Document emDGBV0m1z1D4jz1m4b0en7gg

3M ENVIRONMENTAL LABORATORY METHOD ANALFYLSUIOSROOFCPHOETMAISCSAILUCMOPMEPROFULNUODRSOIONCUTRAINNEESEUXLTFROANCATTSE UOSRIONTGHER HPLC-ELECTROSPRAY/MASS SPECTROMETRY/MASS SPECTROMETRY Method Number: ETS-8.97.0 Adoption Date: F-2B-49 Author: Lisa Clemen, Robert Wynne, GlennLangenburg Approved By: 7 /3. Laboratory Manager filer Ho Group Leader on Aline Technical Reviewer Revision Date: NJ x Ys fos Date al) Date Hazlas Date LOScorpanpAveuieamoy 0000000000000 1.1 HSPcLoCp-ee:leTchtirsomspertahyo/dmadessscrsipbecetsrtohmeetarnya.lysisofurine extracts for fluorochemicalsusing 1.2 Applicable Compounds: Fluorochemicals or `other ionizable compounds. 1.3 rMeaptorrit.ces: Human, rat, and `monkey urine, or other fluids as designated in the validation Word 6/95 AnlysisofUrEnTsS-E8x-9a7c.t0USsg SMS 001.05.9 Page 10f 10 2.0 SUMMARY OF METHOD 2.1 TushiinsgmHePtLhCo-deldeecstcrriobsepsrathye/maansalsysspisecotfrofmleutorryo,choermsiicmaillsarexstyrsatcteemdafsraopmpruorpirinaetoer. otThheer fluids, afnlauloyrsoicsheimsipcearlf,osrumcehd absytmheonpietrofrliunogroaocstianngleesuilofnoncahtaera(ctPeFrOisSt)icaonfioan,pamr/tzic=ul4a9r9. tAhdediitdieonntailtlyyo, fsaamcpolmepsomuanyd be by analyzed detecting udsaiungghtaetrainodnesomfmatshes psapreecnttroiomne.ter to further verify 3.0 DEFINITIONS 3.1 Atmospheric systems allow PfroersvsaurrioeuIsomneiztahtoidosnof(iAoPnIi):zaTthieonMbiycruotimlaiszisngQuvaatrtiroousIlsotruirpcleesq,upardorbueps,olaend Pinrteesrsfuarceesc.heTmhiecsaeliInocnliuzdaetibount(aArPecln)o,t Tlihmeirtmeodstpo:raEyl,ecettcr.ospTrhaey iIoonniizzaattiioonnp(rEoScIe)s,sAitnmtohsepsheeric techniques occurs at atmospheric pressure (i.c., not under a vacuum). 3.2 pErleescsturreo,spwrhaeyreIobnyiziaotnisoinn(sEoSlu,tEioSnI)a:reatmreantshfoedrroefdiotnoitzhaetgiaosnpphearsfeorvimaedtiantyacthmaorsgpehderdircoplets. These charged droplets are produced by the applicationofastrong electrical field. 3.3 `MTahessAPSIpeQcutartotmreoItryt,riMplaesqsuaSdpreucptorloemmeatsesr (spMeSc)t,roTmaetnedreims eMqausipspSedpewcittrhotmweoteqrua(dMrSu/pMolSe): `cmhaasrsgeserlaetcitoi(vem/dze)teacntdorssuabnsedqauecnotllliysidoenteccetlel.d.ToAnssianrgelseeMleSctimvaelyybdeisecmrpimlionyaetdedfobryimoanss to daentdectthieosne ofrraagnmieonntsmmaayybebesealneacltyezdeidnitnhethfeirssetcqounaddrquupaodlreu,poflrea.gmented in the collision cell, 3.4 tCroinplveeqnutaidornuaplolvse.sZy-sstpermsay(pporsotb1e99i8n)teurtfialciez:e aT"hZe-slaptreasyt"mocodneflosromfatiMoinc.roTmhaessspQruaayttermoitIIted dfirroemctalpyraotbteheiscoonrethaopgeorntaurlet,oatfhteecpoansesianpgertthurreo.ugIhnathteorctounovuesnptaitonhawlaycoinnftohremactouinotneirt is aimed. emlaeicnttreodnea.ncTehaoruegthhethseamceo.nfiHgouwreatvieorn,iZs-dsipffrearyencto,mtphoenmeentthsoadnsdofcoonpveernattiioonn,alclceoamnpinogn,enantds are ncootmpcaotmipbalteiwbiltehwistohmoenoethaenrotZh-esrp,rbauytsoynsltyemwsi,thetsc.i)milar systems (i.e., Z-spray