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V 8Document[6]Document Style8..V 8Document[5]Document Style0..V/8Document[2]Document Style 2A.3  Ԁ   V& 8Document[7]Document Style0..0` ..` zU :Right Par[1]Right-Aligned Paragraph Numbers..2I.3  Ԁ..0..zh :Right Par[2]Right-Aligned Paragraph Numbers..` ..2A.3  Ԁ..0` ..` V?8Document[3]Document Style.. 21.3  Ԁ   z{ :Right Par[3]Right-Aligned Paragraph Numbers..` ..`  ..P 21.3  Ԁ` ..` 0 .. z :Right Par[4]Right-Aligned Paragraph Numbers..` ..`  .. .. 2a.3  Ԁ .. 0..z :Right Par[5]Right-Aligned Paragraph Numbers..` ..`  .. ..h..2(1)3  Ԁ..0h..hz :Right Par[6]Right-Aligned Paragraph Numbers..` ..`  .. ..h..h..2(a)3  Ԁh..h0..z :Right Par[7]Right-Aligned Paragraph Numbers..` ..`  .. ..h..h....2i)3  Ԁ..0..z :Right Par[8]Right-Aligned Paragraph Numbers..` ..`  .. ..h..h....p..2a)3  Ԁ..0p..pVX8Document[1]Document Style  @..^  2I.3  Ԁ     Ԉ l2:Technical[5]Technical Document Style.. 2(1)3  Ԁ. l2:Technical[6]Technical Document Style.. 2(a)3  Ԁ. l/%:Technical[2]Technical Document Style 2A.3  Ԁ   .. l,!:Technical[3]Technical Document Style 21.3  Ԁ   .. l(!:Technical[4]Technical Document Style 2a.3  Ԁ   .. l:0:Technical[1]Technical Document Style  2I.3  Ԁ     .. l1:Technical[7]Technical Document Style.. 2i)3  Ԁ. l1:Technical[8]Technical Document Style.. 2a)3  Ԁ. <6X9`(CourierXR& 8BibliogrphyBibliography0....fp2Doc InitInitialize Document StyleS !    I. 1. A. a.(1)(a) i) a)S ($0 ($0 0 (($0 0 0   A_ekqwDocumentDocument StyleI.1.A.a.(1)(a)i)a)jo4Tech InitInitialize Technical StyleS #  1 .1 .1 .1 .1 .1 .1 .1 S CuyTechnicalTechnical Document Style11.11.1.11.1.1.11.1.1.1.11.1.1.1.1.11.1.1.1.1.1.11.1.1.1.1.1.1.1x?t2PleadingHeader for numbered pleading paper %  &(   XXXXX?1''*dE*??1''*dE*?HH1HH2HH3HH4HH5HH6HH7HH8HH910111213141516171819202122232425262728  .+('2$ 7T!   '     0 .   ..@.@('2$ 7T!   2<6N9`("CourierItalic dTable_A&0 d d dTable_B  CRight ParRight-Aligned Paragraph NumbersI.A.1.a.(1)(a)i)a)3|x<6X9`(CourierXx6X@`7X@< 9(CourierBoldXx `7X<6N9`("CourierItalicXx6Nhez7XH( T$  <( 9Z &Courier Regularj%l2((3 $ 7T!    T E '   :XXXX 7T!   9% pP hx(#',81X9  H7::XXdd7@ METHOD7ADETERMINATIONOFNITROGENOXIDEEMISSIONS Z @"FROMSTATIONARYSOURCES@(IONCHROMATOGRAPHICMETHOD)  " $ DXpP $ NOTE: Thismethoddoesnotincludeallofthe   specifications(,XXXXe.g.XXX,X,equipmentandsupplies)andprocedures  X (,XXXXe.g.XXX,X,samplingandanalytical)essentialtoits v  performance.Somematerialisincorporatedbyreferencefromothermethodsinthispart.Therefore,toobtainreliableresults,personsusingthismethodshouldhaveathoroughknowledgeofatleastthefollowingadditionaltestmethods:Method1,Method3,Method5,andMethod7.,XXXX1.0ScopeandApplicationXXX,X.   1.1Analytes.*q./ ddd Xdd Xdd X(#(#q, dd ,dd ,pdd +  /0" < p/Analyte .0!>0 .CASNo. .0!>0 .Sensitivity J119!> p 0 JNitrogenoxides(NOx), N asNO2,including: l Nitricoxide(NO)Nitrogendioxide(NO2) 211!""11 21010243910102440 211!0!'11 265655ppmv1'%N(    11 1 1.2Applicability.ThismethodisapplicableforthedeterminationofNOxemissionsfromstationarysources. n'!,  1.3DataQualityObjectives.Adherencetotherequirementsofthismethodwillenhancethequalityofthedataobtainedfromairpollutantsamplingmethods. ,`&2 ,XXXXH2.0SummaryofMethodXXX,X. Z  Agrabsampleiscollectedinanevacuatedflaskcontainingadilutesulfuricacidhydrogenperoxideabsorbingsolution.Thenitrogenoxides,excludingnitrousoxide(N2O),areoxidizedtonitrateandmeasuredbyion j  chromatography.,XXXX3.0DefinitionsXXX,X.