constructedwww.ddd138.com

www.
epa.
govMethod625:Base/NeutralsandAcidsPromulgated1984APPENDIXATOPART136METHODSFORORGANICCHEMICALANALYSISOFMUNICIPALANDINDUSTRIALWASTEWATERMETHOD625—BASE/NEUTRALSANDACIDS1.
ScopeandApplication1.
1Thismethodcoversthedeterminationofanumberoforganiccompoundsthatarepartitionedintoanorganicsolventandareamenabletogaschromatography.
TheparameterslistedinTables1and2maybequalitativelyandquantitativelydeterminedusingthismethod.
1.
2ThemethodmaybeextendedtoincludetheparameterslistedinTable3.
Benzidinecanbesubjecttooxidativelossesduringsolventconcentration.
Underthealkalineconditionsoftheextractionstep,a-BHC,y-BHC,endosulfanIandII,andendrinaresubjecttodecomposition.
Hexachlorocyclopentadieneissubjecttothermaldecompositionintheinletofthegaschromatograph,chemicalreactioninacetonesolution,andphotochemicaldecomposition.
N-nitrosodimethylamineisdifficulttoseparatefromthesolventunderthechromatographicconditionsdescribed.
N-nitrosodiphenylaminedecomposesinthegaschromatographicinletandcannotbeseparatedfromdiphenylamine.
ThepreferredmethodforeachoftheseparametersislistedinTable3.
1.
3Thisisagaschromatographic/massspectrometry(GC/MS)method2,14applicabletothedeterminationofthecompoundslistedinTables1,2,and3inmunicipalandindustrialdischargesasprovidedunder40CFRPart136.
1.
11.
4Themethoddetectionlimit(MDL,definedinSection16.
1)foreachparameterislistedinTables4and5.
TheMDLforaspecificwastewatermaydifferfromthoselisted,dependinguponthenatureofinterferencesinthesamplematrix.
1.
5Anymodificationtothismethod,beyondthoseexpresslypermitted,shallbeconsideredasamajormodificationsubjecttoapplicationandapprovalofalternatetestproceduresunder40CFRParts136.
4and136.
5.
Dependinguponthenatureofthemodificationandtheextentofintendeduse,theapplicantmayberequiredtodemonstratethatthemodificationswillproduceequivalentresultswhenappliedtorelevantwastewaters.
1.
6Thismethodisrestrictedtousebyorunderthesupervisionofanalystsexperiencedintheuseofagaschromatograph/massspectrometerandintheinterpretationofmassspectra.
EachanalystmustdemonstratetheabilitytogenerateacceptableresultswiththismethodusingtheproceduredescribedinSection8.
2.
2.
SummaryofMethod2.
1Ameasuredvolumeofsample,approximately1L,isseriallyextractedwithmethylenechlorideatapHgreaterthan11andagainatapHlessthan2usingaseparatoryfunneloracontinuousextractor.
2Themethylenechlorideextractisdried,concentratedtoavolumeof1mL,andanalyzedbyGC/MS.
Qualitativeidentificationoftheparametersintheextractisperformedusingtheretentiontimeandtherelativeabundanceofthreecharacteristicmasses(m/z).
Quantitativeanalysisisperformedusinginternalstandardtechniqueswithasinglecharacteristicm/z.
3.
Interferences3.
1Methodinterferencesmaybecausedbycontaminantsinsolvents,reagents,glassware,andothersampleprocessinghardwarethatleadtodiscreteartifactsand/orelevatedbaselinesinthetotalioncurrentprofiles.
AllofthesematerialsmustberoutinelydemonstratedtobefreefrominterferencesundertheconditionsoftheanalysisbyrunninglaboratoryreagentblanksasdescribedinSection8.
1.
3.
3.
1.
1Glasswaremustbescrupulouslycleaned.
3Cleanallglasswareassoonaspossibleafterusebyrinsingwiththelastsolventusedinit.
Solventrinsingshouldbefollowedbydetergentwashingwithhotwater,andrinseswithtapwateranddistilledwater.
Theglasswareshouldthenbedraineddry,andheatedinamufflefurnaceat400°Cfor15-30minutes.
Somethermallystablematerials,suchasPCBs,maynotbeeliminatedbythistreatment.
Solventrinseswithacetoneandpesticidequalityhexanemaybesubstitutedforthemufflefurnaceheating.
ThoroughrinsingwithsuchsolventsusuallyeliminatesPCBinterference.
Volumetricwareshouldnotbeheatedinamufflefurnace.
Afterdryingandcooling,glasswareshouldbesealedandstoredinacleanenvironmenttopreventanyaccumulationofdustorothercontaminants.
Storeinvertedorcappedwithaluminumfoil.
3.
1.
2Theuseofhighpurityreagentsandsolventshelpstominimizeinterferenceproblems.
Purificationofsolventsbydistillationinall-glasssystemsmayberequired.
3.
2Matrixinterferencesmaybecausedbycontaminantsthatareco-extractedfromthesample.
Theextentofmatrixinterferenceswillvaryconsiderablyfromsourcetosource,dependinguponthenatureanddiversityoftheindustrialcomplexormunicipalitybeingsampled.
3.
3Thebase-neutralextractionmaycausesignificantlyreducedrecoveryofphenol,2-methylphenol,and2,4-dimethylphenol.
Theanalystmustrecognizethatresultsobtainedundertheseconditionsareminimumconcentrations.
3.
4Thepackedgaschromatographiccolumnsrecommendedforthebasicfractionmaynotexhibitsufficientresolutionforcertainisomericpairsincludingthefollowing:anthraceneandphenanthrene;chryseneandbenzo(a)anthracene;andbenzo(b)fluorantheneandbenzo(k)fluoranthene.
Thegaschromatographicretentiontimeandmassspectraforthesepairsofcompoundsarenotsufficientlydifferenttomakeanunambiguousidentification.
Alternativetechniquesshouldbeusedtoidentifyandquantifythesespecificcompounds,suchasMethod610.
3.
5Insamplesthatcontainaninordinatenumberofinterferences,theuseofchemicalionization(CI)massspectrometrymaymakeidentificationeasier.
Tables6and7givecharacteristicCIionsformostofthecompoundscoveredbythismethod.
TheuseofCImassspectrometrytosupportelectronionization(EI)massspectrometryisencouragedbutnotrequired.
4.
Safety4.
1Thetoxicityorcarcinogenicityofeachreagentusedinthismethodhavenotbeenpreciselydefined;however,eachchemicalcompoundshouldbetreatedasapotentialhealthhazard.
Fromthisviewpoint,exposuretothesechemicalsmustbereducedtothelowestpossiblelevelbywhatevermeansavailable.
ThelaboratoryisresponsibleformaintainingacurrentawarenessfileofOSHAregulationsregardingthesafehandlingofthechemicalsspecifiedinthismethod.
Areferencefileofmaterialdatahandlingsheetsshouldalsobemadeavailabletoallpersonnelinvolvedinthechemicalanalysis.
Additionalreferencestolaboratorysafetyareavailableandhavebeenidentified4-6fortheinformationoftheanalyst.
4.
2Thefollowingparameterscoveredbythismethodhavebeententativelyclassifiedasknownorsuspected,humanormammaliancarcinogens:benzo(a)anthracene,benzidine,3,3′-dichlorobenzidine,benzo(a)pyrene,a-BHC,P-BHC,o-BHC,y-BHC,dibenzo(a,h)anthracene,N-nitrosodimethylamine,4,4′-DDT,andpolychlorinatedbiphenyls(PCBs).
