Document O97z8qJr0xKRkEvqM9D7R0VK

CentreAnalyticaLlaboratoriEsI,nc. 3048 ResearchDrive Phone: (814)231-8032 StateCollege,PA 16801 Fax:(814)231-1253 or(814)231-1580 AnalyficRaelport Fluorochemicat Characterizationof SurfaceWater Samples Port St.Lucie,Fl(W2363) Centre AnalyticalLaboratory Report No. 023-014F TestingLaboratory 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 KrisJ.Hansen, Ph.D. 3M EnvironmentalTechnology & SafetyServices Bldg.2-3E-09 P.O. Box 33331 St.Paul,MN 55133-3331 PAGE 1 OF5 Introduction Resultasrereportfeodrtheanalysoifsa serieosfsurfacweatersamplesreceivbeydCentre AnalyticaLlaboratoriesI,nc.(Centref)rom the3M EnvironmentaLlaboratoryT.he samples were collectefdrom PortSt.Lucie,Fl.The Centrestudynumber assignedto.thperoj6ctis023-007. Specififcluorochemicaclharacterizatiboynliquicdhromatography/ tandem mass spectrometry (LCIMS/MS) was requestedforallsamples.A totaolf8 samples were receivedforanalysis. The samples were prepa@pdand analyzedby LC/MSIMS forthefoloyanglisotffluorochemicals: Table 1:TargetAnalysis -Comoound Name -PerfluorooctanSeulfonate -PerfluorooctanSeuffon-.,4amide -Perfluorooctanoate Acronym PFOS PFOSA POAA The analyticmaelthod used was validatebdy Centre.The validatiopnrotocoland resultasre on filweithCentre.Data presentedhereisthehighestqualitdyataavailablaetthistime. 2 Sample Receipt The samples were submittedinindividuapllasticontainersand were,not preserved. Eight individusaalmple containerwsere received.Samples were receivedon 05/03/00.The sample collectidoanteswere notsupplied.Chain-of-custodiynformatioinspresentedinAttachment-k 3 Holding Times The anajydcalmethod used was validateadgainsta ma)a*mum holdingtime of 14 days. The stabiliotfytheanalytesofinteresftorlongerperiodshas notbeen determined. PAGE20FS 4 Methods-Analyticaanld Preparatory 4.1 LC/MS/MS 4.1.1 Sample Preparation forLC/MS/MS Analysis Samples were initialtlryeatedwith200 uL of 250 mg/L sodium thiosulfatseolutionto remove residualchlorineS.olidphase extractio(nSPE) was used to prepare the samples for LCIMS/MS analysis.A forty-milliploirtteironof sample was transfe.,retdoa Cla SPE cartridge. The cartridgweas firsetlutedwith5 mL of 40% methanol in water solution.The eluatewas discardedand the SPE column was then elutedwith 100% methanol. A 5 mi portionof methanol was collec*,ed-afnoarlysisby LC/MS/MS. This treatmentresultedinan eight-fold concentratioonf thesamples priortoanalysis. 4.1.2 Sample Analysisby LC/MSIMS In HPLC, an aliquotof extractisinjectedand passed througha liquid-phascehromatographic column. Based on theaffiniotfytheanalyteforthestationarpyhase inthe column relativteo theliquimdobile phase,the analyteisretainedfora characten:staimcount of time. Following HPLC separationE,S/MS providesa rapidand accuratemeans foranalyzinga wide range of organic compounds, includingfluorochemicalsE.lectrosprayisgenerallyoperatedat relatively mild tbmperaturesm;olecules are ionized,fragmented,and detected. Ions characteristoifc known fluorochemicalasre observed and quantitatedagainststandards. A Hewlett-PackardHP1 100 HPLC system coupled toa Micromass UltimaMS/MS was used to analyzethe sample extractsA.nalysis,vas performed using selectedreactionmonitoring (SRM). Samples were extractedon 5/19/00and analyzedby MS/MS between 5/22/00and 5/23/00. An initianlalysiswas performed on 5121/00,however, the data was rejected because of unacceptablestandard curves. The data is includedin Attachment D for informationaplurposes only.The HPLC and MS/MS methods used foranalysisand instrument parameterscan be found inattachmentD. 