Document qdkm6xQmMvYnkaX8Q7pMbznNn

3M ENVIRONMENTAL LABORATORY METHOD ANALYSIS OF POTASSIUM PERFLUOROOCTANESULFONATE OR OTHER FLUOROCHEMICALS IN LIVER EXTRACTS USING HPLC-ELECTROSPRAY/MASS SPECTROMETRY Method Number: ETS-8-7.0 Adoption Date: 0F[2219% Author: Lisa Clemen, Glenn Langenburg Approved By: 7 2 1p Laboratory ager ftom tr Group Leader nh Clysnee Technical Reviewer Revision Date: NA 2h for Date 2/4139 Date o7lilpy Date 1.0 SCOPE AND APPLICATION 1.1 S'HcPoLpCe-:elTehcitsromseptrhaoyd/miasssfosrptehcetraonmaeltyrsyi.s of liver extracts for fluorochemical surfactants using 1.2 Applicable Compounds: Fluorochemical other ionizable compounds. surfactants or other fluorinated compounds, or 1.3 rMeaptorrit.ces: Rabbit, rat, bovine, monkey liver, or other tissues as designated in the validation Word 695 Analysis of LEivTerSE4xt7ra0ct Using ESMS Page lof 10 001035 2.0 SUMMARY OF METHOD. 2.1 THhPiLsC-meeltehcotdrodsepsrcaryi/bemsastshespaneacltyrsoimsetorfy,flourorsoimcihleamricsaylstseurmfaacstaapnptrsoperxitartaec.tedThferoamnalliyvesrisusising ptheerfpoerrfmleudorboyocmtoannietsourlifnognaatesi(nPglFeOiSo)nacnhiaorna,ctme/rizst=ic49o9af. Apadrdtiitciuolnaarllfyl,uosraomcphleemsicmala,ysbuech as analyzed detecting udsaiungghtaetrainodnesmofmathsesssepleecctterdompeatreernttoiofnu.rther verify the identityof a compound by 3.0 DeeiNTIONS 3.1 Atmospheric systems allow PfroresvsaurrioeuIsomneiztahtoidosno(fAPiIon)i:zaTthieonMbiycriolmiazsisngQuvaatrtiroouIs triple quadrupole sources, probes, and interfaces. These Pressure chemical include but Ionization are not (APel), limited to: Electrospray Thermospray, etc. The Ionization ionization (ESI), Atmospheric. process in these techniques occurs at atmospheric pressure (i.e. not under a vacuum), 3.2 pErleescsturreo,spwrhaeyrIeobnyiziaotnisoinn(sEolSu,tiEoSnIa)r:eatmreantshfoedrroefdiotonitzhaetgiaosnpphearsfeorvmiaedtiantyacthmaorsgpehderdirocplets. These charged droplets are produced by the applicationof a strong electrical field. 3.3 `MTahsesAPSIpeQcutartotmreotIrTyt,riMplaesqsuaSdpreucptorloemmeatsesr s(pMeSc)t,roTmaentedreims eMqausipspSepdewcittrhotmweoteqrua(dMrSu/pMoSle): `cmhaasrsgeserlaetcitoiv(em/dze)teacntdorssuabnsedqauecnotllliysidoenteccetlle.d. ToAnssianrgelseeMleSctimvaelyybdeisecmrpilmionyaetdedfobryimoanss to detection and these ofrraagnmfeonntsmmaayybebesealneacltyezdeidn itnhethfeirsset cqounaddrquupaodlreu,poflrea.gmented in the collision cell, 3.4 Ctroinplveeqnutaidornuaplolves.(Zp-osstpr1a9y98p)ruotbileizientae"rfZa-csep:raTyh"ecolnafteosrtmamtoidoenl.s oTfheMiscprroamyaesmsitQtueadttfrroomIla dpirroebcetliys aotrtthheogcoonnael atpoertthuerce,onaeftarpepratusrsei.ng Itnhtrhoeugchonavteonrttiuoonuasl pcaotnhfowramyaitniotnheitciosunatiemred e`lmeacitnrtoedne.ancTehaoruegthhethseamceo.nfiHgouwreatvieorn,iZs-dsipffrearyencto,mtphoenmeentthsodasnodfcoonpveernattiioonn,alclceoamnipnogn,enantds are: cnootmpcaotmipbalteibwliethwiotthheornZe-sapnortahyers,ysbtuetmso,nleytcw.)ith similar systems (i.e. Z-spray components are 3.5 MIatsrisplLeyqnuxadSroufptowlaersey:steSmyss.teCmursroefnttwlayreMdaesssiLgynnedxfhoarsthWeinspdeociwfsic9o5pearnadtiWoinnodfotwhessNeTQu4a.t0tro vienrsstirounmse.ntAl(lMivcerrsoimoansssaQrueastitmriloarI. trFioprlemqouraedrdueptoailles MreafsesrLtyontxheomraMnausaslLsypnecxifNicTtUostehr'es. Guide). 