Primarystandardsofthesetoxiccompoundsshouldbepreparedinahood.
ANIOSH/MESAapprovedtoxicgasrespiratorshouldbewornwhentheanalysthandleshighconcentrationsofthesetoxiccompounds.
5.
ApparatusandMaterials5.
1Samplingequipment,fordiscreteorcompositsampling.
5.
1.
1Grabsamplebottle—1Lor1qt,amberglass,fittedwithascrewcaplinedwithTeflon.
FoilmaybesubstitutedforTeflonifthesampleisnotcorrosive.
Ifamberbottlesarenotavailable,protectsamplesfromlight.
Thebottleandcaplinermustbewashed,rinsedwithacetoneormethylenechloride,anddriedbeforeusetominimizecontamination.
5.
1.
2Automaticsampler(optional)—Thesamplermustincorporateglasssamplecontainersforthecollectionofaminimumof250mLofsample.
Samplecontainersmustbekeptrefrigeratedat4°Candprotectedfromlightduringcompositing.
Ifthesamplerusesaperistalticpump,aminimumlengthofcompressiblesiliconerubbertubingmaybeused.
Beforeuse,however,thecompressibletubingshouldbethroughlyrinsedwithmethanol,followedbyrepeatedrinsingswithdistilledwatertominimizethepotentialforcontaminationofthesample.
Anintegratingflowmeterisrequiredtocollectflowproportionalcomposites.
5.
2Glassware(Allspecificationsaresuggested.
Catalognumbersareincludedforillustrationonly.
)5.
2.
1Separatoryfunnel—2L,withTeflonstopcock.
5.
2.
2Dryingcolumn—Chromatographiccolumn,19mmID,withcoarsefrit5.
2.
3Concentratortube,Kuderna-Danish—10mL,graduated(KontesK-570050-1025orequivalent).
Calibrationmustbecheckedatthevolumesemployedinthetest.
Groundglassstopperisusedtopreventevaporationofextracts.
5.
2.
4Evaporativeflask,Kuderna-Danish—500mL(KontesK-57001-0500orequivalent).
Attachtoconcentratortubewithsprings.
5.
2.
5Snydercolumn,Kuderna-Danish—Threeallmacro(KontesK-503000-0121orequivalent).
5.
2.
6Snydercolumn,Kuderna-Danish—Two-ballmacro(KontesK-569001-0219orequivalent).
5.
2.
7Vials—10-15mL,amberglass,withTeflon-linedscrewcap.
5.
2.
8Continuousliquid-liquidextractor—EquippedwithTeflonorglassconnectingjointsandstopcocksrequiringnolubrication.
(Hershberg-WolfExtractor,AceGlassCompany,Vineland,N.
J.
,P/N6841-10orequivalent.
)5.
3Boilingchips—Approximately10/40mesh.
Heatto400°Cfor30minutesofSoxhletextractwithmethylenechloride.
5.
4Waterbath—Heated,withconcentricringcover,capableoftemperaturecontrol(±2°C).
Thebathshouldbeusedinahood.
5.
5Balance—Analytical,capableofaccuratelyweighing0.
0001g.
5.
6GC/MSsystem5.
6.
1GasChromatograph—Ananalyticalsystemcompletewithatemperatureprogrammablegaschromatographandallrequiredaccessoriesincludingsyringes,analyticalcolumns,andgases.
Theinjectionportmustbedesignedforon-columninjectionwhenusingpackedcolumnsandforsplitlessinjectionwhenusingcapillarycolumns.
5.
6.
2Columnforbase/neutrals—1.
8mlongx2mmIDglass,packedwith3%SP-2250onSupelcoport(100/120mesh)orequivalent.
ThiscolumnwasusedtodevelopthemethodperformancestatementsinSection16.
GuidelinesfortheuseofalternatecolumnpackingsareprovidedinSection13.
1.
5.
6.
3Columnforacids—1.
8mlongx2mmIDglass,packedwith1%SP-1240DAonSupelcoport(100/120mesh)orequivalent.
ThiscolumnwasusedtodevelopthemethodperformancestatementsinSection16.
GuidelinesfortheuseofalternatecolumnpackingsaregiveninSection13.
1.
5.
6.
4Massspectrometer—Capableofscanningfrom35-450amueverysevensecondsorless,utilizinga70V(nominal)electronenergyintheelectronimpactionizationmode,andproducingamassspectrumwhichmeetsallthecriteriainTable9when50ngofdecafluorotriphenylphosphine(DFTPP;bis(perfluorophenyl)phenylphosphine)isinjectedthroughtheGCinlet.
5.
6.
5GC/MSinterface—AnyGCtoMSinterfacethatgivesacceptablecalibrationpointsat50ngperinjectionforeachoftheparametersofinterestandachievesallacceptableperformancecriteria(Section12)maybeused.
GCtoMSinterfacesconstructedofallglassorglass-linedmaterialsarerecommended.
Glasscanbedeactivatedbysilanizingwithdichlorodimethylsilane.
5.
6.
6Datasystem—Acomputersystemmustbeinterfacedtothemassspectrometerthatallowsthecontinuousacquisitionandstorageonmachine-readablemediaofallmassspectraobtainedthroughoutthedurationofthechromatographicprogram.
ThecomputermusthavesoftwarethatallowssearchinganyGC/MSdatafileforspecificm/zandplottingsuchm/zabundancesversustimeorscannumber.
ThistypeofplotisdefinedasanExtractedIonCurrentProfile(EICP).
SoftwaremustalsobeavailablethatallowsintegratingtheabundanceinanyEICPbetweenspecifiedtimeorscannumberlimits.
6.
Reagents6.
1Reagentwater—ReagentwaterisdefinedasawaterinwhichaninterferentisnotobservedattheMDLoftheparametersofinterest.
6.
2Sodiumhydroxidesolution(10N)—Dissolve40gofNaOH(ACS)inreagentwateranddiluteto100mL.
6.
3Sodiumthiosulfate—(ACS)Granular.
6.
4Sulfuricacid(1+1)—Slowly,add50mLofHSO4(ACS,sp.
gr.
1.
84)to50mLof2reagentwater.
6.
5Acetone,methanol,methlylenechloride—Pesticidequalityorequivalent.
6.
6Sodiumsulfate—(ACS)Granular,anhydrous.
Purifybyheatingat400°Cforfourhoursinashallowtray.
6.
7Stockstandardsolutions(1.
00g/L)—standardsolutionscanbepreparedfrompurestandardmaterialsorpurchasedascertifiedsolutions.
6.
7.
1Preparestockstandardsolutionsbyaccuratelyweighingabout0.
0100gofpurematerial.
Dissolvethematerialinpesticidequalityacetoneorothersuitablesolventanddilutetovolumeina10mLvolumetricflask.
Largervolumescanbeusedattheconvenienceoftheanalyst.
Whencompoundpurityisassayedtobe96%orgreater,theweightmaybeusedwithoutcorrectiontocalculatetheconcentrationofthestockstandard.
Commerciallypreparedstockstandardsmaybeusedatanyconcentrationiftheyarecertifiedbythemanufacturerorbyanindependentsource.
6.
7.
2TransferthestockstandardsolutionsintoTeflon-sealedscrew-capbottles.
Storeat4°Candprotectfromlight.
Stockstandardsolutionsshouldbecheckedfrequentlyforsignsofdegradationorevaporation,especiallyjustpriortopreparingcalibrationstandardsfromthem.
