154.0 P q e 7 of 17 BACK TO MAIN w, Note: Samplingequipment, including autosuticsamplas, mustbe firee ofTeflontubing, othap8rts that snay leach intcdkrkg Pnasytesinto the water sample.Automatic 8 a m ~ thhat composite gamPIts over time shoulduserefrigeratedp o l ~ l e nseample ~~ifp4881~~.~le~~ahwldnot~tinsadbcf.bresrrmplcco~octi~ 8.1 Tap Wltm-OpuI the tap and allow the system to flushuntil the water tunpemtm (15*100C) bas stabilized (uually about two minutes). Adjust the flow to abaut - 5 ' aad collect samples &om the flowingstrcam. 8.2 Ground WabP-hrge the well of standingwater usbga pmap or a bailer. Collect the sample directlyfromtbcpump of ibm the baikr. 83 SarfrceW~~~~linnfiromanopcnbodyofwater,611the~le~~~ with watez fromarcprescatativc area 8.4 sampleDechlorination-AU samples shouldbe iced or rcfrigcrated-at 4Oe0Candkept h thadark fromthe time of collcctimuntil axtractiOn.Residual chlorineshouldbe nducadby adding 200pLof a 25om;BknL d m thiosulfate solutionto each water . vie, FB,and FSCS (which may be pIaccd ineachbottlebefore leavingibr the sampling sib). 8 5 Holdhg Time (HT)--Results ofthetimdstoragestudyof all tax-@ aaelytcs showad that the tbra compounds are stable far 14 days in wafer samples when the samples am ddorinatbd and stored as describedin section 8.4 (see also rdimnce 18.3). Thereflaboratorysamplesmust be cxtracttdwithin 14 days andtheatracta aualyzcdwitbin 30 days of sample collection. Ifthe HT exceeds 14 days, great care is u86d when evaluating field spikes to avoid misrepresentation of the sample concentration. 8.6 Field Blanks 8.6.1 * Process a Field Blank Control Sample(FB) dcmgwith tach sample set (smplcs collected fiam the same g e n d sample site at appmximatdythe Sam0 time). At the labowtory, prior to sample callaction, fEll a sample container with filtered type I water, seal, end ship tha FB to the sampling site dong with the empty mnpb containem. Returnthe FB tothe with the filladSUU$~ bottle. 8.63 When sodiumthiorrulfate is addedto sampb, wcthe pFocadure to ~ ~ O S W them. 8.7 FieldDuplicrrks 87.1 Collect a Field Duplicate (FD) for every ten(10) 8funpL~sCoIlScted per each sampling set, iflessthan 10stamplcsare collected. 8.7.2 separateF D s must be oo~ectcdfor eachtypa ofwater sample (groud, tap, etc.) collect4d. 8.7.3 Collect the FD knmaaiatcly after the sample. 8.7.4 Preserve, store and shipFD usingthesamepmcdumsas used fbrthe -1- BACK TO MAIN 8.8 Field Spke ControlSmpk (FSCS) 8.8.1 A Field Spike coatrol Sample (FSCS) must be prepared fbr each sample shipment Ifmultiple coolm amusedto ship a set of samples, each cooler must contain aFSCS. 8.8.2 At the l a b o m , fiIl a samplecmntsinCrwith loOmt of t y p I water. Seal and shiptotbe~ling~~alaagwitbtheemptysamplecon~aadFBs. 