Document jgrbOa2XMBYDqG1oobY1zV64k

CentreA-nalyticLaalboratoriIensc,. 3048ResearchDrive Phone: (814)231-8032 StateCollege,PA 16801 Fax: (814)231-1253 or (814)231-1580 AnalyficRaelport Fluorochemical CharacterizationofSurface Water Samples Mobile,Alabama (W2151) Centre AnalyticalLaboratory Report No. 023-014D Testing Laboratory CentreAnalyticaLlaboratoryI,nc. 3048 Research Drive StateCollege,PA 16801 3M Environmental Laboratory Contact Kent R. Lindstrom Bldg.2-3E-09 P.O. Box 33331 St.Paul,MN 55133-3331 Phone: (651)778-5352 Requester K@s J.Hansen, Ph.D. 3M EnvironmentalTechnology & Safety,Services Bldg.2-3E-09 P.O. Box 33331 St.Paul,MN 55133-3331 PAGElOF5 Introduction Resultasrereportefdortheanalysiosfa serieosfsurfacweatersamplesreceivebdy Centre AnalyticaLlaboratoriesI,nc.(Centre)from the3M EnvironmentalLaboratory.The samples were collectefdrom Mobile,Alabama. The Centre studynumber assigned tothe projectis023-014. Specificfluorochemicaclharacterizatiboyn liquicdhromatography /tandem mass spectrometry (LC/MS/MS) was requestedforallsamples. A totalof8 samples were receivedforanalysis. The samples were prepared and analyzedby LC/MS/MS forthe followinlgisotffluorochemicals: Table 1:TargetAnalysis Compound Name PerfluorooctaneSulfonate PerfluorooctaneSulfonviamide Perfluorooctanoate Acronvm PFOS PFOSA POAA The analyticamlethod used was validatedby Centre. The validatiopnrotocoland resultsare on filweithCentre. Data presentedhere isthe highestqualitydata availablaet thistime. 2 Sample Receipt The samples were submitted in individuapllasticcontainersand were not preserved. Eight individuaslample containerswere received.Samples were receivedon 05/03/00. The sample collectiodnates were not supplied.Chain-of-custodyinformationispresentedinAttachment A- 3 Holding Times The analyticamlethod used was validatedagainsta maximum holdingtime of 14 days. The stabiliotfythe analytesof interesftorlongerperiodshas not been determined. PAGE20F5 4 Methods-AnalyticaanldPreparatory 4.1 LCIMS/MS 4.1.1 SamplePreparatifoonrLCIMS/MSAnalysis Sampleswereinitiatlrleyatewdith200uL of250 mg/Lsodiumthiosulfsaotleutiotnoremove residcuhallorineS.olidphase extracti(oSnPE)was used to preparethe samplesfor LC/MS/MSanalysisA.forty-millpiolrittieoornfsamplewas transferrteoad C18 SPE cartridge. The cartridgweas firsetlutedwith5 mL of40% methanol inwater soluton.The eluatewas discardedand the SPE column was then elutedwith 100% methanol. A 5 mi portionof methanol was collectefdoranalysisby LC/MS/MS. This treatmentresultedinan eight-fold concentratioonfthe samples priortoanalysis. 4.1.2 Sample Analysis by LC/MS/MS In HPLC, an aliquotof extractisinjectedand passed througha liquid-phascehromatographic column. Based on theaffiniotfytheanalyteforthestationarpyhase inthe column relativteo theliquimdobile phase, the analyteisretainedfoea characteristaimcount of time. Following HPLC separationE,S/MS providesa rapidand accuratemeans foranalyzinga wide range of organic compounds, includinfgluorochemicalsE.lectrosprayisgenerallyoperated at relatively mildtemperatures;moleculesare ionizedf,ragmented,and detected. Ionscharacteristoifc known fluorochemicalasre observed and quantitatedagainststandards. A HevAeft-PackardHP1 100 HPLC system coupledto a Micromass UltimaMS/MS was used to analyzethe sample extractsA.nalysiswas performed using selectedreactionmonitoring (SRM). Samples were extractedon 5/17/00and analyzed by MS/MS on 5/20/00.The HPLC and MS/MS methods used foranalysisand instrumentparameters can be found inattachment D. 5 Analysis 5.1 Calibration A 7-pointcalibrationcurve was analyzed at the beginning and end of the analyticalsequence forthe compounds of interestT.he calibratiopnointswere preparedat 0, 25, 50, 100, 250, 500, and 1000 ng/L (ppt)The response ofthe quantitafioinonversus the concentratiownas plottedforeach point.Using linearegressionwith 1/xweighting,the slope,y-intercepatnd correlatiocnoefficien(tr)and coefficienotf determination were determined.A calibrabon curve isacceptableffr > 0.985(@ > 0.970). Calibratiosntandardsare preparedusingthe same SPE procedure used forsamples. Calibratiocnheck standardswere analyzedperiodical(leyverythreetofivesample injections) throughoutthe analysissequence. Compliance is