6.
7.
3Stockstandardsolutionsmustbereplacedaftersixmonths,orsoonerifcomparisonwithqualitycontrolchecksamplesindicateaproblem.
6.
8Surrogatestandardspikingsolution—SelectaminimumofthreesurrogatecompoundsfromTable8.
Prepareasurrogatestandardspikingsolutioncontainingeachselectedsurrogatecompoundataconcentrationof100g/mLinacetone.
Additionof1.
00mLofthissolutionto1000mLofsampleisequivalenttoaconcentrationof100g/Lofeachsurrogatestandard.
Storethespikingsolutionat4°CinTeflon-sealedglasscontainer.
Thesolutionshouldbecheckedfrequentlyforstability.
Thesolutionmustbereplacedaftersixmonths,orsoonerifcomparisonwithqualitycontrolcheckstandardsindicatesaproblem.
6.
9DFTPPstandard—Preparea25g/mLsolutionofDFTPPinacetone.
6.
10Qualitycontrolchecksampleconcentrate—SeeSection8.
2.
1.
7.
Calibration7.
1EstablishgaschromatographicoperatingparametersequivalenttothoseindicatedinTable4or5.
7.
2Internalstandardcalibrationprocedure—Tousethisapproach,theanalystmustselectthreeormoreinternalstandardsthataresimilarinanalyticalbehaviortothecompoundsofinterest.
Theanalystmustfurtherdemonstratethatthemeasurementoftheinternalstandardsisnotaffectedbymethodormatrixinterferences.
SomerecommendedinternalstandardsarelistedinTable8.
Usethebasepeakm/zastheprimarym/zforquantificationofthestandards.
Ifinterferencesarenoted,useoneofthenexttwomostintensem/zquantitiesforquantification.
7.
2.
1Preparecalibrationstandardsataminimumofthreeconcentrationlevelsforeachparameterofinterestbyaddingappropriatevolumesofoneormorestockstandardstoavolumetricflask.
Toeachcalibrationstandardorstandardmixture,addaknownconstantamountofoneormoreinternalstandards,anddilutetovolumewithacetone.
Oneofthecalibrationstandardsshouldbeataconcentrationnear,butabove,theMDLandtheotherconcentrationsshouldcorrespondtotheexpectedrangeofconcentrationsfoundinrealsamplesorshoulddefinetheworkingrangeoftheGC/MSsystem.
7.
2.
2Usinginjectionsof2-5L,analyzeeachcalibrationstandardaccordingtoSection13andtabulatetheareaoftheprimarycharacteristicm/z(Tables4and5)againstconcentrationforeachcompoundandinternalstandard.
Calculateresponsefactors(RF)foreachcompoundusingEquation1.
Equation1where:A=Areaofthecharacteristicm/zfortheparametertobemeasured.
sAis=Areaofthecharacteristicm/zfortheinternalstandard.
Cis=Concentrationoftheinternalstandard.
C=Concentrationoftheparametertobemeasured.
sIftheRFvalueovertheworkingrangeisaconstant(11withsodiumhydroxidesolution.
10.
3Add60mLofmethylenechloridetothesamplebottle,seal,andshakefor30secondstorinsetheinnersurface.
Transferthesolventtotheseparatoryfunnelandextractthesamplebyshakingthefunnelfortwominuteswithperiodicventingtoreleaseexcesspressure.
Allowtheorganiclayertoseparatefromthewaterphaseforaminimumof10minutes.
Iftheemulsioninterfacebetweenlayersismorethanone-thirdthevolumeofthesolventlayer,theanalystmustemploymechanicaltechniquestocompletethephaseseparation.
Theoptimumtechniquedependsuponthesample,butmayincludestirring,filtrationoftheemulsionthroughglasswool,centrifugation,orotherphysicalmethods.
Collectthemethylenechlorideextractina250mLErlenmeyerflask.
Iftheemulsioncannotbebroken(recoveryoflessthan80%ofthemethylenechloride,correctedforthewatersolubilityofmethylenechloride),transferthesample,solvent,andemulsionintotheextractionchamberofacontinuousextractorandproceedasdescribedinSection11.
3.
10.
4Addasecond60mLvolumeofmethylenechloridetothesamplebottleandrepeattheextractionprocedureasecondtime,combiningtheextractsintheErlenmeyerflask.
Performathirdextractioninthesamemanner.
Labelthecombinedextractasthebase/neutralfraction.
10.
5AdjustthepHoftheaqueousphasetolessthan2usingsulfuricacid.
Seriallyextracttheacidifiedaqueousphasethreetimeswith60mLaliquotsofmethylenechloride.
Collectandcombinetheextractsina250mLErlenmeyerflaskandlabelthecombinedextractsastheacidfraction.
10.
6Foreachfraction,assembleaKuderna-Danish(K-D)concentratorbyattachinga10mLconcentratortubetoa500mLevaporativeflask.
OtherconcentrationdevicesortechniquesmaybeusedinplaceoftheK-DconcentratoriftherequirementsofSection8.
2aremet.
10.
7Foreachfraction,pourthecombinedextractthroughasolvent-rinseddryingcolumncontainingabout10cmofanhydroussodiumsulfate,andcollecttheextractintheK-Dconcentrator.
RinsetheErlenmeyerflaskandcolumnwith20-30mLofmethylenechloridetocompletethequantitativetransfer.
10.
8Addoneortwocleanboilingchipsandattachathree-ballSnydercolumntotheevaporativeflaskforeachfraction.
PreweteachSnydercolumnbyaddingabout1mLofmethylenechloridetothetop.
PlacetheK-Dapparatusonahotwaterbath(60-65°C)sothattheconcentratortubeispartiallyimmersedinthehotwater,andtheentirelowerroundedsurfaceoftheflaskisbathedwithhotvapor.
Adjusttheverticalpositionoftheapparatusandthewatertemperatureasrequiredtocompletetheconcentrationin15-20minutes.
Attheproperrateofdistillationtheballsofthecolumnwillactivelychatterbutthechamberswillnotfloodwithcondensedsolvent.
Whentheapparentvolumeofliquidreaches1mL,removetheK-Dapparatusfromthewaterbathandallowittodrainandcoolforatleast10minutes.
RemovetheSnydercolumnandrinsetheflaskanditslowerjointintotheconcentratortubewith1-2mLofmethylenechloride.
A5mLsyringeisrecommendedforthisoperation.
10.
9Addanotheroneortwocleanboilingchipstotheconcentratortubeforeachfractionandattachatwo-ballmicro-Snydercolumn.
PrewettheSnydercolumnbyaddingabout0.
5mLofmethylenechloridetothetop.
PlacetheK-Dapparatusonahotwaterbath(60-65°C)sothattheconcentratortubeispartiallyimmersedinhotwater.
Adjusttheverticalpositionoftheapparatusandthewatertemperatureasrequiredtocompletetheconcentrationin5-10minutes.
Attheproperrateofdistillationtheballsofthecolumnwillactivelychatterbutthechamberswillnotfloodwithcondensedsolvent.
Whentheapparentvolumeofliquidreachesabout0.
5mL,removetheK-Dapparatusfromthewaterbathandallowittodrainandcoolforatleast10minutes.
RemovetheSnydercolumnandrinsetheflaskanditslowerjointintotheconcentratortubewithapproximately0.
2mLofacetoneormethylenechloride.
Adjustthefinalvolumeto1.
0mLwiththesolvent.
Stoppertheconcentratortubeandstorerefrigeratediffurtherprocessingwillnotbeperformedimmediately.
