ÿWPC%# 2ÒÞ‘w¼œ!Á5£E{<‘Üôoº”oNî¡6*3®¢±x‰ÓL7Ãõ•›v~€9iqù‡»M=…5ïZ |3ö—2ñdKHJ„Ð¥4åOviŸ×Ý4Ó;¢ƒüwu8Ù¿Y¼‹Úðº¨FrŒô:Í|B¥¡T€SŒ(U¾¼ú·ÿÜì|Ÿ†z)U/Ïñ³a^GX†W÷,§YêÐm·JŸJ n´·xųÒâ~œK\.'ˆYèA4ç•YNQ»‰¨,Vª=˜”ÿì‹Á·››pläÇt†¾:n .ÃĽfø  Ešÿ¡ÁuˆŠq dÀ©ñ‘qŒ)@_n€‡5·¿÷ò´d»¢@©ô0u“{>#Ùâá3ÔQhs“ù&?’ï:fâaVuâX±”*éU G‹+–ëù(3øøv,öêNmÑ/óÁåS…›PFK´Á "ìAO(üáçk°‡¹gzèó-A¬á8`wòûûšS¬GR8SÖ1ÎX7rzõæê­³è~¨*ïuËÖƒ…«}ï™xää§ØÀ2÷4Ÿs¢;—Ä»oÅ€Üá;sâÿo±¤‡­Ç¤§Üs/¹µ.‚é”7…í*âÖÙ–ö‡`q¶ýËÁ2ìå Õ{B|i%ñç"AǽL¸G/Ü# UN %a 0(gU.UB½wÿ4//////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////// D+>Æi 0O/ 0E~ AYÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃÃd™ pµ"˜Acrobat PDFWriter 3.0PDFWRITR,,,,,,,,0nLHÎ(ÈhH  Z 6Times New Roman RegularX($¡¡<þ6X9`(Courier<þ6X9`(*Courier 12pt10cpiEEj$dxd3|x'ÈÈÈÈdxd… Level 1 Level 2 Level 3 Level 4 Level 5('2§Ý$££Ý ƒ¤T!ÝÓ  ÓÝ  Ý(ÿÿ$––ò ò(Ú  ÚÚ  Ú)ó óz{|yMüÿ << deUUXXéC –gasXX¦éäàDX‚XX˜%(XXÚ%m{ÒiXX÷%âXXÇ%mhÒfXXì%)XX†œvXX†]xXX†xXX†ßxXX†"wXX œ}XX ]XX XX ßXX "~»X®OXXÄÑ(XXÑC‘~avgXX£ÑãXXs ÑbÜ ~cXXn Ñ)XXx•m BcXX˜ %âXX %(XXR %b» ÒiXX7 %âXX%bpÒfXXô%)XXµY2 fFUNC{€C_gas~=~€{€(m_i~+~m_f~)~€€LEFT€[€{€(C_avg~€„~b_c~)~}€OVER€m_c€€RIGHT]Ï~+(b_i~+~b_f~)}€OVER€{2}}ÌÝ ƒ!ÝÝ  ÝññÔ‡XýüXXXÔò òññññ(ññññññProposedññññññPROPOSED)€ññññTEST€METHOD€322€„€MEASUREMENT€OF€HYDROGEN€CHLORIDEÐ ° ÐEMISSIONS€FROM€PORTLAND€CEMENT€KILNS€BY€GFCIRó óÐ à ÐÔ  Ô1.0€€Applicability€and€PrincipleÌÓB.` hÀ£pÈ xÐ (#€%¬&°œXBÓà  à1.1€€Applicability.€€This€method€is€applicable€to€theÏdetermination€of€hydrogen€chloride€(HCl)€concentrations€inÏemissions€from€portland€cement€kilns.€€This€is€an€instrumentalÏmethod€for€the€measurement€of€HCl€using€an€extractive€samplingÏsystem€and€an€infrared€(IR)€gas„filter€correlation€(GFC)Ïanalyzer.€€This€method€is€intended€to€provide€the€cement€industryÏwith€a€direct€interface€instrumental€method.€€A€procedure€forÏanalyte€spiking€is€included€for€quality€assurance.€€This€methodÏis€considered€to€be€self„validating€provided€that€theÏrequirements€in€section€9€of€this€method€are€followed.Ìà  à1.2€€Principle.€€A€gas€sample€is€continuously€extracted€fromÏa€stack€or€duct€over€the€test€period€using€either€a€source„levelÏhot/wet€extractive€subsystem€or€a€dilution€extractive€subsystem.€ÏA€nondispersive€infrared€gas€filter€correlation€(NDIR„GFC)Ïanalyzer€is€specified€for€the€measurement€of€HCl€in€the€sample.€ÏThe€total€measurement€system€is€comprised€of€the€extractiveÏsubsystem,€the€analyzer,€and€the€data€acquisition€subsystem.€ÏTest€system€performance€specifications€are€included€in€thisÏmethod€to€provide€for€the€collection€of€accurate,€reproducibleÏdata.ÌÌÌà  à1.3€€Test€System€Operating€Range.€€The€measurement€rangeÏ(span)€of€the€test€system€shall€include€the€anticipated€HClÏconcentrations€of€the€effluent€and€spiked€samples.€€The€rangeÏshould€be€selected€so€that€the€average€of€the€effluentÏmeasurements€is€between€25€and€75€percent€of€span.€€If€at€anyÏtime€during€a€test€run,€the€effluent€concentration€exceeds€theÏspan€value€of€the€test€system,€the€run€shall€be€consideredÏinvalid.Ì2.0à  àSummary€of€MethodÐ  l! Ðà  à2.1€€Sampling€and€Analysis.€€Kiln€gas€is€continuouslyÏextracted€from€the€stack€or€duct€using€either€a€source€level,Ïhot/wet€extractive€system,€or€an€in„situ€dilution€probe€or€heatedÏout„of„stack€dilution€system.€€The€sample€is€then€directed€by€aÏheated€sample€line€maintained€above€350ð$ðF€to€a€GFC€analyzerÐ @$& Ðhaving€a€range€appropriate€to€the€type€of€sampling€system.€€TheÏgas€filter€correlation€analyzer€incorporates€a€gas€cell€filledÏwith€HCl.€€This€gas€cell€is€periodically€moved€into€the€path€ofÏan€infrared€measurement€beam€of€the€instrument€to€filter€outÏessentially€all€of€the€HCl€absorption€wavelengths.€€SpectralÏfiltering€provides€a€reference€from€which€the€HCl€concentrationÏof€the€sample€can€be€determined.€€Interferences€are€minimized€inÏthe€analyzer€by€choosing€a€spectral€band€over€which€compoundsÏsuch€as€COòò2óó€and€Hòò2óóO€either€do€not€absorb€significantly€or€do€notÐ ´+'/ Ðmatch€the€spectral€pattern€of€the€HCl€infrared€absorption.