Document DMpkYmD1bM21oKeo2yVeEwN05

entreAnalyticLaalboratorieIsn,c,. 048ResearcDhrive StateCollege,PA 16801 wwwcentrelab.com hone:(814)231-8032 Fax:(814)231-1253 or(814)231-1580 AnaWcal Report Fluorochemic,@51 *Characterization of Water and Sediment Samples Port St.Lucie Resamp!ing (EOO-2003) Centre AnalyticalLaboratory Report No. 023-014P Testing Laboratory CentreAnalyticaLlaboratoryI,nc. 3048 Research Ddve State College,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 Dale Bacon Ph.D. 3M Environmental Technology & SafetyServices Bldg. 2-3E-09 P.O. Box 33331 St.Paul,MN 55133-3331 PAW I OF5 Introduction Resultasrereportefdbrtheanalysiosfa serieosfwaterand sedimentsamplesreceivebdy Centre AnalyticaLlaboratoriesI,nc.(Centre)from the 3M EnvironmentalLaboratory.The samples were collectedfrom PortSt.Lucie,Floridaand are partof3M ProjectEOO-2003. The' Centre studynumber assigned to the projectis023-014. Specificfluorochemicaclharacterizatiobny liquidchromatography /tandem mass spectrometry (LCIMS/MS) and ion chromatographywas requestedforallsamples. A totalof 45 samples were receivedforanalysis. The samples were prepared and analyzed by LC/MS/MS forthefollowinglisotffluorochemicals: Table 1:Target Analysis Comoound Name PerfluorooctaneSutfonate -PerfluorooctanSeulfonvlamide Perfluorooctanoate Acronvm PFOS PFOSA POAA The analyticamlethods used forwater samples were validatedby Centre.The validatiopnrotocol and resultsare on filewith Centre. The methods were modifiedforthe sediment samples, however theprocedureshave not been fullvyalidatedforthismatrix.Data presentedhere isthe highestqualitydata availableat thistime. 2 Sample Receipt The samples were submided inindividuapllasticontainersand were not preserved. Forty-five individuaslample containerswere received.Samples were receivedon 7/25/00.The samples were collectedbetween 7/18/00 and 7/19/00.Chain-of-custodiynformatonis presented in Attachment A. 3 Holding Times The analyticamlethod used was validatedagainsta maximum holdingtime of 14 days. Stability afterthistimeperiodhas not been validatedh,owever itshouldbe noted thatfielfdortifications have shown acceptablerecoveriesat the 100 ng/L forperiodslongerthan 14 days. PAGE20FS 4 Methods-Analyticanld Preparatory 4.1 LC/MS/MS 4.1.1 Sample Preparation forLC/MS/MS Analysis Water samples were initialtlryeatedwith 200 uL of 250 mg/L sodium thiosulfatseolubon to remove residualchlorineS.olidphase extracbon(SPE) was used topreparethe samples for. LC/MS/MS analysis.A forty-milliploirtteironofsample was transferretdoa CiaSPE cartridge. The cartridgvem'-s@rit-elutewdith5 mL of40% methanol inwater solution.The eluatewas discardedand the SPE column was then elutedwith 100% methanol. A 5 mL portionof methanolwas collectefdoranalysisby LC/MS/MS. Thistreatmentresultedinan eight-fold concentrationfthesamples priotroanalysis.' For the sedimentand sludgesamples,a representatipvoertionofsample (5 grams) was first extracteidnto5 mi ofmethanol.The extractswere filteraendd dilutetdoa finavlolume of40 mL withType Iwater.The diluteedxtractwsere thentreatedinthesame manner as thewater samples,beginningwiththesolidphase extraction. 