Iftheextractswillbestoredlongerthantwodays,theyshouldbetransferredtoTeflon-sealedscrew-capvialsandlabeledbase/neutraloracidfractionasappropriate.
10.
10Determinetheoriginalsamplevolumebyrefillingthesamplebottletothemarkandtransferringtheliquidtoa1000mLgraduatedcylinder.
Recordthesamplevolumetothenearest5mL.
11.
ContinuousExtraction11.
1WhenexperiencewithasamplefromagivensourceindicatesthataseriousemulsionproblemwillresultoranemulsionisencounteredusingaseparatoryfunnelinSection10.
3,acontinuousextractorshouldbeused.
11.
2Markthewatermeniscusonthesideofthesamplebottleforlaterdeterminationofsamplevolume.
CheckthepHofthesamplewithwide-rangepHpaperandadjusttopH>11withsodiumhydroxidesolution.
Transferthesampletothecontinuousextractorandusingapipet,add1.
00mLofsurrogatestandardspikingsolutionandmixwell.
Add60mLofmethylenechloridetothesamplebottle,seal,andshakefor30secondstorinsetheinnersurface.
Transferthesolventtotheextractor.
11.
3Repeatthesamplebottlerinsewithanadditional50-100mLportionofmethylenechlorideandaddtherinsetotheextractor.
11.
4Add200-500mLofmethylenechloridetothedistillingflask,addsufficientreagentwatertoensureproperoperation,andextractfor24hours.
Allowtocool,thendetachthedistillingflask.
Dry,concentrate,andsealtheextractasinSections10.
6through10.
9.
11.
5Chargeacleandistillingflaskwith500mLofmethylenechlorideandattachittothecontinuousextractor.
Carefully,whilestirring,adjustthepHoftheaqueousphasetolessthan2usingsulfuricacid.
Extractfor24hours.
Dry,concentrate,andsealtheextractasinSections10.
6through10.
9.
12.
DailyGC/MSPerformanceTests12.
1Atthebeginningofeachdaythatanalysesaretobeperformed,theGC/MSsystemmustbecheckedtoseeifacceptableperformancecriteriaareachievedforDFTPP.
10Eachdaythatbenzidineistobedetermined,thetailingfactorcriteriondescribedinSection12.
4mustbeachieved.
Eachdaythattheacidsaretobedetermined,thetailingfactorcriterioninSection12.
5mustbeachieved.
12.
2Theseperformancetestsrequirethefollowinginstrumentalparameters:ElectronEnergy:70V(nominal)MassRange:35-450amuScanTime:Togiveatleastfivescansperpeakbutnottoexceedsevensecondsperscan.
12.
3DFTPPperformancetest—Atthebeginningofeachday,inject2L(50ng)ofDFTPPstandardsolution.
Obtainabackground-correctedmassspectraofDFTPPandconfirmthatallthekeym/zcriteriainTable9areachieved.
Ifallthecriteriaarenotachieved,theanalystmustretunethemassspectrometerandrepeatthetestuntilallcriteriaareachieved.
Theperformancecriteriamustbeachievedbeforeanysamples,blanks,orstandardsareanalyzed.
ThetailingfactortestsinSections12.
4and12.
5maybeperformedsimultaneouslywiththeDFTPPtest.
12.
4Columnperformancetestforbase/neutrals—Atthebeginningofeachdaythatthebase/neutralfractionistobeanalyzedforbenzidine,thebenzidinetailingfactormustbecalculated.
Inject100ngofbenzidineeitherseparatelyorasapartofastandardmixturethatmaycontainDFTPPandcalculatethetailingfactor.
Thebenzidinetailingfactormustbelessthan3.
0.
CalculationofthetailingfactorisillustratedinFigure13.
11Replacethecolumnpackingifthetailingfactorcriterioncannotbeachieved.
12.
5Columnperformancetestforacids—Atthebeginningofeachdaythattheacidsaretobedetermined,inject50ngofpentachlorophenoleitherseparatelyorasapartofastandardmixthatmaycontainDFTPP.
Thetailingfactorforpentachlorophenolmustbelessthan5.
CalculationofthetailingfactorisillustratedinFigure13.
11Replacethecolumnpackingifthetailingfactorcriterioncannotbeachieved.
13.
GasChromatography/MassSpectrometry13.
1Table4summarizestherecommendedgaschromatographicoperatingconditionsforthebase/neutralfraction.
Table5summarizestherecommendedgaschromatographicoperatingconditionsfortheacidfraction.
IncludedinthesetablesareretentiontimesandMDLthatcanbeachievedundertheseconditions.
ExamplesoftheseparationsachievedbythesecolumnsareshowninFigures1through12.
Otherpackedorcapillary(open-tubular)columnsorchromatographicconditionsmaybeusediftherequirementsofSection8.
2aremet.
13.
2AfterconductingtheGC/MSperformancetestsinSection12,calibratethesystemdailyasdescribedinSection7.
13.
3Theinternalstandardmustbeaddedtosampleextractandmixedthoroughlyimmediatelybeforeitisinjectedintotheinstrument.
Thisprocedureminimizeslossesduetoadsorption,chemicalreactionorevaporation.
13.
4Inject2-5LofthesampleextractorstandardintotheGC/MSsystemusingthesolvent-flushtechnique.
12Smaller(1.
0L)volumesmaybeinjectedifautomaticdevicesareemployed.
Recordthevolumeinjectedtothenearest0.
05L.
13.
5Iftheresponseforanym/zexceedstheworkingrangeoftheGC/MSsystem,dilutetheextractandreanalyze.
13.
6PerformallqualitativeandquantitativemeasurementsasdescribedinSections14and15.
Whentheextractsarenotbeingusedforanalyses,storethemrefrigeratedat4°C,protectedfromlightinscrew-capvialsequippedwithunpiercedTeflon-linedsepta.
14.
QualitativeIdentification14.
1ObtainEICPsfortheprimarym/zandthetwoothermasseslistedinTables4and5.
SeeSection7.
3formassestobeusedwithinternalandsurrogatestandards.
Thefollowingcriteriamustbemettomakeaqualitativeidentification:14.
1.
1Thecharacteristicmassesofeachparameterofinterestmustmaximizeinthesameorwithinonescanofeachother.
14.
1.
2Theretentiontimemustfallwithin±30secondsoftheretentiontimeoftheauthenticcompound.
14.
1.
3TherelativepeakheightsofthethreecharacteristicmassesintheEICPsmustfallwithin±20%oftherelativeintensitiesofthesemassesinareferencemassspectrum.
ThereferencemassspectrumcanbeobtainedfromastandardanalyzedintheGC/MSsystemorfromareferencelibrary.
14.
2Structuralisomersthathaveverysimilarmassspectraandlessthan30secondsdifferenceinretentiontime,canbeexplicitlyidentifiedonlyiftheresolutionbetweenauthenticisomersinastandardmixisacceptable.
Acceptableresolutionisachievedifthebaselinetovalleyheightbetweentheisomersislessthan25%ofthesumofthetwopeakheights.
Otherwise,structuralisomersareidentifiedasisomericpairs.
15.
Calculations15.
1Whenaparameterhasbeenidentified,thequantitationofthatparameterwillbebasedontheintegratedabundancefromtheEICPoftheprimarycharacteristicm/zinTables4and5.
Usethebasepeakm/zforinternalandsurrogatestandards.
Ifthesampleproducesaninterferencefortheprimarym/z,useasecondarycharacteristicm/ztoquantitate.