ÌÐ \-¬(1 Ðà  à2.2€€Operator€Requirements.€€The€analyst€must€be€familiarÏwith€the€specifications€and€test€procedures€of€this€method€andÏfollow€them€in€order€to€obtain€reproducible€and€accurate€data.Ð  -ð(4 Ð3.0à  àDefinitionsÐ ° Ðà  à3.1€€Measurement€System.€€The€total€equipment€required€forÏthe€determination€of€gas€concentration.€€The€measurement€systemÏconsists€of€the€following€major€subsystems:Ìà  à3.1.1€€Sample€Interface.€€That€portion€of€a€system€used€forÏone€or€more€of€the€following:€€sample€acquisition,€sampleÏtransport,€sample€conditioning,€or€protection€of€the€analyzersÏfrom€the€effects€of€the€stack€gas.Ìà  à3.1.2€€Gas€Analyzer.€€That€portion€of€the€system€that€sensesÏthe€gas€to€be€measured€and€generates€an€output€proportional€toÏits€concentration.ÌÔ  Ôà  à3.1.3€€Data€Recorder.€€A€strip€chart€recorder,€analogÏcomputer,€or€digital€recorder€for€recording€measurement€data€fromÏthe€analyzer€output.Ìà  à3.2€€Span.€€The€upper€limit€of€the€gas€concentrationÏmeasurement€range€displayed€on€the€data€recorder.Ìà  à3.3€€Calibration€Gas.€€A€known€concentration€of€a€gas€€in€anÏappropriate€diluent€gas€(i.e.,€Nòò2óó).Ð øH  Ðà  à3.4€€Analyzer€Calibration€Error.€€The€difference€between€theÏgas€concentration€exhibited€by€the€gas€analyzer€and€the€knownÏconcentration€of€the€calibration€gas€when€the€calibration€gas€isÏintroduced€directly€to€the€analyzer.Ìà  à3.5€€Sampling€System€Bias.€€The€sampling€system€bias€is€theÏdifference€between€the€gas€concentrations€exhibited€by€theÏmeasurement€system€when€a€known€concentration€gas€is€introducedÏat€the€outlet€of€the€sampling€probe€and€the€known€value€of€theÏcalibration€gas.ÌÔ  Ôà  à3.6€€Response€Time.€€The€amount€of€time€required€for€theÏmeasurement€system€to€display€95€percent€of€a€step€change€in€gasÏconcentration€on€the€data€recorder.Ìà  à3.7€€Calibration€Curve.€€A€graph€or€other€systematic€methodÏof€establishing€the€relationship€between€the€analyzer€responseÏand€the€actual€gas€concentration€introduced€to€the€analyzer.Ìà  à3.8€€Linearity.€€The€linear€response€of€the€analyzer€or€testÏsystem€to€known€calibration€inputs€covering€the€concentrationÏrange€of€the€system.Ìà  à3.9€€Interference€Rejection.€€The€ability€of€the€system€toÏreject€the€effect€of€interferences€in€the€analytical€measurementÏprocesses€of€the€test€system.Ì4.0à  àInterferencesÐ (#x' Ðà  à4.1€€Sampling€System€Interferences.€€An€importantÏconsideration€in€measuring€HCl€using€an€extractive€measurementÏsystem€is€to€ensure€that€a€representative€kiln€gas€sample€isÏdelivered€to€the€gas€analyzer.€€A€sampling€system€interferant€isÏa€factor€that€inhibits€an€analyte€from€reaching€the€analyticalÏinstrumentation.€€Condensed€water€vapor€is€a€strong€samplingÏsystem€interferant€for€HCl€and€other€water€soluble€compounds.€Ï"Cold€spots"€in€the€sampling€system€can€allow€water€vapor€in€theÏsample€to€condense€resulting€in€removal€of€HCl€from€the€sampleÏstream.€€The€extent€of€HCl€sampling€system€bias€depends€onÏconcentrations€of€potential€interferants,€moisture€content€of€theÏgas€stream,€temperature€of€the€gas€stream,€temperature€ofÏsampling€system€components,€sample€flow€rate,€and€reactivity€ofÏHCl€with€other€species€in€the€gas€stream.€€For€measuring€HCl€in€aÐ .h)5 Ðwet€gas€stream,€the€temperatures€of€the€gas€stream€and€samplingÏsystem€components€and€the€sample€flow€rate€are€of€primaryÏimportance.€€In€order€to€prevent€problems€with€condensation€inÏthe€sampling€system,€these€parameters€must€be€closely€monitored.Ìà  à4.1.1€€System€Calibration€Checks.€€Performing€theseÏcalibration€checks€where€HCl€calibration€gas€is€injected€throughÏthe€entire€system€both€before€and€after€each€test€runÏdemonstrates€the€integrity€of€the€sampling€system€and€capabilityÏof€the€analyzer€for€measuring€this€water€soluble€and€otherwiseÏunstable€compound€under€ideal€conditions€(i.e.,€HCl€in€Nòò2óó).