4.0 WARNINGS AND CAUTIONS 41 Health and Safety Warnings: 4.1.1 Uemspelcoayustiaonvowlittahgetohfeavpoplrtoagxeimcaatbleelsyf5o0r0t0heVoplrtosb.e. When engaged, the probe Analysis ofLivEeTrSE.x8tr.a7c0t Using ESMS Page 20f10 001036 4.12 When handling and clothing. samples or solvents wear appropriate protective gloves, eyewear, 42 Cautions: 4.2.1 pOrpeesrsautreetehxecseoeldvsen4t00pubmarp,sthbeeHlPo1aw10b0acwkilplreinsistuiraeteoafu4t0om0abtairc(s5h8u0t0dopwsin).. If the back 4.22 Do not run solvent pumps to dryness. S0 5O.1 InTvo0 emmeineiRme0 ixzeceinst0 erferenc0 es when0 analyz0 ing samp0 les, Te0 flon sh0 all not b0 e used0 for sam0 ple storage or any partof instrumentation that comes in contact with the sample or extract 6.0 Equipment 6.1 `Emqoudiifpimceanttionlisstiendtbheelroawwmdaatyabaes mmoedtihfoideddeivniaotridoenrs.to optimize the system. Document any. 6.1.1 MelieccrtoromsapsrsayQuiaontitzraotiIolntrsiopulrecqeu.adrupole Mass Spectrometer equipped with an 6.1.2 HcoPm1p1a0rt0mleonwt,pualnsdeasuotlovseantmppluemrping system, solvent degasser, column 77..01 SUSPuPpLplIiEeSsANDMATERMALS000000000000 7.1.1 High purity grade air regulated to approximately 100 psi (House air system) 7.1.2 HPLC analytical in the raw data column, specificstobe determined by the analyst and documented 7.13 Capped autovials or capped 15 ml centrifuge tubes 8.0 REAGENTS AND STANDARDS. 81 Reagents SE 8.1.1 Methanol, HPLC grade or equivalent 8.12 tMyipleliI,-oQrTMewqauitvearle(nAt,STanMdtybpeepIr),ovailldewdatbeyrausMeidlliin-tQhiTsOmCetPhlouds sshyosutledmobreoAthTeSrM vendor 81.3 Ammonium acetate, reagent grade or equivalent 8.1.3.1 When preparing different amounts than those listed, adjust accordingly. 8.1.3.2 2a.m0mmonMiuammmaocentaitue.mPaoceutratientsoolau2ti0o0n0: mWeLigvohluampeptrroixcimcaotnetlayin0e.r3c0o0ntgaining t2e0m0p0ermatLureM.illi-QTM water, mix until all solids are dissolved. Store at room AnaolfLyiEvTesS8Ex.it7ra.sc0tUsing ESMS 001Pa0ge3370f 10 82 Standards 82.1 Typically two method blanks, prepared during the extraction two matrix procedure. blanks, and eighteen Refer to ETS-8-6.0. maix standards are 9.0 SAMPLE HANDLING 9.1 Farreesshtomraetdriinxcsatpapndeadrdasutaorveiaplrseoprarceadpwpietdh1e5acmhiacneanltyrsiisf.ugeExtturbaecstuendtisltaannadlayrsdiss.and samples 9.2 Itfemapnearlyastiusrew,ilolrbreefdreilgearyaetde,deaxttarpacptreodxismtaantdealryd4saCn,d usnatmilplaensalmyasiys bceanstboerepderaftorrmoeodm. 10.0 QuALITY CONTRO) 10.1 Method Blanks and Matrix Blanks 10.1.1 Saoclhvebnattbclhatnoksd,etmeertmhionde bcloanntkasm,iannadtimoantroirxcabrlraynokvsera.re prepared and analyzed with 10.1.2 Analyze a method blank and a matrix blank prior to cach calibration curve. 