Calculatetheconcentrationinthesampleusingtheresponsefactor(RF)determinedinSection7.
2.
2andEquation2.
Equation2where:As=Responsefortheparametertobemeasured.
Ais=Responsefortheinternalstandard.
Is=Amountofinternalstandardaddedtoeachextract(g).
Vo=Volumeofwaterextracted(L).
15.
2Reportresultsing/Lwithoutcorrectionforrecoverydata.
AllQCdataobtainedshouldbereportedwiththesampleresults.
16.
MethodPerformance16.
1Themethoddetectionlimit(MDL)isdefinedastheminimumconcentrationofasubstancethatcanbemeasuredandreportedwith99%confidencethatthevalueisabovezero.
1TheMDLconcentrationslistedinTables4and5wereobtainedusingreagentwater.
13TheMDLactuallyachievedinagivenanalysiswillvarydependingoninstrumentsensitivityandmatrixeffects.
16.
2Thismethodwastestedby15laboratoriesusingreagentwater,drinkingwater,surfacewater,andindustrialwastewatersspikedatsixconcentrationsovertherange5-1300g/L.
14Singleoperatorprecision,overallprecision,andmethodaccuracywerefoundtobedirectlyrelatedtotheconcentrationoftheparameterandessentiallyindependentofthesamplematrix.
LinearequationstodescribetheserelationshipsarepresentedinTable7.
17.
ScreeningProcedurefor2,3,7,8-Tetrachlorodibenzo-p-dioxin(2,3,7,8-TCDD)17.
1Ifthesamplemustbescreenedforthepresenceof2,3,7,8-TCDD,itisrecommendedthatthereferencematerialnotbehandledinthelaboratoryunlessextensivesafetyprecautionsareemployed.
Itissufficienttoanalyzethebase/neutralextractbyselectedionmonitoring(SIM)GC/MStechniques,asfollows:17.
1.
1Concentratethebase/neutralextracttoafinalvolumeof0.
2mL.
17.
1.
2Adjustthetemperatureofthebase/neutralcolumn(Section5.
6.
2)to220°C.
17.
1.
3OperatethemassspectrometertoacquiredataintheSIMmodeusingtheionsatm/z257,320and322andadwelltimenogreaterthan333millisecondspermass.
17.
1.
4Inject5-7Lofthebase/neutralextract.
CollectSIMdataforatotalof10minutes.
17.
1.
5Thepossiblepresenceof2,3,7,8-TCDDisindicatedifallthreemassesexhibitsimultaneouspeaksatanypointintheselectedioncurrentprofiles.
17.
1.
6Foreachoccurrencewherethepossiblepresenceof2,3,7,8-TCDDisindicated,calculateandretaintherelativeabundancesofeachofthethreemasses.
17.
2Falsepositivestothistestmaybecausedbythepresenceofsingleorcoelutingcombinationsofcompoundswhosemassspectracontainallofthesemasses.
17.
3Conclusiveresultsofthepresenceandconcentrationlevelof2,3,7,8-TCDDcanbeobtainedonlyfromaproperlyequippedlaboratorythroughtheuseofEPAMethod613orotherapprovedalternatetestprocedures.
References1.
40CFRPart136,AppendixB.
2.
"SamplingandAnalysisProceduresforScreeningofIndustrialEffluentsforPriorityPollutants,"U.
S.
EnvironmentalProtectionAgency,EnvironmentalMonitoringandSupportLaboratory,Cincinnati,Ohio45268,March1977,RevisedApril1977.
AvailablefromEffluentGuidelinesDivision,Washington,DC20460.
3.
ASTMAnnualBookofStandards,Part31,D3694-78.
"StandardPracticesforPreparationofSampleContainersandforPreservationofOrganicConstituents,"AmericanSocietyforTestingandMaterials,Philadelphia.
4.
"Carcinogens-WorkingWithCarcinogens,"DepartmentofHealth,Education,andWelfare,PublicHealthService,CenterforDiseaseControl,NationalInstituteforOccupationalSafetyandHealth,PublicationNo.
77-206,August1977.
5.
"OSHASafetyandHealthStandards,GeneralIndustry,"(29CFRPart1910),OccupationalSafetyandHealthAdministration,OSHA2206(Revised,January1976).
6.
"SafetyinAcademicChemistryLaboratories,"AmericanChemicalSocietyPublication,CommitteeonChemicalSafety,3rdEdition,1979.
7.
Provost,L.
P.
andElder,R.
S.
"InterpretationofPercentRecoveryData,"AmericanLaboratory,15,58-63(1983).
(Thevalue2.
44usedintheequationinSection8.
3.
3istwotimesthevalue1.
22derivedinthisreport.
)8.
ASTMAnnualBookofStandards,Part31,D3370-76.
"StandardPracticesforSamplingWater,"AmericanSocietyforTestingandMaterials,Philadelphia.
9.
"Methods330.
4(Titrimetric,DPD-FAS)and330.
5(Spectrophotometric,DPD)forChlorine,TotalResidual,"MethodsforChemicalAnalysisofWaterandWastes,EPA-600/4-79-020,U.
S.
EnvironmentalProtectionAgency,EnvironmentalMonitoringandSupportLaboratory,Cincinnati,Ohio45268,March1979.
10.
Eichelberger,J.
W.
,Harris,L.
E.
,andBudde,W.
L.
"ReferenceCompoundtoCalibrateIonAbundanceMeasurementinGasChromatography-MassSpectometry,"AnalyticalChemistry,47,995(1975).
11.
McNair,N.
M.
andBonelli,E.
J.
"BasicChromatography,"ConsolidatedPrinting,Berkeley,California,p.
52,1969.
12.
Burke,J.
A.
"GasChromatographyforPesticideResidueAnalysis;SomePracticalAspects,"JournaloftheAssociationofOfficialAnalyticalChemists,48,1037(1965).
13.
Olynyk,P.
,Budde,W.
L.
andEichelberger,J.
W.
"MethodDetectionLimitforMethods624and625,"Unpublishedreport,May14,1980.
14.
"EPAMethodStudy30,Method625,Base/Neutrals,Acids,andPesticides,"EPA600/4-84-053,NationalTechnicalInformationService,PB84-206572,Springfield,Virginia22161,June1984.
Table1—Base/NeutralExtractablesParameterSTORETNo.
CASNo.
Acenaphthene3420583-32-9Acenaphthylene34200208-96-8Anthracene34220120-12-7Aldrin39330309-00-2Benzo(a)anthracene3452656-55-3Benzo(b)fluoranthene34230205-99-2Benzo(k)fluoranthene34242207-08-9Benzo(a)pyrene3424750-32-8Benzo(ghi)perylene34521191-24-2Benzylbutylphthalate3429285-68-7P-BHC39338319-85-7o-BHC34259319-86-8Bis(2-chloroethyl)ether34273111-44-4Bis(2-chloroethoxy)methane34278111-91-1Bis(2-ethylhexyl)phthalate39100117-81-7Bis(2-chloroisopropyl)ethera34283108-60-14-Bromophenylphenylethera34636101-55-3Chlordane3935057-74-92-Chloronaphthalele3458191-58-74-Chlorophenylphenylether346417005-72-3Chrysene34320218-01-94,4'-DDD3931072-54-84,4'-DDE3932072-55-94,4'-DDT3930050-29-3Dibenzo(a,h)anthracene3455653-70-3Di-n-butylphthalate3911084-74-21,3-Dichlorobenzene34566541-73-11,2-Dichlorobenzene3453695-50-11,4-Dichlorobenzene34571106-46-73,3'-Dichlorobenzidine3463191-94-1Dieldrin3938060-57-1Diethylphthalate3433684-66-2Dimethylphthalate34341131-11-32,4-Dinitrotoluene34611121-14-2Table1—Base/NeutralExtractablesParameterSTORETNo.