Ð ¸   ÐÔ  Ôà  à4.1.2€€Analyte€Spiking€Checks.€€For€analyte€spiking€checks,ÏHCl€calibration€gas€is€quantitatively€added€to€the€sample€streamÏat€a€point€upstream€of€the€particulate€filter€and€all€otherÏsample€handling€components€both€before€and€after€each€test€run.€ÏThe€volume€of€HCl€spike€gas€should€not€exceed€10€percent€of€theÏtotal€sample€volume€so€that€the€sample€matrix€is€relativelyÏunaffected.€€Successfully€performing€these€checks€demonstratesÏthe€integrity€of€the€sampling€system€for€measuring€this€waterÏsoluble€and€reactive€compound€under€actual€sample€matrixÏconditions.€€Successfully€performing€these€checks€alsoÏdemonstrates€the€adequacy€of€the€interference€rejectionÏcapability€of€the€analyzer.€€(See€section€9.3€of€this€method.)Ìà  à4.2€€Analytical€Interferences.€€Analytical€interferences€areÏreduced€by€the€GFC€spectroscopic€technique€required€by€theÏmethod.€€The€accuracy€of€HCl€measurements€provided€by€some€GFCÏanalyzers€is€known€to€be€sensitive€to€the€moisture€content€of€theÏsample.€€This€must€be€taken€into€account€in€order€to€acquireÏaccurate€results.€€These€analyzers€must€be€calibrated€for€theÏspecific€moisture€content€of€the€samples.€€ÌÔ  Ô5.0à  àSafetyÐ X¨ Ðà  àThis€method€may€involve€sampling€at€locations€having€highÏpositive€or€negative€pressures,€or€high€concentrations€ofÏhazardous€or€toxic€pollutants,€and€cannot€address€all€safetyÏproblems€encountered€under€these€diverse€sampling€conditions.€€ItÏis€the€responsibility€of€the€tester(s)€to€ensure€proper€safetyÏand€health€practices,€and€to€determine€the€applicability€ofÏregulatory€limitations€before€performing€this€test€method.€ÏBecause€HCl€is€a€respiratory€irritant,€it€is€advisable€to€limitÏexposure€to€this€compound.Ì6.0à  àEquipment€and€SuppliesÐ (#x' Ðà  àNote:€€Mention€of€company€or€product€names€does€notÏconstitute€endorsement€by€the€U.€S.€Environmental€ProtectionÏAgency.Ìà  à6.1€€Measurement€System.€€Use€any€GFC€measurement€system€forÏHCl€that€meets€the€specifications€of€this€method.€€All€samplingÏsystem€components€must€be€maintained€above€the€kiln€gasÏtemperature,€when€possible,€or€at€least€350ð$ðF.€€The€length€ofÐ  (ð#. Ðsample€transport€line€should€be€minimized€and€sampling€rateÏshould€be€as€high€as€possible€to€minimize€adsorption€of€HCl.€€TheÏessential€components€of€the€measurement€system€are€described€inÏsections€6.1.1€through€6.1.12.Ìà  à6.1.1€€Sample€Probe.€€Glass,€stainless€steel,€Hastalloyð)ð,€orÏequivalent,€of€sufficient€length€to€traverse€the€sample€points.€ÏThe€sampling€probe€shall€be€heated€to€a€minimum€of€350ð$ðF€toÐ .h)5 Ðprevent€condensation.€€Dilution€extractive€systems€must€use€aÏdilution€ratio€such€that€the€average€diluted€concentrations€areÏbetween€25€to€75€percent€of€the€selected€measurement€range€of€theÏanalyzer.Ìà  à6.1.2€€Calibration€Valve€Assembly.€€Use€a€heated,€three„wayÏvalve€assembly,€or€equivalent,€for€selecting€either€sample€gas€orÏintroducing€calibration€gases€to€the€measurement€system€orÏintroducing€analyte€spikes€into€the€measurement€system€at€theÏoutlet€of€the€sampling€probe€before€the€primary€particulateÏfilter.Ìà  à6.1.3€€Particulate€Filter.€€A€coarse€filter€or€other€deviceÏmay€be€placed€at€the€inlet€of€the€probe€for€removal€of€largeÏparticulate€(10microns€or€greater).€€A€heated€(Balstonðð€orÏequivalent)€filter€rated€at€1€micron€is€necessary€for€primaryÏparticulate€removal,€and€shall€be€placed€immediately€after€theÏheated€probe.€€The€filter/filter€holder€shall€be€maintained€atÏ350ð$ðF€or€a€€higher€temperature.€€Additional€filters€at€the€inletÐ 0€  Ðof€the€gas€analyzer€may€be€used€to€prevent€accumulation€ofÏparticulate€material€in€the€measurement€system€and€extend€theÏuseful€life€of€components.€€All€filters€shall€be€fabricated€ofÏmaterials€that€are€nonreactive€with€HCl.€€Some€types€of€glassÏfilters€are€known€to€react€with€HCl.