5 Analysis 5.1 Calibration A 7-pointcalibraticounrvewas analyzedatthe beginningand end ofthe analyticaslequence forthe compounds of interestT.he calibrabonpointswere prepared at 0,25, 50, 100, 250, 500, and 1000 ng/L(ppt)The response of the quanfitatioinonversus the concentratiownas plottedforeach point Using linearegressionwith 1/xw(e@,)ghtitnhge,slope,y-intercepatnd correlatiocnoefficien(tr)and coefficienotf determination were determined.A calibration curve-isacceptableifr> 0.985 (r2> 0.970). Calibratiosntandardsare preparedusingthe same SPE procedure used forsamples. Calibratiocnheck standardswere analyzed periodicall(yeverythreetofivesample injecfions) throughoutthe analysissequence. Compliance is obtained if the standard analyte concentrationsare within+/-20% of theactualvalue. For the resultrseportedhere,calibratiocnriteriwaere met. PAGE3OF5 5.2 Blanks Extractiobnlankswere preparedand analyzedwitheveryextractiobnatchofsamples.The extractiobnlanksshouldnothave anytargetanalytepsresentatorabove theconcentrationf thelow-leveclalibratisotnandard.Forthesesamples,theextractiobnlankswere compliant. Instrumenbtlanksintheform ofcleanmethanolsolventwere alsoanalyzedaftereveryhighlevelcalibratisotnandarda,nd afterknown high@eveslamples. Again,theblanksshouldnot have any targeatnalytespresentator above thelow-leveclalibratisotnandard.For the samples presentedheretheinstrumenbtlanksarecompliant. 5.3 Surrogates Surrogatespikes.a,re.n-o-rta component of.thLeC/MSIMS analyticmaelthod. 5.4 MatrixSpikes MaWx spikeswere preparedforeveryfieldsample (excludinbglanks)ata concentrationf 100 ng/Lusingallcompounds ofinterestMatrixspikerecoverieasregiveninAttachmentC. Sample MC-684H had PFOS atlevelsignificangtrleyaterthan 10 timesthespikinglevel, thereforaeccuratematrixspikerecoveriecsouldnotbe determined.Allothercompounds inall samplesshowed matrixspikerecoveriebsetween70-130%. . Fieldspikeswere alsopreparedon sample MC-601 H forallcompounds ata concentratioonf 100 ng/Lusingallcompounds ofinterestFieldspikerecoverieasrealsogiveninAttachment C. AJIcompounds showed recoveriebsetween 70-130% inthefielsdpikes. 5.5 Duplicates Adifielsdamples(excludibnlganksw)ereanalyzeidnduplicatRee.sultasregivenalongwith -thesample resultisnAttachmentB. 5.6 LaboratoryControl Samples Milliwqaterwas spikedwithallcompound ofinteresatt25 and 250 ng/L. PFOS showed a recoveryof133% inthe25 ngILspike.Allrecoveriefsorallothercompounds were between 70-130% ineach LCS. Resultsaregivenalongwiththeraw datainAttachmentD. 5.7 Sample Related Comments Fieldblanksamplesconsisteodfempty containers.FortymillilitoefrtsypeIwaterfiltered througha hypercarbcartridgweas added totheempty containearnd analyzedinthesame manner as theothersamples.The fielbdlankforthissample didshow PFOS above the reportinlgimil 6 Data Summary PleaseseeAttachmentB fora detaileldisfinogftheanalyticraelsults. 7 DatalSample Retention Samples aredisposedofone month afterthereportisissuedunlessotherwissepecifiedA.ll electronidcataisarchivedon retrievabmleedia and hard copy reportsare storedindata foldermsaintainedby Centre. PAGE40F5 8 Attachments 8.1 Attachment A- Chain-of-Custody 8.2 Attachment B:Results. 8.3 Attachment C: MatrixSpike Recoveries (Fieldand LaboratorySpikes) 8.4 Attachment 0: LCIMSIMS Raw AnalyticalData 9 Signatures er- Operations Manager Kevin J LJoyd,Vice President Date Date Other Lab Members Conbibutingto Data Enaksha Wickremesinhe Karen Smith David Bell TiffanyProctor PAGE50F5 ANALYTICALREFORT Centre Analytical Laboratorif=-s,Inc. 3048 Research Drive,State College PA 16801 814-231-8032 FAX 814-231-1253 AnalyticRaelsultWs2'@36P3ortSt.LucieF,l 3M Sample Identification MC-601H MC-603H MC-606H NA MC-607H NA MC-608H MC-684H NA Sample Description Site1 SurfaceWater Site1 SurfaceWater Duplicate Site2 SurfaceWater Site2 SurfaceWater Ouplir-ate Site3 Surface-Weter Site3 SurfaceWater Duplicate FieldBlank-P/NEmpty QuietSurfaceWater QuietSurfaceWater Duplicate PFOS (ng/L) < 25 < 25 138 137 18.8J 23.2 1 43.1 45300 51100 i -Compound ispresentb,utbelowthereportinlgimiotf25 ng/L. The result;san estimatedvalue. Method DeteclioLnimitsareapproximatel2y.5ng!LforPFOS and PFOSA and 7.5ng[LforPOAA. PFOSA (ng/L) < 25 < 25 < 25 < 25 < 25 < 25 < 25 83.6 95.2 POAA (ng/L) < 25 < 25 18.4J 18.81 < 25 < 25 < 25 737 760 Please referto the reverse side for our standard terms and conditions.