CASNo.
2,6-Dinitrotoluene34626606-20-2Di-n-octylphthalate34596117-84-0Endosulfansulfate343511031-07-8Endrinaldehyde343667421-93-4Fluoranthene34376206-44-0Fluorene3438186-73-7Heptachlor3941076-44-8Heptchlorepoxide394201024-57-3Hexachlorobenzene39700118-74-1Hexachlorobutadiene3439187-68-3Hexachloroethane3439667-72-1Indeno(1,2,3-cd)pyrene34403193-39-5Isophorone3440878-59-1Naphthalene3469691-20-3Nitrobenzene3444798-95-3N-Nitrosodi-n-propylamine34428621-64-7PCB-10163467112674-11-2PCB-12213948811104-28-2PCB-12323949211141-16-5PCB-12423949653469-21-9PCB-12483950012672-29-6PCB-12543950411097-69-1PCB-12603950811096-82-5Phenanthrene3446185-01-8Pyrene34469129-00-0Toxaphene394008001-35-21,2,4-Trichlorobenzene34551120-82-1aTheproperchemicalnameis2,2'-oxybis(1-chloropropane).
Table2--AcidExtractablesParameterSTORETNo.
CASNo.
4-Chloro-3-methylphenol2-Chlorophenol2,4-Dichlorophenol2,4-Dimethylphenol2,4-Dinitrophenol2-Methyl-4,6-dinitrophenol2-Nitrophenol4-NitrophenolPentachlorophenolPhenol2,4,6-Trichlorophenol344523458634601346063461634657345913464639032346943462159-50-795-57-8120-83-2105-67-951-28-5534-52-188-75-5100-02-787-86-5108-95-288-06-2Table3—AdditionalExtractableParametersaParameterSTORETNo.
CASNo.
MethodBenzidineP-BHCo-BHCEndosulfanIEndosulfanIIEndrinHexachlorocylopentadieneN-NitrosodimethylamineN-Nitrosodiphenylamine39120393373934034361343563939034386344383443392-87-5319-84-658-89-8959-98-833213-65-972-20-877-47-462-75-986-30-6605608608608608608612607607aSeeSection1.
2.
Table4—ChromatographicConditions,MethodDetectionLimits,andCharacteristicMassesforBase/NeutralExtractablesParameterReten-tiontime(min)Methoddetec-tionlimit(g/L)CharacteristicmassesElectronimpactChemicalionizationPrimarySecond-arySecond-aryMethaneMethaneMethane1,3-Dichlorobenzene.
.
7.
41.
91461481131461481501,4-Dichlorobenzene.
.
7.
84.
4146148113146148150Hexachloroethane.
.
.
.
8.
41.
6117201199199201203Bis(2-chloroethyl)ethera8.
45.
7936395631071091,2-Dichlorobenzene.
.
8.
41.
9146148113146148150Bis(2-chloroisopropyl)ethera9.
35.
745777977135137N-Nitrosodi-n-propylamine13042101Table4—ChromatographicConditions,MethodDetectionLimits,andCharacteristicMassesforBase/NeutralExtractablesParameterReten-tiontime(min)Methoddetec-tionlimit(g/L)CharacteristicmassesElectronimpactChemicalionizationPrimarySecond-arySecond-aryMethaneMethaneMethaneNitrobenzene11.
11.
97712365124152164Hexachlorobutadiene.
.
11.
40.
92252232272232252271,2,4-Trichlorobenzene11.
61.
9180182145181183209Isophorone11.
92.
28295138139167178NaphthaleneBis(2-chloroethoxy)12.
11.
6128129127129157169methaneHexachlorocyclo-12.
25.
3939512365107137pentadienea13.
92372352722352372392-Chloronaphthalene.
.
15.
91.
9162164127163191203Acenaphthylene17.
43.
5152151153152153181Acenaphthene17.
81.
9154153152154155183Dimethylphthalate.
.
.
18.
31.
61631941641511631642,6-Dinitrotoluene.
.
.
.
18.
71.
916589121183211223Fluorene4-Chlorophenylphenyl19.
51.
9166165167166167195ether19.
54.
22042061412,4-Dinitrotoluene.
.
.
.
19.
85.
716563182183211223DiethylphthalateN-Nitrosodiphenyl-20.
11.
9149177150177223251amineb20.
51.
9169168167169170198Hexachlorobenzene.
.
.
21.
01.
9284142249284286288P-BHCb4-Bromophenylphenyl21.
1183181109ether21.
21.
9248250141249251277o-BHCb22.
4183181109Phenanthrene22.
85.
4178179176178179207Anthracene22.
81.
9178179176178179207P-BHC23.
44.
2181183109Heptachlor23.
41.
9100272274o-BHC23.
73.
1183109181Aldrin24.
01.
966263220Dibutylphthalate.
.
.
.
24.
72.
5149150104149205279Heptachlorepoxide.
.
.
25.
62.
2353355351EndosulfanIb26.
4237339341Fluoranthene26.
52.
2202101100203231243Dieldrin27.
22.
5792632794,4'-DDE27.
25.
6246248176Pyrene27.
31.
9202101100203231243Endrinb27.
98126382EndosulfanIIb28.
62373393414,4'-DDD28.
62.
8235237165Table4—ChromatographicConditions,MethodDetectionLimits,andCharacteristicMassesforBase/NeutralExtractablesParameterReten-tiontime(min)tionMethoddetec-limit(g/L)CharacteristicmassesElectronimpactChemicalionizationPrimarySecond-arySecond-aryMethaneMethaneMethaneBenzidineb28.
844184921851852132254,4'-DDT29.
34.
7235237165Endosulfansulfate.
.
.
.
29.
85.
6272387422EndrinaldehydeButylbenzyl67345250phthalateBis(2-ethylhexyl)29.
92.
514991206149299327phthalate30.
62.
5149167279149Chrysene31.
52.
5228226229228229257Benzo(a)anthracene.
.
.
31.
57.
82282292262282292573,3'-Dichlorobenzidine32.
216.
5252254126Di-n-octylphthalate.
.
.
32.
52.
5149Benzo(b)fluoranthene34.
94.
8252253125252253281Benzo(k)fluoranthene34.
92.
5252253125252253281Benzo(a)pyreneIndeno(1,2,3-cd)36.
42.
5252253125252253281pyreneDibenzo(a,h)42.
73.
7276138277276277305anthracene43.
22.
5278139279278279307Benzo(ghi)perylene.
.
.
N-Nitrosodimethyl-45.
14.
1276138277276277305amineb427444Chlordanec19-30373375377Toxaphenec25-34159231233PCB1016c18-30224260294PCB1221c15-3030190224260PCB1232c15-32190224260PCB1242c15-32224260294PCB1248c12-34294330262PCB1254c22-3436294330362PCB1260c23-32330362394aTheproperchemicalnameis2,2'-bisoxy(1-chloropropane).
bSeeSection1.
2.
cThesecompoundsaremixturesofvariousisomers(SeeFigures2through12).
Columnconditions:Supelcoport(100/120mesh)coatedwith3%SP-2250packedina1.