€€Ìà  à6.1.4€€Sample€Transport€Lines.€€Stainless€steel€orÏpolytetrafluoroethylene€(PTFE)€tubing€shall€be€heated€to€aÏminimum€temperature€of€350ð$ðF€(sufficient€to€prevent€condensationÐ pÀ Ðand€to€prevent€HCl€and€NHòò3óó€from€combining€into€ammonium€chlorideÐ 8ˆ Ðin€the€sampling€system)€to€transport€the€sample€gas€to€the€gasÏanalyzer.Ìà  à6.1.5€€Sample€Pump.€€Use€a€leak„free€pump€to€pull€the€sampleÏgas€through€the€system€at€a€flow€rate€sufficient€to€minimize€theÏresponse€time€of€the€measurement€system.€€The€pump€componentsÏthat€contact€the€sample€must€be€heated€to€a€temperature€greaterÏthan€350ð$ðF€and€must€be€constructed€of€a€material€that€isÐ °  Ðnonreactive€to€HCl.€€Ìà  à6.1.6€€Sample€Flow€Rate€Control.€€A€sample€flow€rate€controlÏvalve€and€rotameter,€or€equivalent,€must€be€used€to€maintain€aÏconstant€sampling€rate€within€ðð10percent.€€These€components€mustÏbe€heated€to€a€temperature€greater€than€350ð$ðF.€€(òòNoteóó:€€TheÐ ˜!è% Ðtester€may€elect€to€install€a€back„pressure€regulator€to€maintainÏthe€sample€gas€manifold€at€a€constant€pressure€in€order€toÏprotect€the€analyzer(s)€from€over„pressurization,€and€to€minimizeÏthe€need€for€flow€rate€adjustments.)Ìà  à6.1.7€€Sample€Gas€Manifold.€€A€sample€gas€manifold,€heatedÏto€a€minimum€of€350ð$ðF,€is€used€to€divert€a€portion€of€the€sampleÐ H&˜!+ Ðgas€stream€to€the€analyzer€and€the€remainder€to€the€by„passÏdischarge€vent.€€The€sample€gas€manifold€should€also€includeÏprovisions€for€introducing€calibration€gases€directly€to€theÏanalyzer.€€The€manifold€must€be€constructed€of€material€that€isÏnonreactive€to€the€gas€being€sampled.Ìà  à6.1.8€€Gas€Analyzer.€€Use€a€nondispersive€infrared€analyzerÏutilizing€the€gas€filter€correlation€technique€to€determine€HClÏconcentrations.€€The€analyzer€shall€meet€the€applicableÏperformance€specifications€of€section€8.0€of€this€method.€€(Note:€ÏHousing€the€analyzer€in€a€clean,€thermally„stable,€vibration€freeÐ .h)5 Ðenvironment€will€minimize€drift€in€the€analyzer€calibration.)€ÏThe€analyzer€(system)€shall€be€designed€so€that€the€response€of€aÏknown€calibration€input€shall€not€deviate€by€more€than€ðð3€percentÏfrom€the€expected€value.€€The€analyzer€or€measurement€systemÏmanufacturer€may€provide€documentation€that€the€instrument€meetsÏthis€design€requirement.€€Alternatively,€a€known€concentrationÏgas€standard€and€calibration€dilution€system€meeting€theÏrequirements€of€Method€205€of€appendix€M€to€part€51€of€thisÏchapter,€ð ðVerification€of€Gas€Dilution€Systems€for€FieldÏCalibrationsðð€(or€equivalent€procedure),€may€be€used€to€develop€aÏmulti„point€calibration€curve€over€the€measurement€range€of€theÏanalyzer.Ìà  à6.1.9€€Gas€Regulators.€€Single€stage€regulator€with€€crossÏpurge€assembly€that€is€used€to€purge€the€CGA€fitting€andÏregulator€before€and€after€use.€€(This€purge€is€necessary€toÏclear€the€calibration€gas€delivery€system€of€ambient€water€vaporÏafter€the€initial€connection€is€made,€or€after€cylinderÏchangeover,€and€will€extend€the€life€of€the€regulator.)€€WettedÏparts€are€316€stainless€steel€to€handle€corrosive€gases.Ìà  à6.1.10€€Data€Recorder.€€A€strip€chart€recorder,€analogÏcomputer,€or€digital€recorder,€for€recording€measurement€data.€ÏThe€data€recorder€resolution€(i.e.,€readability)€shall€be€0.5Ïpercent€of€span.€€Alternatively,€a€digital€or€analog€meter€havingÏa€resolution€of€0.5€percent€of€span€may€be€used€to€obtain€theÏanalyzer€responses€and€the€readings€may€be€recorded€manually.€€IfÏthis€alternative€is€used,€the€readings€shall€be€obtained€atÏequally„spaced€intervals€over€the€duration€of€the€sampling€run.€ÏFor€sampling€run€durations€of€less€than€1€hour,€measurements€atÏ1-minute€intervals€or€a€minimum€of€30measurements,€whichever€isÏless€restrictive,€shall€be€obtained.€€For€sampling€run€durationsÏgreater€than€1€hour,€measurements€at€2„minute€intervals€or€aÏminimum€of€96measurements,€whichever€is€less€restrictive,€shallÏbe€obtained.