4.1.2 Sample Analysis by LC/MSIMS InHPLC, an aliquotofextractisinjectedand passed througha liquid-phascehromatographic column. Based on theaffiniotfytheanalyteforthestationarpyhase inthecolumn relativteo theliquimdobile phase,the analyteis-retainefdora charactedstcamount ofUme. Following HPLC separabon,ES/MS providesa rapidand accuratemeans foranalyzinga vade rangeof organiccompounds, includinfgluorochemicalsE.lectrospraiysgeneralloyperatedatrelatively mildtemperaturesm;oleculesare ionizedf,ragmented,and detected.Ionscharacteristoifc known fluorochemicalasreobserved and quantitateadgainststandards. A Hewlett-PackardHPI.100HPLC system coupledtoa Micromass Ultma MS/MS was used to analyzethe sample extractsA.nalysiswas performedusingselectedreactionmonitoring (SRM). Water samples were extractedbetween 8115100and 8/17/00and analyzedby MS/MS between 8/18/00and 8/23/00.Sediment and sludgesamples were extractedon 8/18/00and were analyzedby MS/MS on 8121/00.The HPLC and MS/MS methods used foranalysisand instrumentparameterscan be found inAttachmentsD and E. 5 Analysis 5.1 Calibration A 7-pointcalibraboncurvewas analyzedatthe beginningand end ofthe analyticaslequence forthecompounds of interesTth.e calibratipoonintswere preparedat 0, 25,50, 100,250, 500, and 1000 ng/L (ppt)for LC/MS/MS analysisT.he instrumentresponseversusthe concentratiownas plottefdoreach point.Usinglinearegressiownith1/xweightingt,he slope, y-interceapntd correlaticoonefficie(nrt)and coefficieonftdeterminatio(n@)were determined. A calibrabocnurveisacceptableI r> 0.985(r,>20.970). Calibrabonstandardsarepreparedusingthesame S.PE procedureused forsamples. PAGE30FS Calibratiocnheck standardswere analyzed periodical(leyverythreetofivesample injections) throughoutthe analysissequence. Compliance is obtained ff the standard analyte concentrationasre within+/-20% ofthe actualvalue. For theresultsreportedhere,calibratiocnriteriwaere met. 5.2 Blanks Extracfiobnlanks were prepared and analyzed withevery extractiobnatch of samples. The extractiobnlanksshouldnothave any targetanalytespresentator above theconcentrationof the low-leveclalibratiosntandard.For these samples, the extractiobnlankswere complia6t. Instrumentblanks-int.tleform ofcleanmethanol solventwere alsoanalyzed aftereveryhighlevelcalibratiosnianda@d,and afterknown high-leveslamples. Again,the blanksshould not have any targetanalytespresentat or above the low-levelcalib-rabosnt.andard. For the samples presentedhere the instrumentblanks are compliant. 5.3 Surrogates Surrogatespikesare not a component of the LC/MS/MS analyticamlethods. 5.4 MatrixSpikes Matrixspikeswere preparedforevery fieldsample usingallcompounds of interestMatrix spikerecoveriesare giveninAttachment C. Fieldspikeswere submittedwiththewater samples. Fieldspikerecoveriesare alsoincluded inAttachmentC. The resultfsrom the200 pptfielsdpikeforsample QSW Palm City-C-FMS200pptA indicattehatthissample was spikedat1000 pptratherthan200 ppt. The resultfsor QSW Palm-City-C-FMS-200pptB indicatea 200 ppt spikingconcentrafion. 5.5 Duplicates Allfielsdamples were analyzed induplicate.Resultsare givenalong withthe sample results inAttachment B. 5.6 LaboratoryControlSamples For LC/MS/MS analyses,Milliwqater was spiked withallcompounds of interesatt 25 and 250 ng/L duringeach extractiosnet. Allrecoveriesforallcompounds were between 70-130% in each LCS. Resultsare given along withthe raw data inAttachments D and E. 5.7 Sample RelatedComments There are no othersample relatedcomments forthisdata seL 6 Data Summary Please see Attachment B fora detailedlistinogf the analyticarlesults.Surface water results are reportedinpartsper trilli(opnpt)(ngIL).Sediment and sludgesample resultsare reported inpartsperbillio(nppb)(ng/g)on both an as-receivedand dry-weightbasis. PAG64OFS 7 DatalSample Retention SamplesaredisposeodfonemonthaftetrhereporitsissueudnlesostherwisspeecifieAdJ.I electronidcata isarchivedon retrievablmedia and hard copy reportsare storedin data foldersmaintainedby Centre. 8 Attachments 8.1 AttachmentA-Chah-of-Custody 8.2 Attachment B: Results. 