components are 3.5 MIIatsrisplLeyqnuxadSroufptowlaersey:stSemyss.teCmursroefnttwlayreMdaesssiLgynendxfhoarsthWeisnpdecoiwfiscNoTpe4r.a0tvieornsoifontsh.esFeoQrumaottrreo details see MassLynx the NT manual User's specific Guide) to the instrument (Micromass Quattro II triple quadrupole 4.0 WARNINGS AND CAUTIONS 41 Health and Safety Warnings: 4.11 eUmspelcoayustiaonvowlittahgetohfe vaoplptraogxeicmaabtleelsyf5o0r0t0heVporlosb.e. When engaged, the probe Analysis ofUriEnTeSE8x9t7ra.c0t Using ESMS 001060 Page 20110 4.1.2 aWnhdecnlohtahnidngl.ing samples or solvents wear appropriate protective gloves, eyewear, 42 Cautions: 4.2.1 Oprpeesrsautree tehxecesoeldvsen4t00pubmarp,sthbeeHloPw11ab0a0cwkilplreinsistuiraeteoafu4t0om0abtairc (sSh8u0t0dopwsin).. Ifthe back 4.22 Do not run solvent pumps to dryness. 5.0 INTERFERENCES 5.1 Tstoormaigneiomrizaenyinptaerrtofferiennsctersuwmhenetnataniaolnytzhiantgcsoammeplseisn,ctoenftlaocntswhiotuhldthneotsabmepulseeodrfeoxrtsraacmtple 6.0 EQuipment 6.1 mEoqduiifpimceatnitonlisstiendtbheelroawwmdaatyabaes mmoedtihfoideddeivnioatridoenrs.to optimize the system. Document any. 6.1.1 MelieccrtoromsapsrsayQiuoantitzraotiIoIntrsiopulreceq:uadrupole Mass Spectrometer equipped with an 6.12 HcoPm1p1a0rt0mleontw,pualnsdeasuotlovseanmtppluemrping system, solvent degasser, column 7.0 SUPPLIES AND MATERIALS 7.1 Supplies 7.11 High purity grade nitrogen regulated to approximately 100psi. (House ar system) 7.12 High purity grade argon regulated to approximately 6 psi. 7.13 iHnPtLheCraanwaldyattiac.al column, specifics to be determined by the analyst and documented 7.1.4 Capped autovials or capped 15mLcentrifuge tubes 8.0 REAGENTS AND STANDARDS. 81 Reagents 8.1.1 Methanol, HPLC grade or equivalent 8.1.2 Mtyipleli|,-oQrTMewqautivearle(nAt,STanMdtmyapey)b,eapllrowvaitdeerdubsyedaiMnitlhliis-mQeTtOhoCdPslhuosulsdysbteemAoSrToMther vendor 813 Ammonium acetate, reagentgradeor equivalent 8.1.3.1 When preparing different amounts than those listed, adjust accordingly. 8.132 2a.m0mmonMiuammmaocentiatue.mPaoceutratientsoolaut2i0o0n:0 mWeLivgohluampeptrroixcimcaotnetlayin0e.r3c0o0ntgaining 2000 mL Milli-QTM temperature, water, mix until all solids are dissolved. Store at room Analysis ofUriEnTeS.E8xt9r7a.c0t Using ESMS Page 3010 001061 82 Standards 8.2.1 pTryeppiacraeldlydturwiongmetthheoedxtbrlaacntkiso,n tprwoocemdautrrei.x bSleaenkEsT,Sa-n8d-9t6w.e0n.ty matrix standards are 9.0 SAMPLE HANDLING 9-1 aFrreesshtomraetdriinxcsatpapndeadradustaoveiaplrseoprarceadppweitdh1c5acmhLancaelnytsriisf.ugEextturbaecsteudntsitlaanndaalrydssisa,nd samples 9:2 aIfpapnraolxyismiastewillyl4beCd,eloaryeatd,roexotmratcetmepdersattaunrdea,rdusntainldansaalmypsliesscacnanbebeperrefforrigmeerda.ted at osQuanvconrer, 10.1 Solvent Blanks, Method Blanks and Matrix Blanks 10.1.1 eSaoclhvebnattbclhatnoksd,etmeertmhionde bcloanntkasmiannadtimoantroirxcbalrraynokvsera.re prepared and analyzed with 10.1.2 cAunravley.ze a solvent blank, method blank, and