[Reserved]   ,XXXX4.0InterferencesXXX,X. \   Biasedresultshavebeenobservedwhensamplingunderconditionsofhighsulfurdioxideconcentrations(above2000ppm).,XXXX5.0SafetyXXX,X. l  5.1Thismethodmayinvolvehazardousmaterials,operations,andequipment.Thistestmethodmaynotaddressallofthesafetyproblemsassociatedwithitsuse.Itistheresponsibilityoftheuserofthistestmethodtoestablishappropriatesafetyandhealthpracticesandtodeterminetheapplicabilityofregulatorylimitationspriortoperformingthistestmethod. 5.2Corrosivereagents.Thefollowingreagentsarehazardous.Personalprotectiveequipmentandsafeproceduresareusefulinpreventingchemicalsplashes.Ifcontactoccurs,immediatelyflushwithcopiousamountsof 2-&, wateratleast15minutes.Removeclothingundershoweranddecontaminate.Treatresidualchemicalburnsasthermalburns. 5.2.1HydrogenPeroxide(H2O2).Irritatingtoeyes,  L skin,nose,andlungs. 5.2.2SulfuricAcid(H2SO4).Rapidlydestructiveto .  bodytissue.Willcausethirddegreeburns.Eyedamagemayresultinblindness.Inhalationmaybefatalfromspasmofthelarynx,usuallywithin30minutes.Maycauselungtissuedamagewithedema.3mg/m3willcauselungdamagein > uninitiated.1mg/m3for8hourswillcauselungdamageor,  inhigherconcentrations,death.Provideventilationtolimitinhalation.Reactsviolentlywithmetalsandorganics.,XXXX6.0EquipmentandSuppliesXXX,X.   6.1SampleCollection.SameasinMethod7,Section6.1. 6.2SampleRecovery.SameasinMethod7,Section6.2,exceptthestirringrodandpHpaperarenotneeded. 6.3Analysis.Fortheanalysis,thefollowingequipmentandsuppliesarerequired.Alternative instrumentationandprocedureswillbeallowedprovidedthe n+%* calibrationprecisionrequirementinSection10.1.2andauditaccuracyrequirementinSection11.3canbemet.  6.3.1VolumetricPipets.ClassA;1,2,4,5ml(twoforthesetofstandardsandonepersample),6,10,andgraduated5mlsizes. 6.3.2VolumetricFlasks.50ml(twopersampleandoneperstandard),200ml,and1litersizes. 6.3.3AnalyticalBalance.Tomeasuretowithin0.1mg. 6.3.4IonChromatograph.Theionchromatographshouldhaveatleastthefollowingcomponents: 6.3.4.1Columns.Ananionseparationorothercolumncapableofresolvingthenitrateionfromsulfateandotherspeciespresentandastandardanionsuppressorcolumn(optional).Suppressorcolumnsareproducedasproprietaryitems;however,onecanbeproducedinthelaboratoryusingtheresinavailablefromBioRadCompany,32ndandGriffinStreets,Richmond,California.Peakresolutioncanbeoptimizedbyvaryingtheeluentstrengthorcolumnflowrate,orbyexperimentingwithalternativecolumnsthatmayoffermoreefficientseparation.Whenusingguardcolumnswiththestrongerreagenttoprotecttheseparationcolumn,theanalystshouldallowrestperiodsbetweeninjection 2-&, intervalstopurgepossiblesulfatebuildupintheguardcolumn. 6.3.4.2Pump.Capableofmaintainingasteadyflowasrequiredbythesystem. 6.3.4.3FlowGauges.Capableofmeasuringthespecifiedsystemflowrate. 6.3.4.4ConductivityDetector. 6.3.4.5Recorder.Compatiblewiththeoutputvoltagerangeofthedetector.,XXXX7.0ReagentsandStandardsXXX,X. >  Unlessotherwiseindicated,itisintendedthatallreagentsconformtothespecificationsestablishedbytheCommitteeonAnalyticalReagentsoftheAmericanChemicalSociety,wheresuchspecificationsareavailable;otherwise,usethebestavailablegrade. 7.1SampleCollection.SameasMethod7,Section7.1. 7.2SampleRecovery.SameasMethod7,Section7.1.1. 