8.83 When sodiumthiodfbte is added to samples, use the m eproctdure to add the same a I n O w 8 to the FSCS. a&4 Sed andpffy invat the bm k Storeand theF S a wing the same proceduns 88 uscd farthe samples. Msword97 BTS-8-154.0 pIoe 9 of 17 Detannination ofPPOS, PFOSA, P O MinWater byLiq&Solid Extradon andLc/Ms/MS BACK TO MAIN 9.13.1 9.1392 9.1.93 933A 9.1.93 PgtmL, Follow the extractioa scheme as outlincd fbrn steps 9.1.1 to 9.1.6, except, collect the eluateW o n separately(qprox..SmL), as well as the tar- elution 6iaction. After step 9.1.6, collectapost-elutiOn fiactcmby, elutingsf;th an additional5mL of lW?methanol. AnalyzeallthrccM o n s by HpLc/Ms/Ms. Ifthe target hetion contains aminimumof 85% of therespactiveaualytcs, it maybo . CoDSidcntd acceptable. Iftzw:washcontannssignificautstandad (>IS%), either them hvolume orpcrcdap ofMdlH ahorrld be dccmscd. I f b post-dution&action conbins-@is standard (XS%), the elution volume should be increasad h4SWd97 ms-8-154.0 h g a 10of 17 . . Dcmmmamof PFOS, PFOSA,p o MinWaterby Lipid-SolidExbnctianmadfMMsIMsi BACK TO MAIN HPLC Gradtent Program: Time, . Percent Mobile mfn Phue A - - 0.0 60 0.4 60 1.o 10 7.0 10 75 ' 0 9.0 0 95 60 13.5 60 14.0 60 Perant Mobile Phue B 40 40 90 90 100 100 . 40 40 40 Flow Rate, mumtn 0.3 0.3 0.3 0.3 0.3 0.4 . 0.4 0.4 0.3 MSWnrd97 EIs-8-154.0 Pylc 11of17 Detambfion ofPFOS, PFOSA, POM inWaterby Liquidsolid ExfmctimandLcmds/Ms BACK TO MAIN Ions Monitored: POAA ' 413.0 169.0 5.0 PFOS 499.0 99.0 52 PNSA 498.0 78.0 5.8 Otherprodactions may be chosen at thediscretionofthe analvsf althoughm/z 99 issuggested for PFOS. Use ofthe suggestedprimary ion is rax&muniul. Retention t&s mayvsry slightly, onaday-today basis, depending on thebatch of mobilephase etc.Drift mmentiontimais acccptablcwithinanana2yticalnm, as long as the drift continuesthrough the cntbmalysis and the standadsam intwspasedthrou~uthte analyticalxun. ' . 10.2 TmeFfleParameters 10.2.1 The followingvalues areprovided as an axample.Act& values mayvary from instrumatto ixxmmmt Also, theseduesmaybe changed &om time to timem order to optimize ftx gmtcst sensitivity. I Dwd&rrec ~ POM 0.2-0.4 PFOS 0.244 PFOSA 0.2-0.4 Collision Energy, eV 10-25 3060 20-50 Cone, V 20-30 50-80 3040 capillrny Hcacapola 1 -1 Haxapole 2 SouxceBloclc Tanp. Desolvation Temp. 2.56-3.5kV 0.N 0.2v 0.8V 100-15OOc 250-400"C LhdRcs1 HMRSSI IEakagy1 Entrance Exit 12.0-15.OV 12.0-15.OV 0.m -2v 1v . 11.ov ll.0V BACK TO MAIN prwmrec Gas cell set 3.ob3mbar 11.0 ANALYTICAQLUALITY CONTROL 11.1 Analyticalresultsof the FB,EMS,FD,i d FSCS shouldbe evaiuatedat the conclusion ofthe study to help interpretthe dataquality ofsamplesdata Aaalytical rermlta for these amt~~Vd~~~icatesamplesmustberaportcdwiththesdilnpledata BACK TO MAIN -- 12.1 SampleAnalyris 12.1.1 sct up amlysis sample queue. 12.13 &jmt tha m c aliquot (between5-25pL)of eachstaadard,analyticalsample, =very, controletc. intothe tciIMsNssystem. 12.13 All mmples showing aregponse fixone ormom analytm b v o the reqcmsa of thehighest,active calr'brationcufv~level mustbe diluted end read- . 