Ìà  à6.1.11€€Mass€Flow€Meters/Controllers.€€A€mass€flow€meterÏhaving€the€appropriate€calibrated€range€and€a€stated€accuracy€ofÏðð2€percent€of€the€measurement€range€is€used€to€measure€the€HClÏspike€flow€rate.€€This€device€must€be€calibrated€with€the€majorÏcomponent€of€the€calibration€spike€gas€(e.g.,€nitrogen)€using€anÏNIST€traceable€bubble€meter€or€equivalent.€€When€spiking€HCl,€theÏmass€flow€meter/controller€should€be€thoroughly€purged€before€andÏafter€introduction€of€the€gas€to€prevent€corrosion€of€theÏinterior€parts.ÌÔ  Ôà  à6.1.12€€System€Flow€Measurement.€€A€measurement€device€orÏprocedure€to€determine€the€total€flow€rate€of€sample€gas€withinÏthe€measurement€system.€€A€rotameter,€or€mass€flow€meterÏcalibrated€relative€to€a€laboratory€standard€to€within€ðð2€percentÏof€the€measurement€value€at€the€actual€operating€temperature,Ïmoisture€content,€and€sample€composition€(molecular€weight)€isÏacceptable.€€A€system€which€ensures€that€the€total€sample€flowÏrate€is€constant€within€ðð2percent€and€which€relies€on€anÏintermittent€measurement€of€the€actual€flow€rateÏ(e.g.,calibrated€gas€meter)€is€also€acceptable.Ìà  à6.2€€HCl€Calibration€Gases.€€The€calibration€gases€for€theÏgas€analyzer€shall€be€HCl€in€Nòò2óó.€€Use€at€least€three€calibrationÐ .h)5 Ðgases€as€specified€below:Ìà  à6.2.1€€High„Range€Gas.€€Concentration€equivalent€to€80€toÏ100€percent€of€the€span.Ìà  à6.2.2€€Mid„Range€Gas.€€Concentration€equivalent€to€40€to€60Ïpercent€of€the€span.ÌÔ  Ôà  à6.2.3€€Zero€Gas.€€Concentration€of€less€than€0.25percent€ofÏthe€span.€€Purified€ambient€air€may€be€used€for€the€zero€gas€byÏpassing€air€through€a€charcoal€filter€or€through€one€or€moreÏimpingers€containing€a€solution€of€3percent€Hòò2óóOòò2óó.Ð ð @ Ðà  à6.2.4€Spike€Gas.€€A€calibration€gas€of€known€concentrationÏ(typically€100to€200€ppm)€used€for€analyte€spikes€in€accordanceÏwith€the€requirements€of€section€9.3€of€this€method.Ì7.0à  àReagents€and€StandardsÐ `  Ðà  à7.1€€Hydrogen€Chloride.€€Hydrogen€Chloride€is€a€reactive€gasÏand€is€available€in€steel€cylinders€from€various€commercial€gasÏvendors.€€The€stability€is€such€that€it€is€not€possible€toÏpurchase€a€cylinder€mixture€whose€HCl€concentration€can€beÏcertified€at€better€than€ðð5€percent.€€The€stability€of€theÏcylinder€may€be€monitored€over€time€by€periodically€analyzingÏcylinder€samples.€€The€cylinder€gas€concentration€must€beÏverified€within€1€month€prior€to€the€use€of€the€calibration€gas.€ÏDue€to€the€relatively€high€uncertainty€of€HCl€calibration€gasÏvalues,€difficulties€may€develop€in€meeting€the€performanceÏspecifications€if€the€mid„range€and€high„range€calibration€gasesÏare€not€consistent€with€each€other.€€Where€problems€areÏencountered,€the€consistency€of€the€test€gas€standards€may€beÏdetermined:€€(1)€by€comparing€analyzer€responses€for€the€testÏgases€with€the€responses€to€additional€certified€calibration€gasÏstandards,€(2)€by€reanalysis€of€the€calibration€gases€inÏaccordance€with€sections€7.2.1€or€7.2.2€of€this€method,€or€(3)€byÏother€procedures€subject€to€the€approval€of€EPA.Ìà  à7.2€€Calibration€Gas€Concentration€Verification.€€There€€areÏtwo€alternatives€for€establishing€the€concentrations€ofÏcalibration€gases.€€Alternative€No.€1€is€preferred.Ìà  à7.2.1€€Alternative€No.€1.€€The€value€of€the€calibrationÏgases€may€be€obtained€from€the€vendor's€certified€analysis€withinÏ1€month€prior€to€the€test.€€Obtain€a€certification€from€the€gasÏmanufacturer€that€identifies€the€analytical€procedures€and€dateÏof€certification.Ìà  à7.2.2€€Alternative€No.€2.€€Perform€triplicate€analyses€ofÏthe€gases€using€Method26€of€appendix€A€to€part€60€of€thisÏchapter.€€Obtain€gas€mixtures€with€a€manufacturer's€tolerance€notÏto€exceed€ðð5percent€of€the€tag€value.€€Within€1€month€of€theÏfield€test,€analyze€each€of€the€calibration€gases€in€triplicateÏusing€Method€26€of€appendix€A€to€part€60€of€this€chapter.