Document 2jpa29kR1pw8g9NawOzog33KN

ANALYTICALREPORT Cc=ntrc=Analytical @*Nk ailL6a.boratoriFs, Inc. 3048ResearchDrive,StateCollegePA 16801- 814-231-8032 FAX 814-231-1253 AnalyticRaelsultWs2336 Columbus,GA 3M Sample Identification Sample Description PFOS (ng[L) MC-501 H MC-503H MC-506H NA MC-507H NA MC-508H MC-584H NA Site1 P/N SurfaceWater 63.8 SiteI P/N SurfaceWater Duplicate 59.9 Site2 P/N SurfaceWater 76.6 Site2 PIN SurfaceWater Duplicate 83.3 Site3 P/N SurfaceWater 55.4 Site3 P/N SurfaceWater Duplicate 55.4 FieldBlank-P/N Empty < 25 QuietSurfaceWater < 25 Quiet SurfaceWater Duplicate < 25 i - Compound ispresent,but below thereportinglimiotf 25 ng/L. The resultisan estimatedvalue. Method DetectionUmits areappmximately 2.5 ng/LforPFOS and PFOSA and 7.5 ng/LforPOAA. PFOSA (ngfl) 11.7 1 13.2 J 16.5J 17.6J 12.0J 14.9J < 25 < 25 < 25 POAA (ngtl) 26.1 25.6 26.1 26.7 23.6 J 24.3 J < 25 c 25 < 25 Please referto the reverse side for our standard terms and conditions. CentreAnalyticaLlaboratoriesI,nc. 3048ResearchDrive StateCollege,PA 16801 one: (814)231-8032 Fax:(814)231-1253 or(814)231-1580 Analyd(;Raelport FluorochemicalCharacterizatioonf SurfaceWater Samples Columbus, GA (W2336) Centre AnalyticalLaboratory Report No. 023-014E TestingLaboratory CentreAnalyticaLlaboratoryI,nc. 3048 Research Ddve 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 Kds J.Hansen, Ph.D. 3M EnvironmentalTechnology & SafetyServices Bldg.2-3E-09 P.O. Box 33331 St.Paul,MN 55133-3331 PAGE I OF5 Introduction Resultasrereportefdortheanalysiosfa serieosfsurfacweatersamplesreceivebdyCentre AnalyticaLlaboratoriesI,nc.(Centre)from the 3M EnvironmentalLaboratory.The samples were collectefdrom Columbus, GA. The Centrestudynumber assignedtotheprojectis023-014. Specificfluorochemicaclharacterizatiboyn liquicdhromatography / tandem mass spectrometry (LC/MS/MS) was requestedforallsamples. A totaolf 8 samples were receivedforanalysis. The samples were preparedand analyzedby LC/MSIMS forthefollowinglisotffluorochemicals: Table 1:TargetAnalysis Comt)ound Name PeffluorooctanSeulfonate -PerfluorooctanSeulfonviamide Perfluorooctanoate Acronvm PFOS PFOSA POAA' The analyticamlethod used was validatedby Centre. The validatiopnrotocoland resultsare on filweithCentre. Data presentedhere isthehighestqualitdyataavailableatthistime. 2 Sample Receipt The samples were submitted in individuapllasticontainersand were not preserved. Eight individuaslample containerswere received.Samples were receivedon 05/03100.The sample collectiodnateswere not supplied.Chain-of-custodiynformatioinspresentedinAttachmentA- 3 Holding Times The analyticamlethod used was validatedagainsta maximum holdingtime of 14 days. The stabiliotfytheanalytesofinteresftorlongerperiodshas notbeen determined. PAGE 2OF5 4 Methods -Analyticalnd Preparatory 4.1 LC/MS/MS 4.1.1 Sample PreparatiofnorLC/MSIMS Analysis Samples were initiatlrleyatewdith200 uL of250 mg/L sodiumthiosulfastoelutiotno remove residualchlorineS.olid phase extraction(SPE) was used to prepare the samples for LC/MS/MS analysisA. forty-milliplodretrioonfsamplewas transferretdoa C,8SPE cartridge. The cartridgewas firsetlutedwith5 mL of 40% 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 concentrationofthe samples priorto analysis. 4.1.2 Sample Analysis by LCIMSIMS In HPLC, an aliquotof extractisinjectedand passed through a liquid-phasechromatographic column. Based on the affinitoyf the analyteforthe stationarpyhase inthe column relafivteo theliquidmobile phase, the analytiesretainfeodra charactedsfiacmount of time. Following HPLC separation,ES/MS providesa rapidand accurate means for analyzinga wide range of organic compounds, includingfluorochemicals.Electrosprayisgenerallyoperated at relafively mild temperatures;molecules are ionized,fragmented,and detected. Ions characteristiocf known fluorochemicalsare observed and quantitatedagainststandards. A Hewlett-PackardHP1 100 HPLC system coupled toa Micromass Ulfima MS/MS was used to analyze the sample extracts.Analysiswas performed using selected reactionmonitoring (SRM). Samples were extractedon 5/18/00and analyzed by MS/MS between 5/20/00 and 5121/00.The HPLC and MS/MS methods used foranalysisand instrumentparameters can be found inattachment D. 5 Analysis 5.1 Calibration