matrix blankpriorto each calibration 10.2 Matrix Spikes 10.2.1 Mreactorviexrsypeifkfeiscairenecpyr.epared and analyzed to determine the matrix effect on the 102.2 rMeactorviexrsypfiokreedaucphliacnaatleystea.re prepared and analyzed to measure the precision and the. 102.3 mAnianliymzuemaofm2atrsipxiskpeiskpeearnbdatmcaht.rix spike duplicate per forty samples, with a 10.2.4 tMhaetriinixtisaplickaeliabnrdatmiaontrciuxrvsep.ikAeddduiptliiocnaatle scpoinkceenctornacteinotnrsatwiiolnlsamllaiyntfahlelmiindt-hrealnogwe-of rangeofthe initia calibration curve. 103 Continuing Calibration Verifications 103.1 oCfotnhteincuailnigbrcaatliiobnrcautirovne.verifications are analyzed to verify the continued accuracy 103.2 oAfnoanlyezpeear bmaitdc-hr.ange calibration standard after every tenth sample, with a minimum 11.0 CALIBRATION AND STANDARDIZATION 11.1 waAevniearglahygtzeeeodfth1t/ewx,eoxntosrttaacfntoderadcremddactturhrirvxoeussgtahwinzldelarrbod,eswppilrotithotreIdStobraeyfnredergefrnoeclselso(iwsoiunnrg(rioegnaacctahersieosrtuoostfehdeexratwsriasacent,si.snteTeerhn1ea1l.2), standard) using MassLynx or other suitable software. Avalysis ofUriEnTeS-E8.x97c.0Using BMS (09 06:2 Page dof 10 11:2 Use the following parameters for determining a calibration curve for each compound: [rw roos a Joe ) aSduidtraebsisleitdyboyftchuervaenaflyistti.ng parameters for other Ruorochemical compounds willbe 11.3 Isfttahnedacrudrcvuerdvoe(cisfnnoetcmeseseatryr)eqaunidrermeeanntasl,yzpee.rform routine maintenance or reextract the 114 FuEsxoearmtpphulerepl:ooswwesehonefdnoafacttcthueermapcctayilniwgbhrtaeotniqouqnauncatnuitrtivatetaetriaantpghperlrootxwhialmneavtteehllesoyffu5la0lnarplapynbtgeeo,fofiatntamhlaeytyset,baegnednnaeercrdeasstsuearraey.to rrceaaglnrigebersasotifiootnnhwececuiurgvrhevteicno(ng2os5ifsphtpiibnggthoofc1to0nh0ce0enspttpraban)t.diaorTndhssitfsarnwodiamlrld2sr5.epdupcbetion2a5c0cuprpabcyraattthreirbtutheadn ttohelifnuelalr 12.0 ProcEpuRES 121 Acquisition Set up eee 12.1.1 Set up the sample list. 12.1.1.1 iAnscsriegansiangsalmetptlereolfstthfeilalepnhaambeeutssitnagrtMiOng-DwiAtYh-alast two digitsof year- 12.1.1.2 121.13 Assign a method Assignan HPLC (MS file) for acquiring program (Inlet file) 12.114 Type in sample descriptions and vial position numbers 12.1.2 RTsepoaecccttrieraootmneeMtaoemnreihtteoharodidnignc)gl.sicaSknedotnIseomlneeitczthatoSidIoRninM(StoihdnegeAlceaqsluoianspipRtreiocoponrricdaoitnentgar)onldorpmaManseRlsMtthoe(4nM9um9latosirsploether afacrpqapugriomspeirntitiaaottneimomenatsihsnoefdso..rmaAIftiMfouSlnl/msMacSaynbiinessuctosrluulameleclntytesdc.oalrlReeeceftmeeprdltoaolyoMenidg,crwaoidmtdhiatstishoenMaSalIsRpssrL.oyduSncaxtvefon GUIDE TO DATA ACQUISITION for additional information and MRM. 12.13 `Tmyaptirciaxlsltyantdhaeradnsa.lytical batch run sequence begins and ends with a setof extracted 12.14 aStneaanmtlphyltseeasmcpaalrrere.yaonvSaeolrlyvazenenddtawbriletahnnokatsccsoohnnotsuiilnddueirbneegdacsanalaimlbpyrlzaeetsdiobpnuevrteimroidafiyiccabalteliyointnocilnmujodenceitdteo2drsapsfuotcsrhs,iebvleery 