Document e5prYDaGgMGzj4XpEEbJr4jkg

CentreAnal!jtiLcabloratorieIsn,c. 3048 ResearchDrive Phone: (814)231-8032 StateCollege,PA 16801 Fax:(814)231-1253 or (814)231-1580 Anaw(;alReport Fluorochemical Characterizationof Surface Water Samples Cleveland,Tennessee (W1973) Centre AnalyticalLaboratory Report No. 023-014A 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 I OF 5 Introduction Resultasrereportefdortheanafysiosfa seriesofsurfacweatersamplesreceivebdyCentre AnalyticaLlaboratoriesI,nc.(Centre)from the3M EnvironmentalLaboratory.The samples were collectefdrom Cleveland,Tennessee. The Centre studynumber assignedtotheprojectis023014. Specificfluorochemicaclharacterizatiobny liquidchromatography / tandem mass spectrometry (LC/MS/MS) was requestedforallsamples. A totaolf8 samples were receivedforanalysis. The samples were prepared and analyzed by LC/MS/MS forthefollowinglisotf fluorochemicals: Table 1:TargetAnalysis ComiDound Name PerfluorooctaneSulfonate PerfluorooctaneSulfonviamide Perfluorooctanoate Acronvm PFOS PFOSA POAA The analyticamlethod used here was validatedby Centre. The validatiopnrotocoland resuftsare on filweithCentre. Data presentedhere isthe highestqualitdyata availableatthisfime. 2 Sample Receipt The samples were submitted in individuapllasticcontainersand were not preserved. Eight individuaslample containerswere received.Samples were receivedon 05/03/00.The sample collectiodnateswere notsupplied.Chain-of-custodyinformationispresentedinAttachment A. Sample MC-102H was not analyzedas per dient request.(E-mailcommunication from K@s Hansen on 5/16100). 3 Holding Times The analyticamlethod used was validatedagainsta maximum holdingfime of 14 days. The stabiliotfythe analytesof interesftorlongerperiodshas not been determined. PAGE20F5 4 Methods -Analyticaalnd Preparatory 4.1 LC/MS/MS 4.1.1 Sample PreparationforLC/MSIMS Analysis Samples were initiatlrleyatedwith200 uL of250 mg/L sodium thiosuffatseolutiotno remove residualchlorineS.olid phase extractio(nSPE) was used to prepare the samples for LC/MS/MS analysis.A forty-milliploirtteironof sample was transferretdoa C,8 SPE cartridge. The cartridgweas firsetlutedwith5 mL of40% methanol inwater solution.The eluatewas discardedand the SPE column was then elutedwith 100% methanol. A 5 ml portionof methanol was collectedforanalysisby LC/MS/MS. This treatmentresultedinan eight-fold concentratioonfthe samples priortoanalysis. 4.1.2 Sample Analysis by LC/MSIMS In HPLC, an aliquotof extractisinjectedand passed through a liquid-phascehromatographic column. Based on theaffiniotfythe analyteforthestationarpyhase inthe column relativteo theliquimdobile phase,theanalyteisretainedfora characteristaimcount oftime. Following HPLC separation,ES/MS providesa rapidand accuratemeans foranalyzinga wide range of organic compounds, includinfgluorochemicalsE.lectrosprayisgenerallyoperatedat relatively mildtemperatures;moleculesare ionizedf,ragmented,and detected. Ionscharacteristoifc known fluorochemicalasre observed and quantitateadgainststandards. A Hewlett-PackardHP 1100 HPLC system coupledto a Micromass UltimaMS/MS was used to analyzethe sample extractsA.nalysiswas performed using selectedreactionmonitoring (SRM). Samples were extractedon 5/16/00and analyzedby MS/MS oh 5/18100.Sample MC108H was extractedon 5/22100and analyzedon 5/23/00.The HPLC and MS/MS methods used foranalysisand instrumentparameterscan be found inattachment0. 5 Analysis 5.1 Calibration A 7-pointcalibratiocnurve was analyzedat the beginningand end ofthe analyticaslequence forthe compounds of interestT.he calibratiopnointswer-e prepared at0, 25, 50, 100,250, 500, and 1000 ng/L(ppt)The response ofthe quantitafloinonversus the concentratiownas plottedforeach point.Using linearegressionvath1/xweighting,the slope,y-intercepatnd correlatiocnoefficien(tr)and coefficieonftdetermination were determined.A calibration curve isacceptableifr > 0.985 (@ > 0.970). Calibratiosntandardsare preparedusingthe same SPE procedure used forsamples. Calibratiocnheck standardswere analyzedperiodical(leyverythreetofivesample injections) throughoutthe analysissequence. Compliance is obtained ff the standard analyte concentrationsare within+/-20% ofthe actualvalue. For the resultsreportedhere,calibraticorniteriwaere met. PAGE3QF5 5.2 Blanks ExtractbiloannkwserepreparaenddanalyzweidtehvereyxtractbiaotncohfsampleTsh.e extractbiloanksshoulndothaveanytargaentalytperseseanttorabovetheconcentraotfion thelow-leveclalibratisotnandard.Forthesesamples,theextractiobnlankswere compliant. Instrumenbtlanksintheform ofcleanmethanolsolvenwtere alsoanalyzedaftereveryhighlevelcalibratisotnandard,and afterknown high-levsealmples. Again,theblanksshouldnot have any targetanalytespresentator above thelow-leveclalibratisotnandard.For the samplespresentedheretheinstrumenbtlanksarecompliant. 