epa-1613-hrms-PCBs

Method1613Tetra-throughOcta-ChlorinatedDioxinsandFuransbyIsotopeDilutionHRGC/HRMSOctober1994U.S.EnvironmentalProtectionAgencyOfficeofWaterEngineeringandAnalysisDivision(4303)401MStreetS.W.Washington,D.C.20460AcknowledgmentsThismethodwaspreparedunderthedirectionofWilliamA.TelliardoftheEngineeringandAnalysisDivisionwithintheEPAOfficeofWater.ThisdocumentwaspreparedunderEPAContractNo.68-C3-0337byDynCorpEnvironmentalServicesDivisionwithassistancefromitssubcontractorInterface,Inc.DisclaimerThismethodhasbeenreviewedbytheEngineeringandAnalysisDivision,U.S.EnvironmentalProtectionAgency,andapprovedforpublication.Mentionoftradenamesorcommercialproductsdoesnotconstituteendorsementorrecommendationforuse.Method1613IntroductionMethod1613wasdevelopedbytheUnitedStatesEnvironmentalProtectionAgency'sOfficeofScienceandTechnologyforisomer-specificdeterminationofthe2,3,7,8-substituted,tetra-throughocta-chlorinated,dibenzo-p-dioxinsanddibenzofuransinaqueous,solid,andtissuematricesbyisotopedilution,highresolutioncapillarycolumngaschromatography(HRGC)/highresolutionmassspectrometry(HRMS).Questionsconcerningthismethodoritsapplicationshouldbeaddressedto:W.A.TelliardUSEPAOfficeofWaterAnalyticalMethodsStaffMailCode4303401MStreet,SWWashington,D.C.20460202/260-7120Requestsforadditionalcopiesshouldbedirectedto:WaterResourceCenterMailCodeRC-4100401MStreet,SWWashington,D.C.20460202/260-7786or202/260-2814October1994iiiMethod1613Method1613,RevisionBTetra-throughOcta-ChlorinatedDioxinsandFuransbyIsotopeDilutionHRGC/HRMS1.0 ScopeandApplication1.1 Thismethodisfordeterminationoftetra-throughocta-chlorinateddibenzo-p-dioxins(CDDs)anddibenzofurans(CDFs)inwater,soil,sediment,sludge,tissue,andothersamplematricesbyhighresolutiongaschromatography/highresolutionmassspectrometry(HRGC/HRMS).ThemethodisforuseinEPA'sdatagatheringandmonitoringprogramsassociatedwiththeCleanWaterAct,theResourceConservationandRecoveryAct,theComprehensiveEnvironmentalResponse,CompensationandLiabilityAct,andtheSafeDrinkingWaterAct.ThemethodisbasedonacompilationofEPA,industry,commerciallaboratory,andacademicmethods(References1-6).1.2 Theseventeen2,3,7,8-substitutedCDDs/CDFslistedinTable1maybedeterminedbythismethod.Specificationsarealsoprovidedforseparatedeterminationof2,3,7,8-tetrachloro-dibenzo-p-dioxin(2,3,7,8-TCDD)and2,3,7,8-tetrachloro-dibenzofuran(2,3,7,8-TCDF).1.3 Thedetectionlimitsandquantitationlevelsinthismethodareusuallydependentonthelevelofinterferencesratherthaninstrumentallimitations.Theminimumlevels(MLs)inTable2arethelevelsatwhichtheCDDs/CDFscanbedeterminedwithnointerferencespresent.TheMethodDetectionLimit(MDL)for2,3,7,8-TCDDhasbeendeterminedas4.4pg/L(parts-per-quadrillion)usingthismethod.1.4 TheGC/MSportionsofthismethodareforuseonlybyanalystsexperiencedwithHRGC/HRMSorundertheclosesupervisionofsuchqualifiedpersons.EachlaboratorythatusesthismethodmustdemonstratetheabilitytogenerateacceptableresultsusingtheprocedureinSection9.2.1.5 Thismethodisperformance-based.Theanalystispermittedtomodifythemethodtoovercomeinterferencesorlowerthecostofmeasurements,providedthatallperformancecriteriainthismethodaremet.TherequirementsforestablishingmethodequivalencyaregiveninSection9.1.2.1.6 Anymodificationofthismethod,beyondthoseexpresslypermitted,shallbeconsideredamajormodificationsubjecttoapplicationandapprovalofalternatetestproceduresunder40CFR136.4and136.5.2.0 SummaryofMethodFlowchartsthatsummarizeproceduresforsamplepreparation,extraction,andanalysisaregiveninFigure1foraqueousandsolidsamples,Figure2formulti-phasesamples,andFigure3fortissuesamples.October19941Method16132.1Extraction2.1.1 Aqueoussamples(samplescontaininglessthan1%solids)—Stableisotopicallylabeledanalogsof15ofthe2,3,7,8-substitutedCDDs/CDFsarespikedintoa1Lsample,andthesampleisextractedbyoneofthreeprocedures:2.1.1.1Samplescontainingnovisibleparticlesareextractedwithmethylenechlorideinaseparatoryfunnelorbythesolid-phaseextractiontechniquesummarizedinSection2.1.1.3.Theextractisconcentratedforcleanup.2.1.1.2Samplescontainingvisibleparticlesarevacuumfilteredthroughaglass-fiberfilter.ThefilterisextractedinaSoxhlet/Dean-Stark(SDS)extractor(Reference7),andthefiltrateisextractedwithmethylenechlorideinaseparatoryfunnel.ThemethylenechlorideextractisconcentratedandcombinedwiththeSDSextractpriortocleanup.2.1.1.3Thesampleisvacuumfilteredthroughaglass-fiberfilterontopofasolid-phaseextraction(SPE)disk.ThefilteranddiskareextractedinanSDSextractor,andtheextractisconcentratedforcleanup.2.1.2 Solid,semi-solid,andmulti-phasesamples(butnottissue)—Thelabeledcompoundsarespikedintoasamplecontaining10g(dryweight)ofsolids.Samplescontainingmultiplephasesarepressurefilteredandanyaqueousliquidisdiscarded.Coarsesolidsaregroundorhomogenized.Anynon-aqueousliquidfrommulti-phasesamplesiscombinedwiththesolidsandextractedinanSDSextractor.Theextractisconcentratedforcleanup.2.1.3 Fishandothertissue—Thesampleisextractedbyoneoftwoprocedures:2.1.3.1SoxhletorSDSextraction—A20galiquotofsampleishomogenized,anda10galiquotisspikedwiththelabeledcompounds.Thesamplei