12.2 Using the Autosampler 12.2.1 Set up sample tray according to the sample list prepared in Section 12.1.1. Analysis ofUriEnTeSE8xt9r7ac0t Using ESIMS 001063Page sof 10 12.2.2 ment logbook Set-up the HP1 100/autosampler at the following conditions or at conditions the analyst considers appropriate for optimal response. Record actual conditions inthe 12.2.2.1 Sample size = 10 uL injection 12.2.2.2 Inject/sample = | 12.2.2.3 Cycletime = 9.0 minutes 12.2.2.4 Solvent ramp = Time MeOH 2.0mM [7 oECoEm | awe |a`Ammooniunm ace]tate [CsEmn 9557% T-- s-- o Comin |awe |aon 12.2.2.5 Press the "Start" button. 12.3 Instrument Set-up 12.3.1 TRreifpelretQouEaTdSr-u9p-o2l4e.0M,as"sOpSepreacttiroonmaentderMFaiitnttedenwaintcheoanftAhtmeoMsipchreroimcasPsreQsusautrtero II Ionization Source," for more details. 12.3.2 Check the solvent level in reservoirs and refillif necessary. 12.3.3 Cthheetcipk. thTehsetatiipnlsehssousltdeeblecafplaitllwairtyhant othjeagegneddoeftdhgees.proIbfet.heUtsipeiasnfeoyuenpdietcoebteo check unsatisfactory, disassemble the probe and replace the stainless steel capillary. 12.3.4 Tum on the nitrogen. 12.3.5 Ohepaetenrst.he tune page. Click on `operate to initiate source block and desolvation 12.3.6 Open the Inlet Editor. 12.3.6.1 Set HPLC pump to "On" 12.3.6.2 Set the flow to 10 - 500 uL/minoras appropriate 12.3.6.3 Observe expelled droplets coming outof the tipof the with no nitrogen leaking around the probe. A fine mist should tipof the probe. Readjust be the tipof the probeifno mist is observed 12.3.6.4 Allow to equilibrate for `approximately 10 minutes. 12.3.7 The instrument uses these parameters at the following settings. These settings may change in order to optimize theTesponse: 12.3.7.1 Drying gas 250-400 liters/hour AvisofUEtresausnno Using BSS Paesotio 001064 12.3.7.2 ESInebulizinggas 10-15 liters/hour 12.3.7.3 HPLC constant flow mode, flow rate 10 - 500 uL/min 12.3.7.4 Pressure HPLC is <op4e0r0atbianrg(cTohrirsecptalyr.a)meter is not set, it is a guide to ensure the 123.7.5 Source block temperature 150 12.3.7.6 Desolvation temperature 250 12.3.8 Ptraipnetdtihnetotutnhee piangset,ruwmietnhtiltosgp.arameters, and store it in the study binder with a copy 12.3.9 `CMelanidscsskLaomynpnlxsetavrnetrusbmiubotentsro,nirniencfleturhdeteosAcaaqplulpirssoaipmtrpiilaotenesCMotoantsbrseoLlaynPanalxnyezUelsde.(rth'issGmuaidyev)a.ryEansmuornegstart and 13.0 DATA ANALYSIS AND CALCULATIONS 13.1 Calculations: 13.1.4 Calculate matrix spike percent recoveries using the following equation: %Recovery= Observed Result -Background Result x 100 Expected Result 13.15 Calculate percent difference using the following equation: . % Difference = Expected CoEnxcp.ec-tCeadlcCuolnact.ed Cone, x 100 13.1.6 Calculate actual concentration of PFOS, or other fluorochemical, in matrix (ng/mL): (ng/mL ofPFO cale. Initial from std. Curve x Volumeof