EPA Method 16B

1023METHOD16B-DETERMINATIONOFTOTALREDUCEDSULFUREMISSIONSFROMSTATIONARYSOURCESNOTE:Thismethoddoesnotincludeallofthespecifications(e.g.,equipmentandsupplies)andprocedures(e.g.,samplingandanalytical)essentialtoitsperformance.Somematerialisincorporatedbyreferencefromothermethodsinthispart.Therefore,toobtainreliableresults,personsusingthismethodshouldhaveaknowledgeofatleastthefollowingadditionaltestmethods:Method6C,Method16,andMethod16A.1.0ScopeandApplication.1.1Analytes.AnalyteCASNo.Totalreducedsulfur(TRS)including:Dimethyldisulfide(DMDS),[(CH3)2S2]Dimethylsulfide(DMS),[(CH3)2S]Hydrogensulfide(H2S)Methylmercaptan(MeSH),[CH4S]N/A62-49-2075-18-37783-06-474-93-1Reportedas:Sulfurdioxide(SO2)7449-09-51.2Applicability.ThismethodisapplicablefordeterminingTRSemissionsfromrecoveryfurnaces(boilers),limekilns,andsmeltdissolvingtanksatkraftpulpmills,andfromothersourceswhenspecifiedinanapplicablesubpartoftheregulations.Thefluegasmustcontainat1024least1percentoxygenforcompleteoxidationofallTRStoSO2.1.3DataQualityObjectives.Adherencetotherequirementsofthismethodwillenhancethequalityofthedataobtainedfromairpollutantsamplingmethods.2.0SummaryofMethod.2.1Anintegratedgassampleisextractedfromthestack.TheSO2isremovedselectivelyfromthesampleusingacitratebuffersolution.TheTRScompoundsarethenthermallyoxidizedtoSO2andanalyzedasSO2bygaschromatography(GC)usingflamephotometricdetection(FPD).3.0Definitions.[Reserved]4.0Interferences.4.1Reducedsulfurcompoundsotherthanthoseregulatedbytheemissionstandards,ifpresent,maybemeasuredbythismethod.Therefore,carbonylsulfide,whichispartiallyoxidizedtoSO2andmaybepresentinalimekilnexitstack,wouldbeapositiveinterferant.4.2Particulatematterfromthelimekilnstackgas(primarilycalciumcarbonate)cancauseanegativebiasifitisallowedtoenterthecitratescrubber;theparticulatematterwillcausethepHtoriseandH2Stobeabsorbedbeforeoxidation.Properuseoftheparticulatefilter,1025describedinSection6.1.3ofMethod16A,willeliminatethisinterference.4.3Carbonmonoxide(CO)andcarbondioxide(CO2)havesubstantialdesensitizingeffectsontheFPDevenafterdilution.AcceptablesystemsmustdemonstratethattheyhaveeliminatedthisinterferencebysomeproceduresuchaselutingthesecompoundsbeforetheSO2.CompliancewiththisrequirementcanbedemonstratedbysubmittingchromatogramsofcalibrationgaseswithandwithoutCO2indiluentgas.TheCO2levelshouldbeapproximately10percentforthecasewithCO2present.ThetwochromatogramsshouldshowagreementwithintheprecisionlimitsofSection13.0.5.0Safety.5.1Disclaimer.Thismethodmayinvolvehazardousmaterials,operations,andequipment.Thistestmethodmaynotaddressallofthesafetyproblemsassociatedwithitsuse.Itistheresponsibilityoftheuserofthistestmethodtoestablishappropriatesafetyandhealthpracticesanddeterminetheapplicabilityofregulatorylimitationspriortoperformingthistestmethod.5.2HydrogenSulfide(H2S).Aflammable,poisonousgaswiththeodorofrotteneggs.H2Sisextremelyhazardousandcancausecollapse,coma,anddeathwithina1026fewsecondsofoneortwoinhalationsatsufficientconcentrations.Lowconcentrationsirritatethemucousmembranesandmaycausenausea,dizziness,andheadacheafterexposure.6.0EquipmentandSupplies.6.1SampleCollection.ThesamplingtrainisshowninFigure16B-1.ModificationstotheapparatusareacceptedprovidedthesystemperformancecheckinSection8.4.1ismet.6.1.1Probe,ProbeBrush,ParticulateFilter,SO2Scrubber,CombustionTube,andFurnace.SameasinMethod16A,Sections6.1.1to6.1.6.6.1.2SamplingPump.LeaklessTeflon-coateddiaphragmtypeorequivalent.6.2Analysis.6.2.1DilutionSystem(optional),GasChromatograph,Oven,TemperatureGauges,FlowSystem,FlamePhotometricDetector,Electrometer,PowerSupply,Recorder,CalibrationSystem,TubeChamber,FlowSystem,andConstantTemperatureBath.SameasinMethod16,Sections6.2.1,6.2.2,and6.3.6.2.2GasChromatographColumns.SameasinMethod16,Section6.2.3.OthercolumnswithdemonstratedabilitytoresolveSO2andbefreefromknowninterferencesareacceptablealternatives.Singlecolumnsystemssuchasa10277-ftCarbsorbBHT100columnhavebeenfoundsatisfactoryinresolvingSO2fromCO2.7.0ReagentsandStandards.SameasinMethod16,Section7.0,exceptforthefollowing:7.1CalibrationGas.SO2permeationtubegravimetricallycalibratedandcertifiedatsomeconvenientoperatingtemperature.ThesetubesconsistofhermeticallysealedFEPTeflontubinginwhichaliquefiedgaseoussubstanceisenclosed.Theenclosedgaspermeatesthroughthetubingwallataconstantrate.Whenthetemperatureisconstant,calibrationgasescoveringawiderangeofknownconcentrationscanbegeneratedbyvaryingandaccuratelymeasuringtheflowrateofdiluentgaspassingoverthetubes.InplaceofSO2permeationtubes,cylindergasescontainingSO2innitrogenmaybeusedforcalibration.ThecylindergasconcentrationmustbeverifiedaccordingtoSection8.2.1ofMethod6C.ThecalibrationgasisusedtocalibratetheGC/FPDsystemandthedilutionsystem.7.2RecoveryCheckGas.7.2.1Hydrogensulfide[100partspermillionbyvolume(ppmv)orless]innitrogen,storedinaluminumcylinders.VerifytheconcentrationbyMethod11,theprocedurediscussedinSection16.0ofMethod16A,orgas1028chromatographywheretheinstrumentiscalibratedwithanH2Spermeationtubeasdescribedbelow.Forthewet-chemical