5.3 Surrogates Surrogatespikesarenota componentoftheLC/MS/MS analyticmaelthod. 5.4 Matrix Spikes Matrixspikeswere preparedforeveryfieldsample (excludinbglanks)ata concentratioonf 100 ng/Lusingallcompounds ofinterestM.atrixspikerecoverieasregiveninAttachmentC. Alllaboratormyatrixspikesshowed recoverieosfallcompounds between 70-130%. Fieldspikeswere preparedon sample MC-101H at a concentratiofn100 ng/Lusingall compounds of interestF.ieldspikerecoverieasre alsogiveninAttachmentC. PFOSA showed lowrecoveryinthefielsdpike.AJIothercompounds showed recoveriebsetween 70130%. 5.5 Duplicates Allfieldsamples (excludinbglanks)were analyzedinduplicate.Resultsare givenalong with thesample resultisnAttachmentB. 5.6 Laboratory Control Samples Milliwqaterwas spikedwithallcompound ofinteresatt25 and 250 ng/L.Allrecoveriefsorall compounds were between 70-130% ineach LCS. Recoveriesaregivenwiththeraw datain AttachmentD. 5.7 Sample Related Comments Fieldblanksamples consistedof empty containers.FortymillilitoefrtsypeIwater filtered througha hypercarbcartridgweas added totheempty containearnd analyzedinthesame manner as theothersamples. 6 Data Summary PleaseseeAttachmentB fora detaileldisbnogftheanalyficraeisults. 7 DatalSample Retention Samples aredisposedofone month afterthereportisissuedunlessotherwisespecifiedA.JI electronidcataisarchivedon retrievabmledia and hardcopy reportasre storedindata foldermsaintainedby Centre. PAGE40F5 8 Attachments 8.1 Attachmentk Chain-of-Custody 8.2 AttachmentB: Results. 8.3 AttachmentC: MatrixSpike Recoveries(Fieldand LaboratorySpikes) 8.4 Attachment D: LC/MSIMS Raw AnalyticaDlata 9 Signatures do ohn M. Flah OpAatiods Manager Date Kevin J Lloyd,Vice F@resident Date Other Lab Members Contributintgo Data Enaksha Wickremesinhe Karen Smith David Bell PAGE5QF5 ANALYTICALREPORT -lie 4 CentreAnrc3lytiCal boratorieIsn.c. 814-231-803F2AX814-31-1253 3048ResearcDhrivber,arC;ollePgAe16801 AnalytiRceaslulWt1s973ClevelaTnedn,nesSe 3M Sample Identification MC-101H MC-103H MC-106H NA MC-107H NA MC-108H Sample Description Site1 P/N SurfaceWater SiteI P/N SurfaceWater Duplicate Site2 P/N SurfaceWater Site2 PIN SurfaceWater Duplicate Site3 PIN SurfaceWater Site3 PIN SurfaceWater Duplicate FieldBlankPIN Empty - PFOS (ng/L) 14.7 J < 25 < 25 < 25 < 25 < 25 < 25 J - Compound ispresent,but below the reportinglimiotf 25 ng/L. The resultisan estimatedvalue. PFOSA 5.6 1 < 25 < 25 < 25 < 25 < 25 < 25 (ng/L) Method DetectionLimitsare approximately2.5 ng/LforPFOS and PFOSA and 7.5 ng/L forPOAA. POAA (ng/L) 16.7 J < 25 < 25 < 25 < 25 < 25 < 25 ------------Pleaserefertotnereversesideforour standardtermsand conditions. @artit0 te.,Carlostates E4 e wemiew Acko Are, e-;d9eleoAa@d urtkai lot PC30@ III ap on itftwe%AAtCfes C, PA-W.iiii I r i@states ntvryl;i 60 Fig optr'@cre I ton Hills Maple,t ff FaiFui re 1 Hiwassee Ddnldng Water Plant hd I15o IH4Iogto5ts$ alurrie IIs 0 @%. ohnsioncl le/ Akwgtd id v -c vkv- ro ntajnbfl % a eq60 rcoye ngton g 74 Hie4IV 4t$ o a#oak ,4 a !iA ales re aftey 312 k -,o re a r hard,.. I cres clim .... A) ric eritage Dm Inc.O:IQW GDT. I Addition;gsamplingsites shown on north renvironmentalSampling Sitesfor.Cleveland A r Eriwa&see River Site#3 la 'k EH[iw River Site#2 Rive Site ntville ..,y v Nr,@ ills n FarM SUbd'IYisi0 Ltony Cleveland Municipal POTW emuent) 163 alh L-ca@io Estates urekd Hiw ee Drinidng Water Plant withdrawal so Olga Ee *lot 30 weilLEswl op,@niiq/ 'ew*g@igh6 RinA rw;ke@4atpg I oQimmt=n%l=;OlGWGDT.Im f. t% v oR r 'Acr arri e Hijs 0 es @f ritonHills % h st n circle, Additional sampling sites shown on south map renvironmentalSampline SitesNorth ofCleveland,