A 7-pointcalibratiocnurve was analyzed at the beginningpnd end of the analyticaslequence forthe compounds of interestT.he calibratiopnointswere prepared at 0, 25, 50, 100, 250, 500, and 1000 ng/L (ppt)The response of the quantitabonion versus the concentrationwas plottedforeach point. Using linearregressionwith 1/xweighfing,the slope,y-intercepatnd correlatiocnoefficien(tr)and coefficienotf detenninabon(r2)were determined. A calibration curve isacceptableffr> 0.985 (r2> 0.970). Calibrationstandardsare prepared usingthe same SPE procedure used forsamples. Calibratiocnheck standards were analyzed periodicall(yeverythree to fivesample injecbons) throughout the analysissequence. Compliance is obtained if the standard analyte concentrationsare within+/-20% ofthe actualvalue. For the resultsreportedhere,calibratiocnriteriwaere met. PAGE 3 OF 5 5.2 Blanks Extracfibolnankswereprepared'anadnalyzewditheveryextractiboantchofsamples.The extractiobnlanksshouldnothave any targetanalytespresentat or above the concentratioonf thelow-leveclalibratisotnandard.For thesesamples, theextractiobnlankswere compliant. Instrumentblanksinthe form of clean methanol solventwere alsoanalyzedaftereveryhighlevelcalibratisotnandard,and afterknown high-leveslamples. Again,the blanksshould not have any targetanalytespresentat or above the low-leveclalibratiosntandard. For the samples presentedherethe instrumentblanksare compliant. 5.3 Surrogates Surrogatespikesarenot a component of theLC/MS/MS analyticamlethod. 5.4 MatrixSpikes Matrixspikeswere preparedforeveryfieldsample (excludingblanks)ata concentratioonf 100 ng/Lusingallcompounds of interestM.atrixspikerecoveriesare giveninAttachment C. Allcompounds showed matrixspikerecoveriesbetween 70-130% inallsamples. Fieldspikeswere prepared-onsample MC-501H at a concentratioonf 100 ng/L using all compounds ofinterestF.ieldspikerecoveriesare alsogiven inAttachment C. The fieldspike resultshowed low recoveryforPFOSK AJIothercompounds showed matrixspikerecoveries between 70-130%. 5.5 Duplicates Ad]samples (excludinbglanks)were analyzedinduplicate.Resultsare givenalongwiththe sample resultsinAttachment B. 5.6 LaboratoryControlSamples Milliwqaterwas spikedwithallcompound of interesatt 25 and 250 ng/L.Allrecoveriesforall compounds were between 70-130% in each LCS. Resultsare givenalong withthe raw data inAttachment D. 5.7 Sample RelatedComments Fieldblanksamples consistedof empty containers.Fortymillilitoefrtsype Iwater filtered througha hypercarbcartridgweas added to the empty containerand analyzedinthe same manner as the othersamples. 6 Data Summafy Please see AttachmentB fora detailedlistinogfthe analyticarlesults. 7 DatalSample Retention Samples are disposedof one month afterthe reportisissuedunless otherwisespecified.All electronidcata isarchivedon retrievablmeedia and hard copy reportsare storedin data foldersmaintainedby Centre. PAGE 4 OF S 8 Attachments 8.1 Attachmentk Chain-of-Custody 8.2 AttachmentB:Resufts. 8.3 AttachmentC: MatrixSpikeRecove6es (Fieldand LaboratorySpikes) 8.4 AttachmentD: LC/MS/MS Raw AnalyticaDlata 9 Signatures //,Ohn M. Fl e a a er-OperabonsManager KevinJ Uoyd, VicePresident Date .7-4m 2,elDate Other Lab Members Conthbubng toData Enaksha Wickremesinhe Karen Smith David Bell PAGE50F5 ENVIRONMENTAL MONITORING: MULTI-CITY STUDY SURFACE WATER August 2000 As fullydescribedintheMay 4,2000 submittaltoEPA, themulti-citsytudywas designedtoobtainpreliminarydata about dispersioonffluorochemicalisnthe environment,uptake intofoods,and presenceindrinkingwater tounderstand the potentiaslourcesofhuman and environmentalexposuresthatmight resultfrom this typeofdispersionT.he multi-citsytudypaireda cityhavingmanufacturingor commercial use offluorochemicalproductsbased on customer saleswith a citythat doesnot.Initiallsyixcities(,threepairs)are beingexamined. The studymay be expanded depending on furtherresults. Based on furtherreviewand analysisofinformationpertainingto manufacturingor commercial use offluorochemicalsi,thas been learnedthatfiveofthe sixcity locationfsallintothatcategoryofsupplylocationsT.hus, thesix-citsytudyprogram shouldbe consideredasa broad based environmentalmonitoringprogram only, withouttheabilittyodifferentiastuepplychainfrom non-supplychaincities. The