matrix Dilution (mL) Factor) x 1 ug 1000 ng Final Volume (mL) 14.0 METHOD PERFORMANCE 14.1. MmMaeDttrLhioxadsnpdDeecLtiefOiccQt.iovPnallLeuiaessm.eitse(eMEDTLS)-8a-n9d6.L0i,miAttotfacQuhamnetnittatBi,ofnor(LaOlQis)tainrgeofmectuhrorden,tavnaalliydtea,teadnd 142 Solvent Blanks, Method Blanks, and Matrix Blanks 14.2.1 sStoalnvdeanrtdbilnantkhse,cmaleitbhroatdiobnlacnukrsv,eand matrix blanks values must be below the lowest 143 Calibration Curves 143.1 The * value for the calibration curve must be 0.980 or better. 14.4 Matrix Spikes 14.4.1 Matrix spike percent recoveries must be within 30%ofthe spiked concentration. Analysis ofUEriTnSe8E.xt9r7ac0t Using ESMS Page7of 10 001065 14.5 Continuing Calibration Verifications 145.1. sCpoinkteidnucionncgecnatlriabtriaotni.on verification percent recoveries must be within + 30%ofthe 14:6 apInecarrlfyisottrr.mieaDdloiocsntuemtdheientstyhasiltsleammcetatinhodondssiapnmeptrlhfeeosramprpaernaocnpearlisyaeztceetdilooonrgaobrtoehoenkrotacmteito,nsmaaisndteetnearnmcienemdabyybtehe 147 fIofodtantoataerdeotno tbaeblreespoarntdeddiwshceunsspederifnotrhmeantecxetcorfittehreiarhepaovretnot been me, the data must be 5.0 POLLUTION PREVENTION AND WASTE MANAGEMENT 15:1. pSiapmepttleeweaxsttreacitswdaisstpeosaenddifnlbarmomkaebnlgelassoslvceonnttaisindeirsspolsoecaditedhiingthheBlTaUborcaotnotrayi.ners, and glass 16.0 Recoros 16.1 ihEneatacedhgerrpaotairgoenhgamenendtehrwoardti,etdsefnaomropanletshtneuadpmyaeg,meu:esxttsrthauacdtvyieoontrhdpeartfoejo,elcldtiolwnuiutnmigobneinrff,eocartcomqra(utiiisfoiantpipiolnnicclmauebdtlehed)oe,di.tahnedrin the analyst. 162 aPrpipnrtoptrhieatteunsetpuadgyef,olsdaerm.plCeolpisyt, tahnedseacpqaugiessitainond mteaptehnotdofrthoemiMnasstrsuLmyennxt rtuonilnocg,lude in the 16:3 (Psluortrotghaetec)a,liwbreaitgihotnecdurxv,e btyheanlpirnienatrtohresqeuagdrraapthics afint,drsetfoerreenincetdhetostthuedyinftoelrdnearl. standard 164. aPrnidntstdoarteaiinnttehgersattiuodny sfoulmdnera.ry, integration method, and chromatograms, from MassLyn, 16:5 ASutmtmaacrhizmeendAattfaoursainngesxuaimtapblleeosfofatwsaurmem(aErxcyeslpr7e.0a)dsahnedets.tore in the study folder, see 16.6 aBnadckloucpateiloencotrfobnaicckduatpaetloecatprpornoipcrdiaattae,medium. Record in study notebook the file name 17.0 TABLES, DIAGRAMS. FLOWCHARTS. AND VALIDATION DATA 17.1 Attachment A: ETS-8-97.0 Data summary spreadsheet. 8.0 RereRENCES 18.1 TEoTnSi-z9a-t2i4o.n0/,Ma"sOspeSrpaetcitornomaentderMaQiunattetnroanIcetroiftplheequMaidcrruopomlaessSyAsttmeomsep~heric Pressure _ 18:2 The validation report associated with this method is FACT-TOX-131, W2067 Analysis ofUriEnTeSE8x.tr9a7c0t Using ESMS Page Sof 10 001066 19.0 AFFECTED DOCUMENTS 19.1CoEmTpS-o8u-n9d6s.0f,r"oEmxtUrraicnteiofnoroAfPnoaltyassissiUusmiPnegrfHlPuLoCr-oEolcteacntersouslpfroanayt/eMaosrsOtShpeerctFrloumoertorcyh"emical 20.0 Revisions ReNvuimsbiero.n Reason For Revision ReDvaitseion AnalyysissisofUrEiTnSe-E8x.t9r7a.ct0UssiingESMS 001067Page9of 10