7.3Analysis.Thefollowingreagentsandstandardsarerequiredforanalysis:  7.3.1Water.SameasMethod7,Section7.1.1. n+%*  7.3.2StockStandardSolution,1mgNO2/ml.Dryan Z  adequateamountofsodiumnitrate(NaNO3)at105to110$C  (221to230$F)foraminimumof2hoursjustbefore   preparingthestandardsolution.Thendissolveexactly1.847gofdriedNaNO3inwater,anddilutetolliterina j  volumetricflask.Mixwell.Thissolutionisstableforlmonthandshouldnotbeusedbeyondthistime. 7.3.3WorkingStandardSolution,25g/ml.Dilute5mlofthestandardsolutionto200mlwithwaterinavolumetricflask,andmixwell. 7.3.4EluentSolution.Weigh1.018gofsodiumcarbonate(Na2CO3)and1.008gofsodiumbicarbonate l (NaHCO3),anddissolvein4litersofwater.Thissolution 0 is0.0024MNa2CO3/0.003MNaHCO3.Othereluentsappropriate N tothecolumntypeandcapableofresolvingnitrateionfromsulfateandotherspeciespresentmaybeused. 7.3.5QualityAssuranceAuditSamples.SameasMethod7,Section7.3.8.,XXXX8.0SampleCollection,Preservation,Storage,and "&$ TransportXXX,X. '!&  8.1Sampling.SameasinMethod7,Section8.1. 8.2SampleRecovery.SameasinMethod7,Section8.2,exceptdeletethestepsonadjustingandcheckingthe 2-&, pHofthesample.Donotstorethesamplesmorethan4daysbetweencollectionandanalysis.9.0QualityControl.*q23 dd dd dd pdd ./(#(#q,xdd ,Hdd ,`dd +  /0"  L 8/Section .0!0 0 .QualityControlMeasure .0!0  0 .Effect F19!0   8 0 F10.1 71*@ 1 7Ionchromatographcalibration .1!^ 1 .Ensurelinearityofionchromatographresponsetostandards J19!^   1 xJ11.3 ;1*^ 1 ;Auditsampleanalysis 21!@ 1 2Evaluateanalyticaltechnique,preparationofstandards1'%|"  x   1 110.0CalibrationandStandardizations. P  10.1IonChromatograph 10.1.1DeterminationofIonChromatographCalibrationFactorS.Prepareaseriesoffivestandardsbyadding1.0,2.0,4.0,6.0,and10.0mlofworkingstandardsolution(25g/ml)toaseriesoffive50mlvolumetricflasks.(Thestandardmasseswillequal25,50,100,150,and250g.)Diluteeachflasktothemarkwithwater,andmixwell.AnalyzewiththesamplesasdescribedinSection11.2,andsubtracttheblankfromeachvalue.Prepareorcalculatealinearregressionplotofthestandardmassesing(xaxis)versustheirpeakheightresponsesinmillimeters(yaxis).(Takepeakheightmeasurementswithsymmetricalpeaks;in allothercases,calculatepeakareas.)Fromthiscurve,or 8,%4 equation,determinetheslope,andcalculateitsreciprocaltodenoteasthecalibrationfactor,S.  10.1.2IonChromatographCalibrationQualityControl.Ifanypointonthecalibrationcurvedeviatesfromthelinebymorethan7percentoftheconcentrationatthatpoint,remakeandreanalyzethatstandard.ThisdeviationcanbedeterminedbymultiplyingStimesthepeakheightresponseforeachstandard.Theresultantconcentrationsmustnotdifferbymorethan7percentfromeachknownstandardmass(,XXXXi.e.XXX,X,25,50,100,150,and250g). >  10.2ConductivityDetector.Calibrateaccordingtomanufacturer'sspecificationspriortoinitialuse. 10.3Barometer.Calibrateagainstamercurybarometer. 10.4TemperatureGauge.Calibratedialthermometersagainstmercuryinglassthermometers. 10.5VacuumGauge.Calibratemechanicalgauges,ifused,againstamercurymanometersuchasthatspecifiedinSection6.1.6ofMethod7. 10.6AnalyticalBalance.Calibrateagainststandardweights.,XXXX11.0AnalyticalProceduresXXX,X. n+%*  11.1SamplePreparation. 2-&,  11.1.1Noteontheanalyticaldatasheet,theleveloftheliquidinthecontainer,andwhetheranysamplewaslostduringshipment.Ifanoticeableamountofleakagehasoccurred,eithervoidthesampleorusemethods,subjecttotheapprovaloftheAdministrator,tocorrectthefinalresults.Immediatelybeforeanalysis,transferthecontentsoftheshippingcontainertoa50mlvolumetricflask,andrinsethecontainertwicewith5mlportionsofwater.Addtherinsewatertotheflask,anddilutetothemarkwithwater.Mixthoroughly. 