102 Matrix Spikes 10.2.1 rMeactorviexrsypeifkfeisciaernecyp.repared and analyzed to determine the matrix effect on the 10.2.2 Matrix spike duplicatesareprepared recovery for each analyte. and analyzed to measure the precision and the 10.2.3 Analyze a matrix spikeand matrix minimumof 2 spikes per batch. spike duplicateper forty samples. Witha 10.2.4 Mthaetriinixtisaplickaeliabnrdatmiaontrciuxrvsep.ikAeddduiptliiocnaatle scpoinkceenctornacteinotnrsatwiilolnsfamlaliynftahlle imnidth-eralnogwe-of range of the initial calibration curve. 103 Continuing Calibration Checks 10.3.1 Continuing calibration verifications of the calibration curve. are analyzed to verify the continued accuracy 10.3.2 Analyze a mid-range one per batch. calibration standard every tenth sample, with a minimum of 11.0 CALIBRATION AND STANDARDIZATION 11.1 TAhnaelayvzeerathgeeoefxttrwacotesdtamnadtarridxcsutravnedsarwdislplrbieorptloottaenddbfyolllionweairngreegarcehsssieotno(fys=ammpxle+ebx)t,racts. `weighted 1/x, not forced through the origin, using MassLynx or other suitable software. 11.2 sIttahnedacrudrcvuerdvoee(sifnneoctemseseatryr)eqaunidrermeeanntaslypzee.rform routine maintenance or reextract the Analysis of LivEeTrSE.x8t.ra7c0t Using ESMS. Page dof 10 001038 11.3 uFsoer tphuerploosweseonfdaocfctuhreaccayliwbhraetnioqnuacnutrivteatriantghelrotwhalnevtehlesoffulalnralayntgeeo,fitt hmeaystbaendnaercdescsuarvrey.to cEaxlaimbprlaeti:onwchurevneactotnesmipsttiinngg otfotqhueansttitaantdearadpsprforxoimma5tpeplyb t1o0 1p0p0bopfpabnraaltyhteer,tgheannetrhaetefuall rangeof the curve (5 regression weighting ppb to of high 1c0o0n0cepnptbr).atiTohnisstawnidlalrrdse.duce inaccuracy attributed to linear 2.0 PROCEDURES 12.1 Acquisition Set up 12.1.1 Setup the sample lst 12.1.1.1 lAsesitgotnfeathsreamapllpehalbsettfsitlaretnianmgewuistihnag MO-DAY.-last digitofyear-increasing 12.1.1.2 Assign a method (MS file) for acquiring 12.1.1.3 Assign an HPLC program (Inlet file) 121.14 Type in sample descriptions and vial position numbers 12.1.2 sTpoecctreraotmeetaermehtehaoddincglsicakndonsemleectthoSdIRin(SthiengAlceqIuoinsiRteicoonrcdoinntgr)olorpaMneRlMthe(nMumlatsipsle aRpeparcotpiroinatMeonmiatsosreisn.g)A. fSueltl sIocnainziastiuosnuaMlolydecoalsleacptperdoaplroiantgewaintdh tmhaesSsItRos.49S9aovreother facrqaugimseinttiaotnimoentihnofdo.rmIatFiMoSn/mMaSy ibnesctorlulmeecnttesd.arReeefmeprltooyMeid,craodmdaitsisonMaalspsrLodyuncxt ion GUIDE TO DATA ACQUISITION for additional information and MRM. 12.1.3 Typically the analyticalbatchrun matrix standards. sequence begins and ends withasetofextracted 12.1.4 aSfatmerpleevserayreteanntahlsyazmepdlew.ithSoalvcoennttibnluainnkgscsalhioburladtiboen verification injected standard analyzed periodically to `imnocnliutdoerdpaossssiubchl.e analyte carryover and are not considered samples but may be 122 Using the Autosampler 1222.1 Set up sample tray according to the sample list prepared in Section 12.1.1 12.22 aSneatl-yuspttchoensHiPd1e1r0s0a/papurtoopsriaamtpeleforraoptthiemaflolrleoswpionngsec.onRdeictoiorndsaocrtuaatlccoonnddiittiioonnsstihnethe instrument logbook: 122.21 Samplesize = 10 uL injection 12.222 Inject'sample = 1 1222.3 Cycle time = 9 minutes `Analysis of LEivTerSE8xt7r.ac0t Using ESMS. Page Saf 10 001039 12.2.2.4 Solvent ramp conditions Time MeOH Ammo2n.iu0mmMacetate ((0L0o0mmi |wdw% |60Go%n ]| [(7o0ommi.n aawv | |e eoon] ] 12.2.2.5 Press the "Start" button. 