Chapter 4 Selective MRMs

PesticideAnalyticalManualVol.I400–1TransmittalNo.96-E1(9/96)FormFDA2905a(6/92)TableofContentspagedate401:MethodforN-MethylcarbamatesBasicReferences401-11/94GeneralPrinciples401-11/94Applicability401-11/94ReferenceStandards401-11/94Stepsofthemethod401-11/94Validation401-21/94E1Extractionwithmethanol401-31/94E2Extractionwithmethanol,reducedsamplesize401-41/94C1Liquid-LiquidPartitioningandCharcoal/Celite401-51/94ColumnCleanupDL1HPLC,Post-ColumnDerivatization,401-91/94FluorescenceDetectionChapter1RegulatoryOperationsChapter2GeneralAnalyticalOperationsandInformationChapter3MulticlassMRMsChapter5GLCChapter4SelectiveMRMsChapter6HPLCPesticideAnalyticalManualVol.ISECTION400400–2TransmittalNo.96-E1(9/96)FormFDA2905a(6/92)pagedateDL2HPLC,FluorescenceDetection401-131/94Confirmation401-131/94402:MethodforAcidsandPhenolsBasicReference402-11/94GeneralPrinciples402-11/94Applicability402-11/94ReferenceStandards402-11/94Stepsofthemethod402-11/94Validation402-21/94E1Extractionwithsolventsfromacidified,402-31/94denaturedproductsE2Extractionwithacidifiedmethylenechloride402-71/94E3Extractionwithacidifiedmethanol402-91/94E4Extractionwithacidifiedwater/methanol402-101/94E5Extractionwithacidifiedmethanol402-111/94E6Dissolutioninmethylenechloride/hexane402-131/94E7Extractionwithacidifiedmethylenechloride402-151/94C1GPCCleanup,methylation,andFlorisil402-171/94columncleanupC1aGPCCleanup402-171/94C1bMethylation402-211/94C1cFlorisilcolumncleanup402-221/94Determination402-251/94Confirmation402-251/94403:MethodforPhenylureaHerbicidesBasicReference403-11/94GeneralPrinciples403-11/94Applicability403-11/94ReferenceStandards403-11/94Stepsofthemethod403-11/94Validation403-21/94E1ExtractionwithMethanol403-31/94C1Liquid-LiquidPartitioningandFlorisil403-51/94ColumnCleanupDL3HPLC,Post-ColumnPhotolysisand403-71/94Derivatization,FluorescenceDetectionDL4HPLC,Differentmobilephase403-101/94Confirmation403-111/94404:MethodforBenzimidazolesBasicReference404-11/94GeneralPrinciples404-11/94PesticideAnalyticalManualVol.I400–3TransmittalNo.96-E1(9/96)FormFDA2905a(6/92)pagedateApplicability404-11/94ReferenceStandards404-11/94StepsoftheMethod404-11/94Validation404-31/94E1Extractionwithmethanol,transferto404-51/94methylenechlorideE2Extractionwithmethanol,removalofoilwith404-71/94hexane,transfertomethylenechlorideE3Extractionwithmethanol,removalofoilwith404-81/94methylenechloride,transfertomethylenechlorideDL5HPLC,IonPairMobilePhase,UVand404-91/94FluorescenceDetectorDL6HPLC,ConcentratedIonPairMobilePhase,404-121/94UVandFluorescenceDetectorDL7HPLC,IonPairMobilePhase,Changesin404-141/94DetectorSettingsConfirmation404-141/94Figures401-aMethodforN-Methylcarbamates401-21/94401-bVacuumRotaryEvaporator401-31/94401-cHPLCSystemforDeterminationof401-91/94N-Methylcarbamates401-dHPLCChromatogramofCarbamates401-121/94andMetabolites402-aMethodforAcidsandPhenols402-21/94402-bDeliveryTubeApparatus402-31/94403-aMethodforPhenylureas403-21/94403-bHPLCSystemforDeterminationof403-71/94PhenylureaHerbicides403-cHPLCChromatogramsofCarrotExtract403-101/94403-dChromatographicPatternComparison403-111/94404-aMethodforBenzimidazoles404-21/94404-bChromatogramsofBenzimidazoleCompounds404-129/96404-cEffectofIonPairingSolutionConcentration404-131/94onChromatographyofMBCTables401-a:RecoveryofChemicalsThroughMethod401401-a–19/96(E1-E2+C1+DL1)401-b:RecoveryofChemicalsThroughMethod401401-b–19/96(E1-E2+C1+DL2)402-a:RecoveryofChemicalsThroughMethod402402-a–19/96(E1-E7+C1+DG1orDG3orDG4)403-a:RecoveryofChemicalsThroughMethod403403-a–19/96(E1+C1+DL3andDL4)PesticideAnalyticalManualVol.ISECTION400400–4TransmittalNo.96-E1(9/96)FormFDA2905a(6/92)pagedate404-a:RecoveryofChemicalsThroughMethod404404-a–19/96(E1-E3+DL5)TransmittalNo.94-1(1/94)FormFDA2905a(6/92)401–1SECTION401PesticideAnalyticalManualVol.I401:METHODFORN-METHYLCARBAMATESBASICREFERENCESKrause,R.T.(1979)J.Chromatogr.185,615-624Krause,R.T.(1980)J.Assoc.Off.Anal.Chem.63,1114-1124Krause,R.T.(1985)J.Assoc.Off.Anal.Chem.68,734-741GENERALPRINCIPLESN-methylcarbamateinsecticideresidues,includingcarbamatemetabolites,areex-tractedwithmethanol.Theextractiscleanedupbypartitioningandcolumnchromatographyonacharcoal/Celitecolumn.ResiduesareselectivelydeterminedwithanHPLCsystemconsistingofareversephase(RP)column,post-columnhydrolysisandderivatization,anddetectionoftheresultantderivativewithafluo-rescencedetector.VariationsinthedeterminativestepmaybeusedforadditionalresiduesnotoftheN-methylcarbamatestructure.APPLICABILITYConsultGuidetoPAMIforadditionalinformationpertinenttotheappropriateapplicationofmultiresiduemethodology.MethodisapplicabletoresidueswithanN-methylcarbamatestructureineithernonfattyorfattyfoodswhendeterminativestepincludespost-columnhydrolysisandderivatization.SeeTable401-a,followingmethoddescription,forchemicalstestedthroughthemethod.Methodisapplicabletonaturallyfluorescentresidueswhenpost-columnhydrolysisandderivatizationarenotperformed.SeeTable401-b,followingTable401-a.Certaincommodities,e.g.,oranges,containnaturallyfluorescentco-extractivesthat