€€TheÏtester€must€follow€all€of€the€procedures€in€Method26€(e.g.,€useÏmidget€impingers,€heated€Pallflex€TX40H175€filter€(TFE„glassÏmat),€etc.€if€this€analysis€is€performed.€€Citation€3€in€sectionÏ13€of€this€method€describes€procedures€and€techniques€that€may€beÏused€for€this€analysis.€€Record€the€results€on€a€data€sheet.€ÏEach€of€the€individual€HCl€analytical€results€for€eachÏcalibration€gas€shall€be€within€5percent€(or€5ppm,€whichever€isÏgreater)€of€the€triplicate€set€average;€otherwise,€discard€theÏentire€set€and€repeat€the€triplicate€analyses.€€If€the€average€ofÐ .h)5 Ðthe€triplicate€analyses€is€within€5€percent€of€the€calibrationÏgas€manufacturer's€cylinder€tag€value,€use€the€tag€value;Ïotherwise,€conduct€at€least€three€additional€analyses€until€theÏresults€of€six€consecutive€runs€agree€within€5€percent€(or€5€ppm,Ïwhichever€is€greater)€of€the€average.€€Then€use€this€average€forÏthe€cylinder€value.Ìà  à7.3€€Calibration€Gas€Dilution€Systems.€€Sample€flow€rates€ofÏapproximately€15€L/min€are€typical€for€extractive€HCl€measurementÏsystems.€€These€flow€rates€coupled€with€response€times€of€15€toÏ30€minutes€will€result€in€consumption€of€large€quantities€ofÏcalibration€gases.€€The€number€of€cylinders€and€amount€ofÏcalibration€gas€can€be€reduced€by€the€use€of€a€calibration€gasÏdilution€system€in€accordance€with€Method€205€of€appendix€M€toÏpart€51€of€this€chapter,€"Verification€of€Gas€Dilution€SystemsÏfor€Field€Instrument€Calibrations."€€If€this€option€is€used,€theÏtester€shall€also€introduce€an€undiluted€calibration€gasÏapproximating€the€effluent€HCl€concentration€during€the€initialÏcalibration€error€test€of€the€measurement€system€as€a€qualityÏassurance€check.Ì8.0à  àTest€System€Performance€Specifications€Ð ˆØ Ðà  à8.1€€Analyzer€Calibration€Error.€€This€error€shall€be€lessÏthan€ðð5€percent€of€the€emission€standard€concentration€or€ðð1Ïppm,(whichever€is€greater)€for€zero,€mid„,€and€high„range€gases.Ìà  à8.2€€Sampling€System€Bias.€€This€bias€shall€be€less€thanÏðð7.5€percent€of€the€emission€standard€concentration€or€ðð1.5€ppmÏ(whichever€is€greater)€for€zero€and€mid„range€gases.Ìà  à8.3€€Analyte€Spike€Recovery.€€This€recovery€shall€be€betweenÏ70€to€130€percent€of€the€expected€concentration€of€spiked€samplesÏcalculated€with€the€average€of€the€before€and€after€run€spikes.€ÌÔ  Ô9.0à  àSample€Collection,€Preservation,€and€StorageÐ X¨ Ðà  à9.1€€Pretest.€€Perform€the€procedures€of€sections€9.1.1Ïthrough€9.1.3.3€of€this€method€before€measurement€of€emissionsÏ(procedures€in€section9.2€of€this€method).€€It€is€important€toÏnote€that€after€a€regulator€is€placed€on€an€HCl€gas€cylinderÏvalve,€the€regulator€should€be€purged€with€dry€Nòò2óó€or€dryÐ @" Ðcompressed€air€for€approximately€10€minutes€before€initiating€anyÏHCl€gas€flow€through€the€system.€€This€purge€is€necessary€toÏremove€any€ambient€water€vapor€from€within€the€regulator€andÏcalibration€gas€transport€lines;€the€HCl€in€the€calibration€gasÏmay€react€with€this€water€vapor€and€increase€system€responseÏtime.€€A€purge€of€the€system€should€also€be€performed€at€theÏconclusion€of€a€test€day€prior€to€removing€the€regulator€from€theÏgas€cylinder.€€Although€the€regulator€wetted€parts€are€corrosionÏresistant,€this€will€reduce€the€possibility€of€corrosionÏdeveloping€within€the€regulator€and€extend€the€life€of€theÏequipment.Ìà  à9.1.1€€Measurement€System€Preparation.€€Assemble€theÏmeasurement€system€by€following€the€manufacturer's€writtenÏinstructions€for€preparing€and€preconditioning€the€gas€analyzerÏand,€as€applicable,€the€other€system€components.€€Introduce€theÏcalibration€gases€in€any€sequence,€and€make€all€necessaryÏadjustments€to€calibrate€the€analyzer€and€the€data€recorder.€€IfÏnecessary,€adjust€the€instrument€for€the€specific€moistureÏcontent€of€the€samples.€€Adjust€system€components€to€achieveÐ .h)5 Ðcorrect€sampling€rates.