12.3 Instrument Set-up 12.3.1 `RTerfieplretQouEaTdSr-u9p-o2l4e.0M,as"sOpSepreacttiroonmaentderMFaiitnttedenwaintcheoanfAtthmeoMsipchreormiacsPsreQsusautrtero II Ionization Source," for more details. 12.3.2 Check the solvent level in reservoirs and refill if necessary. 12.3.3 12.3.4 12.3.5 Check the stainless steel capillaryatthe endofthe probe. Use an eyepiece to check the tip. The tip should be flat withnojagged edges. Ifthe tip is found to be unsatisfactory, disassemble the probe and replace the stainless steel capillary. Turn on the nitrogen. Open the tune page. Clicks on operate to initiate source block and desolvation heaters. 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/min or as appropriate 12.3.6.3 eOxbpseelrlveed dwriotphlentos nciotmriognegnoluetakoifntghaertoipunodftthhee tpirpoobfet.heApfrionbeem.isRteasdhjouusltd be the tipofthe probeif no mist is observed. 123.64 Allow to equilibrate for approximately 10 minutes. 12.3.7 cThhaenignestinruomrednetr utsoeosptthiemsiezepatrhaemreetseprosnsaet:the following settings. These settings may 12.3.7.1 Drying gas 250-400 liters/hour 12.3.7.2 ESI nebulizing gas 10-15liters/hour 12.3.7.3 HPLC constant flow mode flow rate 10 -- 500 uL/min 12.3.7.4 Pressu HPLC re is <op4e0r0atbianrg(cTohrirsecptalry.a)m e te r is not set, it is a guide to ensure the 12.3.7.5 Source block temperature 150 12.3.7.6 Desolvation temperature 250 AntsofivFe vnsUsingESAS rgesorto 001040 12.3.8 Print the tune taped into the piangset,ruwmietnht iltosgp.arameters, and store it in the study binder with a copy 12.3.9 CMlaiscskLoynnxstavretrsbiuotntso,nrienfetrhetoAcaqpupirsoiptriioanteCMonatsrsoLlyPnaxneUlse(rth'iss Gmuaiydev).aryEnasmuornegstart and end sample number includes all samples to be analyzed. 13.0 DATA ANALYSIS AND CALCULATIONS 13.4 Calculations: 13.1.4 Calculate matrix spike percent recoveries using the following equation: % Recovery = Observed Result- Background Result x 100 Expected Result 13.1.5 Calculate percent difference using the following equation: % Difference = Expected Cone. - Calculated Cone. x 100 Expected Conc, 13.1.6 Calculate actual concentrations in matrix (ug/g): {ng of PFOS cal. from std. Curve x Dilution Factor) x Lug (Initial Weight of Liver () 1000 ng Final Volume (mL) 14.0 METHOD PERFORMANCE. 14.1 mMaettrhioxdspDeectieficct.ioRneLfiemritto(EMTSD-L8)-6a.n0d,LAitmtiatcohfmQeunatntBitafotrioanl(isLtOinQgo)farceurmreetnhtovda,liadnaatleydteM, DanLd and LOQ values. 142 Solvent Blanks, Method Blanks and Matrix Blanks 14.2.1 sStoalnvdeanrtdbilnantkhse,cmaleitbhroatdiobnlacnukrsv,e.and matrix blanks must be below the lowest 143 Calibration Curves 14.3.1 The value for the calibration must be 0.980 or better. 14.4 Matrix Spikes 14.4.1 Matrix spike percent recoveries must be within + 30%ofthe spiked concentration. 