EPA Method 16A

983METHOD16A-DETERMINATIONOFTOTALREDUCEDSULFUREMISSIONSFROMSTATIONARYSOURCES(IMPINGERTECHNIQUE)NOTE:Thismethoddoesnotincludeallofthespecifications(e.g.,equipmentandsupplies)andprocedures(e.g.,samplingandanalytical)essentialtoitsperformance.Somematerialisincorporatedbyreferencefromothermethodsinthispart.Therefore,toobtainreliableresults,personsusingthismethodshouldhaveathoroughknowledgeofatleastthefollowingadditionaltestmethods:Method1,Method6,andMethod16.1.0ScopeandApplication.1.1Analytes.AnalyteCASNo.SensitivityTotalreducedsulfur(TRS)including:Dimethyldisulfide[(CH3)2S2]Dimethylsulfide[(CH3)2S]Hydrogensulfide[H2S]Methylmercaptan[CH4S]N/A62-49-2075-18-37783-06-474-93-1SeeSection13.1Reducedsulfur(RS)includingH2SCarbonylsulfide[COS]Carbondisulfide[CS2]Reportedas:Sulfurdioxide(SO2)N/A7783-06-4463-58-175-15-07449-09-59841.2Applicability.ThismethodisapplicableforthedeterminationofTRSemissionsfromrecoveryboilers,limekilns,andsmeltdissolvingtanksatkraftpulpmills,reducedsulfurcompounds(H2S,carbonylsulfide,andcarbondisulfidefromsulfurrecoveryunitsatonshorenaturalgasprocessingfacilities,andfromothersourceswhenspecifiedinanapplicablesubpartoftheregulations.Thefluegasmustcontainatleast1percentoxygenforcompleteoxidationofallTRStoSO2.1.3DataQualityObjectives.Adherencetotherequirementsofthismethodwillenhancethequalityofthedataobtainedfromairpollutantsamplingmethods.2.0SummaryofMethod.2.1Anintegratedgassampleisextractedfromthestack.SO2isremovedselectivelyfromthesampleusingacitratebuffersolution.TRScompoundsarethenthermallyoxidizedtoSO2,collectedinhydrogenperoxideassulfate,andanalyzedbytheMethod6barium-thorintitrationprocedure.3.0Definitions.[Reserved]4.0Interferences.4.1Reducedsulfurcompoundsotherthanthoseregulatedbytheemissionstandards,ifpresent,maybemeasuredbythismethod.Therefore,carbonylsulfide,which985ispartiallyoxidizedtoSO2andmaybepresentinalimekilnexitstack,wouldbeapositiveinterferant.4.2Particulatematterfromthelimekilnstackgas(primarilycalciumcarbonate)cancauseanegativebiasifitisallowedtoenterthecitratescrubber;theparticulatematterwillcausethepHtoriseandH2Stobeabsorbedpriortooxidation.Furthermore,ifthecalciumcarbonateentersthehydrogenperoxideimpingers,thecalciumwillprecipitatesulfateion.ProperuseoftheparticulatefilterdescribedinSection6.1.3willeliminatethisinterference.5.0Safety.5.1Disclaimer.Thismethodmayinvolvehazardousmaterials,operations,andequipment.Thistestmethodmaynotaddressallofthesafetyproblemsassociatedwithitsuse.Itistheresponsibilityoftheuserofthistestmethodtoestablishappropriatesafetyandhealthpracticesanddeterminetheapplicabilityofregulatorylimitationspriortoperformingthistestmethod.5.2Corrosivereagents.Thefollowingreagentsarehazardous.Personalprotectiveequipmentandsafeproceduresareusefulinpreventingchemicalsplashes.Ifcontactoccurs,immediatelyflushwithcopiousamountsofwaterforatleast15minutes.Removeclothingundershower986anddecontaminate.Treatresidualchemicalburnsasthermalburns.5.2.1HydrogenPeroxide(H2O2).Irritatingtoeyes,skin,nose,andlungs.5.2.2SodiumHydroxide(NaOH).Causesseveredamagetoeyesandskin.Inhalationcausesirritationtonose,throat,andlungs.Reactsexothermicallywithlimitedamountsofwater.5.2.3SulfuricAcid(H2SO4).Rapidlydestructivetobodytissue.Willcausethirddegreeburns.Eyedamagemayresultinblindness.Inhalationmaybefatalfromspasmofthelarynx,usuallywithin30minutes.Maycauselungtissuedamagewithedema.3mg/m3willcauselungdamageinuninitiated.1mg/m3for8hourswillcauselungdamageor,inhigherconcentrations,death.Provideventilationtolimitinhalation.Reactsviolentlywithmetalsandorganics.5.3HydrogenSulfide(H2S).Aflammable,poisonousgaswiththeodorofrotteneggs.H2Sisextremelyhazardousandcancausecollapse,coma,anddeathwithinafewsecondsofoneortwoinhalationsatsufficientconcentrations.Lowconcentrationsirritatethemucousmembranesandmaycausenausea,dizziness,andheadacheafterexposure.6.0EquipmentandSupplies.9876.1SampleCollection.ThesamplingtrainisshowninFigure16A-1andcomponentpartsarediscussedbelow.Modificationstothissamplingtrainareacceptableprovidedthesystemperformancecheckismet(seeSection8.5).6.1.1Probe.Teflontubing,6.4-mm(¼-in.)diameter,sequentiallywrappedwithheat-resistantfiberstrips,arubberizedheattape(plugatoneend),andheat-resistantadhesivetape.AflexiblethermocoupleorothersuitabletemperaturemeasuringdeviceshouldbeplacedbetweentheTeflontubingandthefiberstripssothatthetemperaturecanbemonitoredtopreventsofteningoftheprobe.Theprobeshouldbesheathedinstainlesssteeltoprovidein-stackrigidity.Aseriesofbored-outstainlesssteelfittingsplacedatthefrontofthesheathwillpreventmoistureandparticulatefromenteringbetweentheprobeandsheath.A6.4-mm(¼-in.)Teflonelbow(boredout)shouldbeattachedtotheinletoftheprobe,anda2.54cm(1in.)pieceofTeflontubingshouldbeattachedattheopenendoftheelbowtopermittheopeningoftheprobetobeturnedawayfromtheparticulatestream;thiswillreducetheamountofparticulatedrawnintothesamplingtrain.TheprobeisdepictedinFigure16A-2.6.1.2ProbeBrush.Nylonbristlebrushwithhandleinsertedintoa3.2-mm(c-in.)Teflontubing.TheTeflon988tubingshouldbelo