8mlongx2mmIDglasscolumnwithheliumcarriergasat30mL/min.
flowrate.
Columntemperatureheldisothermalat50°Cforfourminutes,thenprogrammedat8°C/min.
to270°Candheldfor30minutes.
Table5—ChromatographicConditions,MethodDetectionLimits,andCharacteristicMassesforAcidExtractablesParameterReten-tiontime(min)tionMethoddetec-limit(g/L)CharacteristicmassesElectronimpactChemicalionizationPrimarySecond-arySecond-aryMethaneMethaneMethane2-Chlorophenol5.
93.
3128641301291311572-Nitrophenol6.
53.
613965109140168122Phenol8.
01.
5946566951231352,4-Dimethylphenol.
.
.
9.
42.
71221071211231511632,4-Dichlorophenol.
.
.
9.
82.
7162164981631651672,4,6-Trichlorophenol.
.
11.
82.
71961982001971992014-Chloro-3-methyl-phenol13.
23.
01421071441431711832,4-Dinitrophenol.
.
.
.
15.
942184631541852132252-Methyl-4,6-dinitrophenol16.
22419818277199227239Pentachlorophenol.
.
.
.
17.
53.
62662642682672652694-Nitrophenol20.
32.
465139109140168122Columnconditions:Supelcoport(100/120mesh)coatedwith1%SP-1240DApackedina1.
8mlongx2mmIDglasscolumnwithheliumcarriergasat30mL/min.
flowrate.
Columntemperatureheldisothermalat70°Cfortwomintuesthenprogrammedat8°C/min.
to200°C.
Table6—QCAcceptanceCriteria—Method625ParameterTestconclu-sion(g/L)Limitsfors(g/L)Rangefor(g/L)RangeforP,P(Percent)sAcenaphthene10027.
660.
1-132.
347-145Acenaphthylene10040.
253.
5-126.
033-145Aldrin10039.
07.
2-152.
2D-166Anthracene10032.
043.
4-118.
027-133Benzo(a)anthracene10027.
641.
8-133.
033-143Benzo(b)fluoranthene10038.
842.
0-140.
424-159Benzo(k)fluoranthene10032.
325.
2-145.
711-162Benzo(a)pyrene10039.
031.
7-148.
017-163Benzo(ghi)perylene10058.
9D-195.
0D-219Benzylbutylphthalate10023.
4D-139.
9D-152P-BHC10031.
541.
5-130.
624-149o-BHC10021.
6D-100.
0D-110Bis(2-chloroethyl)ether10055.
042.
9-126.
012-158Bis(2-chloroethoxy)methane.
.
.
10034.
549.
2-164.
733-184Bis(2-chloroisopropyl)ether.
.
.
a10046.
362.
8-138.
636-166Bis(2-ethylhexyl)phthalate.
.
.
10041.
128.
9-136.
88-1584-Bromophenylphenylether.
.
10023.
064.
9-114.
453-1272-Chloronaphthalene10013.
064.
5-113.
560-1184-Chlorophenylphenylether.
.
10033.
438.
4-144.
725-158Table6—QCAcceptanceCriteria—Method625ParameterTestconclu-sion(g/L)Limitsfors(g/L)Rangefor(g/L)RangeforP,P(Percent)sChrysene10048.
344.
1-139.
917-1684,4'-DDD10031.
0D-134.
5D-1454,4'-DDE10032.
019.
2-119.
74-1364,4'-DDT10061.
6D-170.
6D-203Dibenzo(a,h)anthracene10070.
0D-199.
7D-227Di-n-butylphthalate10016.
78.
4-111.
01-1181,2-Dichlorobenzene10030.
948.
6-112.
032-1291,3-Dichlorobenzene10041.
716.
7-153.
9D-1721,4,-Dichlorobenzene10032.
137.
3-105.
720-1243,3'-Dhlorobenzidine10071.
48.
2-212.
5D-262Dieldrin10030.
744.
3-119.
329-136Diethylphthalate10026.
5D-100.
0D-114Dimethylphthalate10023.
2D-100.
0D-1122,4-Dinitrotoluene10021.
847.
5-126.
939-1392,6-Dinitrotoluene10029.
668.
1-136.
750-158Di-n-octylphthalate10031.
418.
6-131.
84-146Endosulfansulfate10016.
7D-103.
5D-107Endrinaldehyde10032.
5D-188.
8D-209Fluoranthene10032.
842.
9-121.
326-137Fluorene10020.
771.
6-108.
459-121Heptachlor10037.
2D-172.
2D-192Heptachlorepoxide10054.
770.
9-109.
426-155Hexachlorobenzene10024.
97.
8-141.
5D-152Hexachlorobutadiene10026.
337.
8-102.
224-116Hexachloroethane10024.
555.
2-100.
040-113Indeno(1,2,3-cd)pyrene10044.
6D-150.
9D-171Isophorone10063.
346.
6-180.
221-196Naphthalene10030.
135.
6-119.
621-133Nitrobenzene10039.
354.
3-157.
635-180N-Nitrosodi-n-propylamine.
.
.
10055.
413.
6-197.
9D-230PCB-126010054.
219.
3-121.
0D-164Phenanthrene10020.
665.
2-108.
754-120Pyrene10025.
269.
6-100.
052-1151,2,4-Trichlorobenzene10028.
157.
3-129.
244-1424-Chloro-3-methylphenol10037.
240.
8-127.
922-1472-Chlorophenol10028.
736.
2-120.
423-1342,4-Dichlorophenol10026.
452.
5-121.
739-1352,4-Dimethylphenol10026.
141.
8-109.
032-1192,4-Dinitrophenol10049.
8D-172.
9D-1912-Methyl-4,6-dinitrophenol.
.
.
10093.
253.
0-100.
0D-1812-Nitrophenol10035.
245.
0-166.
729-1824-Nitrophenol10047.
213.
0-106.
5D-132Table6—QCAcceptanceCriteria—Method625ParameterTestconclu-sion(g/L)Limitsfors(g/L)Rangefor(g/L)RangeforP,P(Percent)sPentachlorophenolPhenol2,4,6-Trichlorophenol10010010048.
922.
631.
738.
1-151.
816.
6-100.
052.
4-129.
214-1765-11237-144s=Standarddeviationforfourrecoverymeasurements,ing/L(Section8.
2.
4).
=Averagerecoveryforfourrecoverymeasurements,in/L(Section8.
2.
4).
P,P=Percentrecoverymeasured(Section8.
3.
2,Section8.
4.
2).
sD=Detected;resultmustbegreaterthanzero.
NOTE:ThesecriteriaarebaseddirectlyuponthemethodperformancedatainTable7.
Wherenecessary,thelimitsforrecoveryhavebeenbroadenedtoassureapplicabilityofthelimtstoconcentrationsbelowthoseusedtodevelopTable7.
aTheproperchemicalnameis2,2'oxybis(1-chloropropane).
Table7—MethodAccuracyandPrecisionasFunctionsofConcentration—Method625Parameterrecovery,X′Accuracy,as(g/L)precision,s′Singleanalyst(g/L)rOverallpreci-sion,S′(g/L)Acenaphthene0.
96C+0.
190.
15-0.
120.
21-0.
67Acenaphthylene0.
89C+0.
740.
24-1.
060.
26-0.
54Aldrin0.
78C+1.
660.
27-1.
280.
43+1.
13Anthracene0.
80C+0.
680.
21-0.
320.
27-0.
64Benzo(a)anthracene0.
88C-0.
600.