8.3 AttachmentC: MatrixSpikeRecoveries 8.4 AttachmentD: LC/MS/MS Raw AnalyticaDlata (SurfaceWater Samples) 8.5 AttachmentE: LC/MSIMS Raw AnalyticaDlata (Sedimentand SludgeSamples) 9 Signatures l@7 ohn M. Flaherty, a O0perafionsManager Date KevinJ Uoyd, Vice President Date OtherLab Members ContributintgoData Karen Smith PAGESOF5 ANALYTICARLEPORT771 Centre Analytical Laboratoric=sI,nc. 3048 Research Drive,State CollegePA 16801 814-231-8032 FAX 814-231-1253 AnalyticalResults EOO-2003 PortSt.Lucie,FL Resampling (watersamples) 3M Sample Identification MDWPIN-R-0-C MDWPIN-R-0-C dup MDWPIN-Lime-C MDWPIN-Lime-C dup MDWPOut -C MDWPOut-C dup NPWWTPEff -C NPWWTPEff-C dup NPWWTPCC-C NPWWTPCC-C dup PSLF Leach-C PSLF Leach-C dup TW#2 FireDept-C TW#2 FireDept-C dup SW#3 SH-C SW#3 SH-C dup TW#3 Penpark-C TW#3 Penpark-C dup SW#l Penpark-C SW#l Penpark-C dup TW#l HolidayInn-C TW#l Holiday Inn-C dup SW#2 MCM-C SW#2 MCM-C dup OSW Palm City-C QSW Palm City-Cdup BlindDup Cl BlindDup Cl dup BlindDup C2 Blind Dup C2 dup PFOS (ng/L) <25 < 25 < 25 -c2.5 <25 <25 14.7 J 16.6 J 85.5 78.8 429 425 < 25 < 25 7.8 J 5.4 J < 25 < 25 5.2 J 4.1 J <25 <25 7.7 J 9.3 J 2930 2850 <25 < 25 8.0 J 9.8 J PFOSA (ng/L) or < 25 < 25 < 25 < 25 < 25 < 25 < 25 4.4 J 3.5 J 7.0 1 8.0 J < 25 < 25 < 25 < 25 < 25 < 25 < 25 < 25 < 25 < 25 < 25 < 25 30.0 27.5 < 25 < 25 < 25 < 25 POAA (ng/L) < 25 < 25 < 25 < 25 < 25 < 25 15.11 14.1 J 42.9 40.2 1030 1020 < 25 < 25 < 25 < 25 < 25 < 25 < 25 < 25 <25 < 25 < 25 < 25 96.9 97.1 < 25 < 25 < 25 < 25 J - Compound ispresent,but below the reportinglimitof 25 ng/L. The resultisan estimated value. Method Detection Limitsare approximately 2.5 ng/L forPFOS and PFOSA and 7.5 ng/L forPOAA. pl@assrefertoft reveme sideforourstandardtonnsand conditions. jot" ANALYTICALREPORT,;,@@, Centrc=.Analytical ao\k\W@ Laboratoric=s,Inc. 3048 Research Drive,State College PA 16801 814-231-8032 FAX 814-231-1253 AnalyticalResults EOO-2003 Port St.Lucie,FL Resampling (solids) 3M Sample Identification NPWWTP Sludge-C NPWWTP Sludge-C dup SED #3 SH-C SED #3 SH-C dup SED#L Penpark-C SED#L Penpark-C dup SED#2 MCM-C SED#2 MCM-C dup PFOS (ug/Kg) (as received) 1.36 1.30 < 0.200 < 0.200 < 0.200 < 0.200 < 0.200 < 0.200 PFOSA (ug/Kg) (asreceived) < 0.200' < 0.200 < 0.200 < 0.200 < 0.200 < 0.200 < 0.200 < 0.200 POAA (ug/Kg) (as received) < 0.200 < 0.200 < 0.200 < 0.200 < 0.200 < 0.200 < 0.200 < 0.200 3M Sample Identification NPWWTP Sludge-C NPWWTP Sludge-C dup SED #3 SH-C SED #3 SH-C dup SED#L Penpark-C SED#L Penpark-C dup SED#2 MCM-C SED#2 MCM-C dup. PFOS (ug/Kg) (dryweight) 62.9 60.2 < 0.261 < 0.261 < 0.263 < 0.263 < 0.304 < 0.304 PFOSA (ug/Kg) (dryweight) < 9.3 < 9.3 < 0.261 < 0.261 < 0.263 < 0.263 < 0.304 < 0.304 POAA (ug/Kg) (dryweight) < 9.3 < 9.3 < 0.261 < 0.261 < 0.263 < 0.263 < 0.304 < 0.304 J - Compound ispresent,but below the reportinglimit.The resultisan estimated value. A!Tk pleaserefertothervversesideforourstandardtermsand conditions. 70 r ....... .7-. ............. xa6rt 709 707 . .......... E PortsL IAI ic .....r Landcfi ...... rn . ........... .......... ............... v........................... T- .11..1............. Northport WWTP 709 t;A't Drinking Water riant OL ry 019M hiAPQI stcom no.:01mg Additionalsamplingsites I shown on imuthmap lenvironmentalSampling SitesNorth,ofPortSt.Lucie, Additionalsampling sites shown on northmap 0 jensen4 A, Skyln r L ':.6pc@5.1 t :Tilt, e par -cig Stuart Harbor Rite#3 Pen d rvis Cove Park ........... Site#1 LI Pal ity, I FL quiet w ater 7 A Martin County Marina Site#2 01 ON Nobpq mm ccn% I= 01090 G DT. Ino. EnvironmentalSampling SitesSouth ofPort St.Lucie,FL