multi-citsytudywillyieldenvironmentaldistributiodnata aswellas dataon potentiaslourcesof human exposure.The citiewsere selectedtorepresenturban locationwsith variouslevelsoffluorochemicalreleasesand varioustypesof municipalwater supplies.The samples tobe obtained,where possiblei,nclude: urban air,surfacewater column and surfacemicrolayer,sediment,riverfish, drinkingwater intake,treateddrinkingwater,tapwater,theinfluentoand effluenftrom publicly-ownedwaste treatmentworks,sludge,and municipallandfill leachate.Additionallya, "market basket"ofseveralfoodproductswillbe sampled. These include:beef,pork,chicken,hot dogs,catfishe,ggs,milk,bread,green beans, applesfrom grocerystoresand,ifpossiblep,roduce from localfarmers'markets. The May 4,2000 data provided detailon thedesignand structureofthestudyand representtshefirstresultsfrom themulti-citsytudy.Incl" udedinthatsubmittal were reportson thequalityassuranceplan and fieldsampling proceduresused and theresultosfthedrinkingwater samples takenfrom thesixcitiesT.he results indicatethatdrinkingwater infourcitie(sDecatur,Alabama; Cleveland, Tennessee;Mobile,Alabama; and Port St.Lucie,Florida)did not containdetectable levelosffluorochemicals.Only two citie(sColumbus, Georgia,and Pensacola, Florida)containeddetectablelevelsof sulfonatedfluorochemicalisn the drinking water. See theMay 4,2000 submittalformore detailregardingthesedrinking water resultsI.ncludedagaininthissubmittalarethefieldreportsforuse in reviewingthesurfacewater data. Subsequenttothe originalsubmittalofinformationfortheMulti-citsytudy, additionaalnalyticadlata has been obtainedforvariouswater column samplesfrom thesixcitiesS.amples were collectefdrom surfacewater sources,both flowing streamsand inareasofquietwater.Analyseswere performed forPFOS, PFOA, and PFOSA. Maps of the sample locationsand the data are presented in the attacheddata sheets. In summary, the data indicatesthat in most samples ofthe water column in flowing streams, the levelofPFOS was eitherbelow the detectionlimitof25 ppt or at levels ranging from 25ppt to 83ppt. Analyses of samples collectedfrom quietwaters in three citiesM,obile, Al, Decatur, Al, and Port St.Lucie Fl,showed the presence of PFOS in varying concentrations.There are two setsofdata and reportsfor the quietwater samples in the Port St.Lucie location.The firstsetof data, May 2000, showed anomalous results.Thus, a second setof samples were collectedand analyzed, and summarized in the report dated August 2000. The analysesof samples of the quietwater for Mobile, Decatur, and Port St.Lucie showed levelsof approximately 30ppt, 110ppt, and 2900ppt, respectively.In general,the levelsfound in allsamples are well below the chronic No Observable EffectLevel for PFOS in both fathead minnows, and daphnia magna, both ofwhich have been determined to be 0.30 ppm. This would yielda safetyfactorsof 100 to 10,000.Itisunclear the reason for the findingin the Port St.Lucie quietwater samples, other than to note thatthe sample locationindicatedthe presence of considerablemanmade debris. The concentrationsof the other analytes,PFOA and PFOSA, are very low,with most resultsator below the levelsof quantificationof 25ppt. At three citylocations, PFOA was found in levelslessthan 100ppt. There are no environmental effects expected at these levels. The overallmulti-citystudy iscontinuing.Samples of the leachateand publicly owned treatment works (POTW) plantinfluentand effluentare being analyzed. Validated analyticalprocedures have been developed recentlyforvarious food stuffs,and the market basket sampling program willcommence shortly. Bettler's LaJke ik u-iit.,w.at@r 103 MiRd r bus rizifluei m I ai!iipa c Municipal 7 Marina Marina Site#2 0 r rystwvo e qh tulg* wn-E es Pine Grove Landfill 1-4 r.4- n n tt. A L 01999 Mnpquestoofm lrnme.: 990 GUT, lno.@ @e Additionalsampling sites I shown on south map Environmental Sampling SitesN & E ofColumbus, GA Mzunic!n,iaipal [3!uni!ipal ari arina Site#2 Site#3 %,UIUUIUU3 IU3 Water Works so inn mun 52 anna Site#1 as r c r rv--a, ibb. lu h 7 si 44+: AiEr 7 i lTf a n alin age % Ri@erl&nd v..a&-,a"nPdaLrk ar g t hft PQ--+,coffL Inc.; 01900 GDT. lm Additional sampung sitw shown on north map ri d %@6 Columbus :@2@ YAM e uent Environmental Sampling Sitesfor.Columbus, ri r