Ìà  à9.1.2€€Analyzer€Calibration€Error.€€Conduct€the€analyzerÏcalibration€error€check€in€the€field€by€introducing€calibrationÏgases€to€the€measurement€system€at€any€point€upstream€of€the€gasÏanalyzer€in€accordance€with€sections€9.1.2.1€and€9.1.2.2€of€thisÏmethod.Ìà  à9.1.2.1€€After€the€measurement€system€has€been€prepared€forÏuse,€introduce€the€zero,€mid„range,€and€high„range€gases€to€theÏanalyzer.€€During€this€check,€make€no€adjustments€to€the€systemÏexcept€those€necessary€to€achieve€the€correct€calibration€gasÏflow€rate€at€the€analyzer.€€Record€the€analyzer€responses€to€eachÏcalibration€gas.€€òòNoteóó:€€A€calibration€curve€established€prior€toÐ H ˜  Ðthe€analyzer€calibration€error€check€may€be€used€to€convert€theÏanalyzer€response€to€the€equivalent€gas€concentration€introducedÏto€the€analyzer.€€However,€the€same€correction€procedure€shall€beÏused€for€all€effluent€and€calibration€measurements€obtainedÏduring€the€test.Ìà  à9.1.2.2€€The€analyzer€calibration€error€check€shall€beÏconsidered€invalid€if€the€difference€in€gas€concentrationÏdisplayed€by€the€analyzer€and€the€concentration€of€theÏcalibration€gas€exceeds€ðð5€percent€of€the€emission€standardÏconcentration€or€ðð1€ppm,€(whichever€is€greater)€for€the€zero,Ïmid„,€or€high„range€calibration€gases.€€If€an€invalid€calibrationÏis€exhibited,€cross„check€or€recertify€the€calibration€gases,Ïtake€corrective€action,€and€repeat€the€analyzer€calibration€errorÏcheck€until€acceptable€performance€is€achieved.Ìà  à9.1.3€€Sampling€System€Bias€Check.€€For€nondilutionÏextractive€systems,€perform€the€sampling€system€bias€check€byÏintroducing€calibration€gases€either€at€the€probe€inlet€or€at€aÏcalibration€valve€installed€at€the€outlet€of€the€sampling€probe.€ÏFor€dilution€systems,€calibration€gases€for€both€the€analyzerÏcalibration€error€check€and€the€sampling€system€bias€check€mustÏbe€introduced€prior€to€the€point€of€sample€dilution.€€ForÏdilution€and€nondilution€systems,€a€zero€gas€and€either€a€mid„¼range€or€high„range€gas€(whichever€more€closely€approximates€theÏeffluent€concentration)€shall€be€used€for€the€sampling€systemÏbias€check.Ìà  à9.1.3.1€€Introduce€the€upscale€calibration€gas,€and€recordÏthe€gas€concentration€displayed€by€the€analyzer.€€Then€introduceÏzero€gas,€and€record€the€gas€concentration€displayed€by€theÏanalyzer.€€During€the€sampling€system€bias€check,€operate€theÏsystem€at€the€normal€sampling€rate,€and€make€no€adjustments€toÏthe€measurement€system€other€than€those€necessary€to€achieveÏproper€calibration€gas€flow€rates€at€the€analyzer.€€AlternatelyÏintroduce€the€zero€and€upscale€gases€until€a€stable€response€isÏachieved.€€The€tester€shall€determine€the€measurement€systemÏresponse€time€by€observing€the€times€required€to€achieve€a€stableÏresponse€for€both€the€zero€and€upscale€gases.€€Note€the€longer€ofÏthe€two€times€and€note€the€time€required€for€the€measurementÏsystem€to€reach€95€percent€of€the€step€change€in€the€effluentÏconcentration€as€the€response€time.Ìà  à9.1.3.2€€For€nondilution€systems,€where€the€analyzerÏcalibration€error€test€is€performed€by€introducing€gases€directlyÏto€the€analyzer,€the€sampling€system€bias€check€shall€beÐ .h)5 Ðconsidered€invalid€if€the€difference€between€the€gasÏconcentrations€displayed€by€the€measurement€system€for€theÏsampling€system€bias€check€and€the€known€gas€concentrationÏstandard€exceeds€ðð7.5€percent€of€the€emission€standard€or€ðð1.5Ïppm,€(whichever€is€greater)€for€either€the€zero€or€the€upscaleÏcalibration€gases.€€If€an€invalid€calibration€is€exhibited,€takeÏcorrective€action,€and€repeat€the€sampling€system€bias€checkÏuntil€acceptable€performance€is€achieved.€€If€adjustment€to€theÏanalyzer€is€required,€first€repeat€the€analyzer€calibration€errorÏcheck,€then€repeat€the€sampling€system€bias€check.