11.1.2Pipeta5mlaliquotofthesampleintoa50mlvolumetricflask,anddilutetothemarkwithwater.Mixthoroughly.Foreachsetofdeterminations,prepareareagentblankbydiluting5mlofabsorbingsolutionto50mlwithwater.(Alternatively,eluentsolutionmaybeusedinsteadofwaterinallsample,standard,andblankdilutions.) 11.2Analysis. 11.2.1PrepareastandardcalibrationcurveaccordingtoSection10.1.1.Analyzethesetofstandardsfollowedbythesetofsamplesusingthesameinjectionvolumeforbothstandardsandsamples.Repeatthisanalysissequencefollowedbyafinalanalysisofthestandardset.Average 2-&, theresults.Thetwosamplevaluesmustagreewithin5percentoftheirmeanfortheanalysistobevalid.Performthisduplicateanalysissequenceonthesameday.Diluteanysampleandtheblankwithequalvolumesofwateriftheconcentrationexceedsthatofthehigheststandard. 11.2.2Documenteachsamplechromatogrambylistingthefollowinganalyticalparameters:injectionpoint,injectionvolume,nitrateandsulfateretentiontimes,flowrate,detectorsensitivitysetting,andrecorderchartspeed. 11.3AuditSampleAnalysis.SameasMethod7,Section11.4.,XXXX12.0DataAnalysisandCalculationsXXX,X. 0  Carryoutthecalculations,retainingatleastoneextrasignificantfigurebeyondthatoftheacquireddata.Roundofffiguresafterfinalcalculations. 12.1SampleVolume.CalculatethesamplevolumeVsc "@  (inml),onadrybasis,correctedtostandardconditions,usingEquation72ofMethod7. 12.2SampleConcentrationofNOxasNO2. '!&  12.2.1CalculatethesampleconcentrationC(inmg/dscm)asfollows:@!C=(H)(S)(F)(104)/Vsc󀀈hhC(# Eq.7A1  2-&,  where: H=Samplepeakheight,mm. S=Calibrationfactor,g/mm. F=Dilutionfactor(requiredonlyifsample dilutionwasneededtoreducetheconcentration  intotherangeofcalibration),dimensionless. 104=1:10dilutiontimesconversionfactorof:     (mg/103g)(106ml/m3). \   12.2.2Ifdesired,theconcentrationofNO2maybe z  calculatedasppmNO2atstandardconditionsasfollows: > @"ppmNO2=0.5228ChhC(# Eq.7A2   0 where:  (# (#  0.5228=ml/mgNO2. 4 ,XXXX13.0MethodPerformanceXXX,X. R  13.1Range.Theanalyticalrangeofthemethodisfrom125to1250mgNOx/m3asNO2(65to655ppmv),and   higherconcentrationsmaybeanalyzedbydilutingthesample.Thelowerdetectionlimitisapproximately19mg/m3 b$" (10ppmv),butmayvaryamonginstruments.,XXXX14.0PollutionPreventionXXX,X.[Reserved] '!& ,XXXX15.0WasteManagementXXX,X.[Reserved] )T#(  ,XXXX16.0ReferencesXXX,X. r+%*  1.Mulik,J.D.,andE.Sawicki.IonChromatographic AnalysisofEnvironmentalPollutants.AnnArbor,AnnArborSciencePublishers,Inc.Vol.2,1979. 2.Sawicki,E.,J.D.Mulik,andE.Wittgenstein.IonChromatographicAnalysisofEnvironmentalPollutants.AnnArbor,AnnArborSciencePublishers,Inc.Vol.1.1978. 3.Siemer,D.D.SeparationofChlorideandBromidefromComplexMatricesPriortoIonChromatographicDetermination.Anal.Chem.52(12):18741877.October1980. z   4.Small,H.,T.S.Stevens,andW.C.Bauman.NovelIonExchangeChromatographicMethodUsingConductimetricDetermination.Anal.Chem.47(11):1801.1975. l  5.Yu,K.K.,andP.R.Westlin.EvaluationofReferenceMethod7FlaskReactionTime.SourceEvaluationSocietyNewsletter.4(4).November1979.10pp.   6.StackSamplingSafetyManual(Draft).U.S.EnvironmentalProtectionAgency,OfficeofAirQualityPlanningandStandard,ResearchTrianglePark,NC.September1978.17.0Tables,Diagrams,Flowcharts,andValidationData. '!& [Reserved]