15+0.
930.
26-0.
28Benzo(b)fluoranthene0.
93C-1.
800.
22+0.
430.
29+0.
96Benzo(k)fluoranthene0.
87C-1.
560.
19+1.
030.
35+0.
40Benzo(a)pyrene0.
90C-0.
130.
22+0.
480.
32+1.
35Benzo(ghi)perylene0.
98C-0.
860.
29+2.
400.
51-0.
44Benzylbutylphthalate0.
66C-1.
680.
18+0.
940.
53+0.
92P-BHC0.
87C-0.
940.
20-0.
580.
30-1.
94o-BHC0.
29C-1.
090.
34+0.
860.
93-0.
17Bis(2-chloroethyl)ether0.
86C-1.
540.
35-0.
990.
35+0.
10Bis(2-chloroethoxy)methane1.
12C-5.
040.
16+1.
340.
26+2.
01Bis(2-chloroisopropyl)ethera1.
03C-2.
310.
24+0.
280.
25+1.
04Bis(2-ethylhexyl)phthalate0.
84C-1.
180.
26+0.
730.
36+0.
674-Bromophenylphenylether0.
91C-1.
340.
13+0.
660.
16+0.
662-Chloronaphthalene0.
89C+0.
010.
07+0.
520.
13+0.
344-Chlorophenylphenylether0.
91C+0.
530.
20-0.
940.
30-0.
46Chrysene0.
93C-1.
000.
28+0.
130.
33-0.
094,4'-DDD0.
56C-0.
400.
29-0.
320.
66-0.
964,4'-DDE0.
70C-0.
540.
26-1.
170.
39-1.
044,4'-DDT0.
79C-3.
280.
42+0.
190.
65-0.
58Dibenzo(a,h)anthracene0.
88C+4.
720.
30+8.
510.
59+0.
25Table7—MethodAccuracyandPrecisionasFunctionsofConcentration—Method625ParameterDi-n-butylphthalate1,2-Dichlorobenzene1,3-Dichlorobenzene1,4-Dichlorobenzene3,3'-DichlorobenzidineDieldrinDiethylphthalateDimethylphthalate2,4-Dinitrotoluene2,6-DinitrotolueneDi-n-octylphthalateEndosulfansulfateEndrinaldehydeFluorantheneFluoreneHeptachlorHeptachlorepoxideHexachlorobenzeneHexachlorobutadieneHexachloroethaneIndeno(1,2,3-cd)pyreneIsophoroneNaphthaleneNitrobenzeneN-Nitrosodi-n-propylaminePCB-1260PhenanthrenePyrene1,2,4-Trichlorobenzene4-Chloro-3-methylphenol2-Chlorophenol2,4-Dichlorophenol2,4-Dimethylphenol2,4-Dinitrophenol2-Methyl-4,6-Dinitrophenol2-Nitrophenol4-NitrophenolPentachlorophenolAccuracy,asrecovery,X′(g/L)0.
59C+0.
710.
80C+0.
280.
86C-0.
700.
73C-1.
471.
23C-12.
650.
82C-0.
160.
43C+1.
000.
20C+1.
030.
92C-4.
811.
06C-3.
600.
76C-0.
790.
39C+0.
410.
76C-3.
860.
81C+1.
100.
90C-0.
000.
87C-2.
970.
92C-1.
870.
74C+0.
660.
71C-1.
010.
73C-0.
830.
78C-3.
101.
12C+1.
410.
76C+1.
581.
09C-3.
051.
12C-6.
220.
81C-10.
860.
87C-0.
060.
84C-0.
160.
94C-0.
790.
84C+0.
350.
78C+0.
290.
87C+0.
130.
71C+4.
410.
81C-18.
041.
04C-28.
041.
07C-1.
150.
61C-1.
220.
93C+1.
99Singleanalystprecision,sr′(g/L)0.
13+1.
160.
20+0.
470.
25+0.
680.
24+0.
230.
28+7.
330.
20-0.
160.
28+1.
440.
54+0.
190.
12+1.
060.
14+1.
260.
21+1.
190.
12+2.
470.
18+3.
910.
22-0.
730.
12+0.
260.
24-0.
560.
33-0.
460.
18-0.
100.
19+0.
920.
17+0.
670.
29+1.
460.
27+0.
770.
21-0.
410.
19+0.
920.
27+0.
680.
35+3.
610.
12+0.
570.
16+0.
060.
15+0.
850.
23+0.
750.
18+1.
460.
15+1.
250.
16+1.
210.
38+2.
360.
05+42.
290.
16+1.
940.
38+2.
570.
24+3.
03Overallpreci-sion,S′(g/L)0.
39+0.
600.
24+0.
390.
41+0.
110.
29+0.
360.
47+3.
450.
26-0.
070.
52+0.
221.
05-0.
920.
21+1.
500.
19+0.
350.
37+1.
190.
63-1.
030.
73-0.
620.
28-0.
600.
13+0.
610.
50-0.
230.
28+0.
640.
43-0.
520.
26+0.
490.
17+0.
800.
50+0.
440.
33+0.
260.
30-0.
680.
27+0.
210.
44+0.
470.
43+1.
820.
15+0.
250.
15+0.
310.
21+0.
390.
29+1.
310.
28+0.
970.
21+1.
280.
22+1.
310.
42+26.
290.
26+23.
100.
27+2.
600.
44+3.
240.
30+4.
33Table7—MethodAccuracyandPrecisionasFunctionsofConcentration—Method625Parameterrecovery,X′Accuracy,as(g/L)precision,s′Singleanalyst(g/L)rOverallpreci-sion,S′(g/L)Phenol2,4,6-Trichlorophenol0.
43C+1.
260.
91C-0.
180.
26+0.
730.
16+2.
220.
35+0.
580.
22+1.
81X'=ExpectedrecoveryforoneormoremeasurementsofasamplecontainingaconcentrationofC,ing/L.
s'=Expectedsingleanalyststandarddeviationofmeasurementsatanaverageconcentrationrfoundof,ing/L.
S'=Expectedinterlaboratorystandarddeviationofmeasurementsatanaverageconcentrationfoundof,ing/L.
C=Truevaluefortheconcentration,ing/L.
=AveragerecoveryfoundformeasurementsofsamplescontainingaconcentrationofC,ing/L.
aTheproperchemicalnameis2,2'oxybis(1-chloropropane).
Table8—SuggestedInternalandSurrogateStandardsBase/neutralfractionAcidfractionAniline-d52-FluorophenolAnthracene-d10PentafluorophenolBenzo(a)anthracene-d12Phenol-d54,4'-Dibromobiphenyl2-Perfluoromethylphenol4,4'-DibromooctafluorobiphenylDecafluorobiphenyl2,2'-Difluorobiphenyl4-Fluoroaniline1-Fluoronaphthalene2-FluoronaphthaleneNaphthalene-d8Nitrobenzene-d52,3,4,5,6-PentafluorobiphenylPhenanthrene-d10Pyridine-d5Table9—DFTPPKeyMassesandAbundanceCriteriaMassm/zAbundancecriteria5130-60percentofMass198.
68Lessthan2percentofMass69.
70Lessthan2percentofMass69.
12740-60percentofMass198.
197Lessthan1percentofMass198.
198Basepeak,100percentrelativeabundance.
1995-9percentofMass198.
27510-30percentofMass198.
365Greaterthan1percentofMass198.
441PresentbutlessthanMass443.
442Greaterthan40percentofMass198.
44317-23percentofMass442.