123 CaUbratfonCurve 13.0 DATA ANALYSIS AND CALULA"IONS 133 calcntatethe percentrecoveryof the MSsusingthe following equation: BACK TO MAIN 14.0 METHOD PERFORMANCE PARAMI&TERS Note Aaymethodperfh~~~~parametersthantrortraechicvcdmustbeumsidaed m&e Ml~andthcdataN~~toanyspecifiedparametasrrmstbcdcscn"lwd9nd discus& in trry rcpadngof the dah 1481 Und+Lbearstmdard curvesfbrqUantitatiOngcncrat4fortach analytoby linear regression with l/x weightingof peak area VCGPUScalibratioc standard concentration. Tho cornlationd u c a t (r) fin the c a l i i n curves must be 20.990 (?20.980), 14.2 Calibration Curvc'Stnndrudr--Themeasuredvalue for fach CUTVC point must be Within f 30?! oft h d c a l valueswhencurveisevaluatedover amge approPriatetothc data. Highor low points maybe deactivatedto achievethestcriteria, but `anacccisfablccurve must containat least fiveactivecurvepoints. 143 ccv PerforInmce-Mid and low level Caliim checks tobe analyzedritary 5-10 injections. The analyte level m d inthe CCVSShOuM be within f 30% ofthemetical values. IfCCVs f&ll butsideof thisrange, data collectedmbscquenttothe bt passing CCV shouldnot be used. onlydata coaectedbetween acceptableCCVscanbe used. I484 Limit of Detectfon (LOD)=Tb lowest calibrationstandadwith a peak areaat le& 2X the peak areaof the exhetion bfank tbatcanbe measuradat aconccntrationgreatar than ZCTO. - 1445 LtmlQ of Quanthtion@,01Q)--ThalowerLOQ 0isthe lowastnon-zero active s t d a d inthe calibration curve; the peak a f c o~fthe UOQmust be at i d 2X that of the Gxtractianblarrk.By definition,the mearmredvatat ofthe LLOQmustbe within 30?A of the &coretical value. 14.6 M a ~ S ~ ~ ~ ~ s p i k t p e r c m t T e c o v a i t s m u s t b c w i t h i n f 3 ~ o f ~ s p i k e d C0nc-m. Id7 Solvrnt Blanks, Method Blanks, and MItrix BInnlrp-Vduesmust be below the lowest non-mactive~taadardmthe calibrationm e . Matrix blaqke arc considered compbnt ifm test substanceis detected above the LOD for that anafyte. 14.8 Ilnprodadbillty-Reproducibjlity ofae method isdefinedby the resultsofthematrix spikesandmatrix spikeduplicatas.Tbt MS/MSD ahouldbe mw%Ieto Within20?A 1 4 3 Use of ConfirmatmyMethocls--None 14.10 Demonstration ofSpedficity-SpuScity is demonstratedby chromatographic retcntkm time (within3% of stadad) andthenvss s p a c t r a l n % p o~f~ produd imgencrattdhmach;practcnst*!cprhnaryian. . 14.11 Documeutation 14.11.1 Sfcritcdia listed in tbis method parfmmancc section are not met, mainfcnwrcs maybepcrfbmedon the system and samplc~mdyzedo,r other actionstaken as determu* & by the analyst Document all actionsin the appropriatelogbook. 14.133 Ifdata arc to be reportedwhen @ m w critfrk havenotbeenmet,the data mitst be fbotnoted on tsblw and discussed in the text of the repork MsWd97 BT6-8454.0 P w 15 of 17 D e t u d W hof PFOS, PFOSA, P O M in Water by L@d-Solid Bxtnctioa andLctMsIMs BACK TO MAIN 19.0 l&vIsIoNs Revision Number. Rtason For Revision Ravision * D BACK TO MAIN 0 PFOS Note: Stamids memade &omthe salt, potassiumperflrorooctrneputfonata[CgF17SO3q, mhv 538. . Figure2 PFOSA ChemidName * Molecular ion' = . PcdwmesulfonyIamidc 498(c;FnS02Mt) PFOSA Figure 3: POAA ChCmicalNamc = Molecular ion P~rooctanoat! 413(GF1sC003 C7F&OPOAA