obtainedif the standard analyte concentrationasre within+/-20% ofthe actualvalue. For the resultsreportedhere,calibraticorniteriwaere met. PAGE 3 OF 5 5.2 Blanks Extradon blankswere preparedand analyzedwitheveryextractiobnatchof samples.The extractiobnlanksshould nothave any targetana@tes presentator above the concentratioonf the low-leveclalibratiosntandard.For these samples,the extractiobnlankswere compliant. Instrumentblanks inthe form of cleanmethanol solventwere also analyzedafterevery highlevelcalibratiosntandard,and afterknown high-leveslamples. Again,the blanksshouldnot have any targetanalytespresentat or above the low-leveclalibratiosntandard. For the samples presentedhere theinstrumentblanksare compliant. 5.3 Surrogates Surrogatespikesare nota component ofthe LC/MS/MS analyticamlethod. 5.4 MatrixSpikes Matrixspikeswere preparedforeveryfieldsample (excludingblanks)at a concentratioonf 100 ng/L usingallcompounds of interest.Matrixspikerecoveriesare given inAttachment C. POAA showed low matrixspikerecoveriesinsamples MC-407H and MC-484H. Allother compounds showed matrixspikesrecoveriesbetween 70-130% inallsamples. Fieldspikes were preparedon sample MC-401H at a concentratioonf 100 ng/L using all compounds of interestF.ieldspikerecoveriesare alsogiveninAttachment C. AJIcompounds showed recoveriesbetween 70-130%. 5.5 Duplicates Allfielsdamples (excludingblanks)were analyzedinduplicate.Resultsaregivenalongwith the sample resultsinAttachmentB. 5.6 LaboratoryControl Samples Milliwqater was spikedwithallcompound of interesatt25 and 250 ng/L. Allrecoveriesforall compounds were between 70-130% ineach LCS. Recoveriesaregivenwiththe raw data in Attachment D. 5.7 Sample Related Comments Fieldblank samples consistedof empty containers.Fortymillilitoefrstype Iwater filtered througha hypercarbcartridgweas added to the empty containerand analyzedinthe same manner as theothersamples. 6 Data Summary Please see Attachment B fora detailedlistinogfthe analyticarlesults. 7 DatalSample Retention Samples are disposed of one month afterthe reportisissued unlessotherwisespecified.All electronidcata isarchivedon retrievablmeedia and hard copy reportsare stored indata foldersmaintainedby Centre. PAGE40F5 8 Attachments 8.1 AttachmentA Chain-of-Custody 8.2 AttachmentB: Results. 8.3 AttachmentC:MatrixSpikeRecoveries(Fieldand LaboratorySpikes) 8.4 Attachment D: LC/MS/MS Raw AnalyticaDlata 9 Signatures ,@John M. FiMt@r-Operafions Manager Date Kevin J Lloyd,Vice President Date Other Lab Members Contributintgo Data Enaksha Wickremesinhe Karen Smith David Bell PAGE50FS Ifilfllq&il Cc=ntre Analytical LaboratoriFs, Inc. 3048 Research Drive,State CollegePA 16801 814-231-8032 FAX 814-231-1253 #IA f JAAMMWW AnalyticRaelsultWs2151MobileA,labama 3M Sample Identification Sample Description PFOS (ng/L) PFOSA (ngIL) MC-401H MC-403H MC-406H NA MC-407H NA MC-408H MC-484H NA SiteI-P/NSurfaceWater SiteI-P/NSurfaceWater Duplicate Site2-P/NSurfaceWater Site2-P/NSurfaceWater Duplicate Site3-P/NSurfaceWater Site3-P/NSurfaceWater Duplicate FieldBlank-P/NEmpty QuietSurfaceWater QuietSurfaceWater Duplicate 23.9 J 22.0 J 39.6 42.8 34.7 36.3 < 25 33.3 31.5 6.6 J 6.2 J 12.9 J 13.3 J 8.6 1 9.81. < 25 7.9J 7.6J J -Compound ispresent,butbelowthereportinlgimiotf25 ng/L The resultisan estimatedvalue. Method DetectionUmitsare appro)dmatel2y.5ng[L forPFOS and PFOSA and 7.5 ng/LforPOAA. POAA (ng/L) 25.5 27 53.9 59.8 82.6 a2.8 < 25 27 24.9J AMk Pi"serefetrothereversseideforourstandarfdormsand conditfons. ri Mobile River Site#3 r .,TOiii 3 Mile Cre I.I.I.K 43 quietwater 7n Mobile River Site#2 Mi km i@TrI- C.C.Williams WWTP (discharge) 01mg m Inc.-0.1990 DT,*ino. Additionalsampling sites shown on west map Environmental Sampling Sitesand Supply Chain FacilitiefsorMobile,AL 70 jPalmer Guftrd ,-IPwmping Station Wuent) e-2-Ilnderosa 31 ........ anat"oEiiat!j etalumzs en Acres- r adiboo 37 Pat ul IE tg. c:ouny I 70 I k-m FJ Wlin squ Ven Hi@ll id@rbrock: -.GroM M7 Iree ood abrak'% g 59 co t $!"C-' ri iaun kE --Co ge 39 SO' 31 37 o wi @re (@rbv P;d Alternativesample i siteatHalb NU Creek near Schfllengers Road oiwc wwpQuawLeoffl%ncl0-1.909(3DT.I i Additionalsampling sites shown on eastmap _@ ....... 28 Environmental Sampling SitesWest ofMobile,AL