145 Continuing Calibration Verification 145.1 sCpoinkteidnucionncgenctarlaitbiroant.ion verification percent recoveries must be within + 30%of the 14.6 pIfecrrfioterrmieadloisntetdhienstyhsetmeemtahnoddspaemrpfloersmraenacnealseyczteidoonraroethneortamcetti,onmsaaisntdeentaenrcmeinmeadybybethe analyst. Document all actions in the appropriate logbook. Analysis ofLivEeTrSE.x8t.ra7c0t Using ESMS Page 70f 10 001041 14.7 fIofdoattnoataerdeotno tbaeblreespoarntdeddiwshceunsspederifnotrhmeantecxetcorfittehreiarehpaovret.not been met, the data must be 15.0 POLLUTION PREVENTION AND WASTE MANAGEMENT 15.1 pSiapmepttleeweaxsttreacitswdaisstpeosaenddifnlbarmomkaebnlgelsaosslvceonnttaisindeirsspolsoecadteind hiingthheBlTaUborcaotnotrayi.ners, and glass 16.0 Recorps 161 hEeaacdherpaogrehgaennderwartiettdfenorona tshteudpyagmeu:ststhuadvyeotrhperfoojelcltowniunmgbienrf,oracmqautiisointiionnclmuedtehdoedi,ther in the integration analyst. method, sample name, extraction date, dilution factor (if applicable), and 162 aPpripnrtoptrhieattuensetpuadgyef,olsdaemr.plCeolipsyt, tahnedseacpqaugiessitainodn mtaeptehoindtofrthoemiMnasstrsuLmyennxt rtuonilnocg.lude in the 163 Pstloortetihnetchaelisbtruadtyiofnolcduerrv.e by linear regression, weighted 1/x, then print these graphs and 16.4 Parnidntstdoarteaiinnttehgersattiuodnysfuolmdmear.ry, integration method, and chromatograms from MassLynx 165 SAtutmamcahrmieznetdaAtafoursianngesxuaimtapbllee osoffatwsaurmem(aErxyceslpr5e.a0d+s)heaentd. store in the study folder, refer to 16.6 Banadckloucpateiloenctorfobnaiccdkautpateloecatprpornoipcrdiaattae.medium. Record in study notebook the file name 17.0 TABLES, DIAGRAMS, FLOWCHARTS, AND VALIDATION DATA 17.1 Attachment A: ETS-8-7.0 Data summary spreadsheet 18.0 REFERENCES 18.1 FCAoCmTp-oMu-n2d.s1,fr"oEmxtLriavcetriofnoorfAPnoatlayssissiuUsmiPnegrfHlPuLoCr-oEolcteacntersouslpfronaayt/eMaosrsOtShpeerctFrloumoertorcyh"emical 182 EToTnSi-z9a-t2i4o.n0/,Ma"sOspeSrpaetcitornomaentderMaQiunattetnroanIcTetorifpltehqeuMaidcrruopomlaessSyAsttmeomssp"heric Pressure 18.3 The validation report associated with this method is ETS-8-6.0 & 7.0-V-1 19.0 AFFECTED DOCUMENTS 19.1 E`TCSo-m8p-o6.u0n,ds"EfxrtormacLtiivoenorfoPrFoltuaisdsifuomr APnearlfylsuiosroUoscitnangeHsPulLfCo-nEalteecotrroOsthperrayF/lMuaosrsochemical Spectrometry" Analysis ofLivEeTrSE8xt:r7ac0t Using ESMS Page8of 10 001042 20.0 Revisions Revision Number Reason For Revision Revision Date AnalysisofLivEeTrSE8x:tr7a.c0t Using ESMS Page 9of 10 001043 Laboratory Study # TSeusdtyMaterial MMaettshioxd//FRienvalisSioolnvent AInnasltyrtuimceanltSEoqfutiwpamreenVterSsyisotne:m Number: RFi-lSeqnuaamreed Value: SloIpne:rcep DDaatteeooffAEnxatlryascitso/nA/nAanlayslty:st [oT d[ S SReETToT nTrw | oDTl Te [oaeCe] GSroopuepr/DoTsaker e: TaromkenTfeaorm_ the stu_ dy fEolrd] er IEE `SCaomnpcelnet;ratTiaokne(nfg/ogm):thTeaksetnudfyroolmdetrh.e MassLynx integration summary. DIniiltuitailoWneF.ac(8t)o:r:TaTkaeknenfrformomthtehstsutduydyfoflodledrer Final Conc. (ug/g); Calculated by dividing the inital volume fom the concentration tachmenAt: Summary Spreadsheet AnalysisofLiEvTerS8Ex.tr7ac0t Using ESMS Page 100610 001044