Ìà  à9.1.3.3€€For€dilution€systems€(and€nondilution€systems€whereÏall€calibration€gases€are€introduced€at€the€probe),€theÏcomparison€of€the€analyzer€calibration€error€results€and€samplingÏsystem€bias€check€results€is€not€meaningful.€€For€these€systems,Ïthe€sampling€system€bias€check€shall€be€considered€invalid€if€theÏdifference€between€the€gas€concentrations€displayed€by€theÏanalyzer€and€the€actual€gas€concentrations€exceed€ðð7.5€percent€ofÏthe€emission€standard€or€ðð1.5€ppm,€(whichever€is€greater)€forÏeither€the€zero€or€the€upscale€calibration€gases.€€If€an€invalidÏcalibration€is€exhibited,€take€corrective€action,€and€repeat€theÏsampling€system€bias€check€until€acceptable€performance€isÏachieved.€€If€adjustment€to€the€analyzer€is€required,€firstÏrepeat€the€analyzer€calibration€error€check.ÌÔ  Ôà  à9.2€€Emission€Test€ProceduresÌà  à9.2.1€€Selection€of€Sampling€Site€and€Sampling€Points.€ÏSelect€a€measurement€site€and€sampling€points€using€the€sameÏcriteria€that€are€applicable€to€Method€26€of€appendix€A€to€partÏ60€of€this€chapter.ÌÌà  à9.2.2€€Sample€Collection.€€Position€the€sampling€probe€atÏthe€first€measurement€point,€and€begin€sampling€at€the€same€rateÏas€used€during€the€sampling€system€bias€check.€€Maintain€constantÏrate€sampling€(i.e.,€ðð10€percent)€during€the€entire€run.€€FieldÏtest€experience€has€shown€that€conditioning€of€the€sample€systemÏis€necessary€for€approximately€1„hour€prior€to€conducting€theÏfirst€sample€run.€€This€conditioning€period€should€be€repeatedÏafter€particulate€filters€are€replaced€and€at€the€beginning€ofÏeach€new€day€or€following€any€period€when€the€sampling€system€isÏinoperative.€€Experience€has€also€shown€that€prior€to€adequateÏconditioning€of€the€system,€the€response€to€analyte€spikes€and/orÏthe€change€from€an€upscale€calibration€gas€to€a€representativeÏeffluent€measurement€may€be€delayed€by€more€than€twice€the€normalÏmeasurement€system€response€time.€€It€is€recommended€that€theÏanalyte€spikes€(see€section€9.3€of€this€method)€be€performed€toÏdetermine€if€the€system€is€adequately€conditioned.€€The€samplingÏsystem€is€ready€for€use€when€the€time€required€for€theÏmeasurement€system€to€equilibrate€after€a€change€from€aÏrepresentative€effluent€measurement€to€a€representative€spikedÏsample€measurement€approximates€the€calibration€gas€response€timeÏobserved€in€section€9.1.3.1€of€this€method.Ìà  à9.2.3€€Sample€Duration.€€After€completing€the€samplingÏsystem€bias€checks€and€analyte€spikes€prior€to€a€test€run,Ïconstant€rate€sampling€of€the€effluent€should€begin.€€For€eachÏrun,€use€only€those€measurements€obtained€after€all€residualÐ .h)5 Ðresponse€to€calibration€standards€or€spikes€are€eliminated€andÏrepresentative€effluent€measurements€are€displayed€to€determineÏthe€average€effluent€concentration.€€At€a€minimum,€this€requiresÏthat€the€response€time€of€the€measurement€system€has€elapsedÏbefore€data€are€recorded€for€calculation€of€the€average€effluentÏconcentration.€€Sampling€should€be€continuous€for€the€duration€ofÏthe€test€run.€€The€length€of€data€collection€should€be€at€leastÏas€long€as€required€for€sample€collection€by€Method€26€of€part€60Ïof€this€chapter.€€One€hour€sampling€runs€using€this€method€haveÏprovided€reliable€data€for€cement€kilns.ÌÔ  Ôà  à9.2.4€€Validation€of€Runs.€€Before€and€after€each€run,€or€ifÏadjustments€are€necessary€for€the€measurement€system€during€theÏrun,€repeat€the€sampling€system€bias€check€procedure€described€inÏsection9.1.3€of€this€method.€€(Make€no€adjustments€to€theÏmeasurement€system€until€after€the€drift€checks€are€completed.)€ÏRecord€the€analyzer's€responses.Ìà  à9.2.4.1€€If€the€post„run€sampling€system€bias€for€either€theÏzero€or€upscale€calibration€gas€exceeds€the€sampling€system€biasÏspecification,€then€the€run€is€considered€invalid.€€TakeÏcorrective€action,€and€repeat€both€the€analyzer€calibration€errorÏcheck€procedure€(section9.1.2€of€this€method)€and€the€samplingÏsystem€bias€check€procedure€(section€9.1.3€of€this€method)€beforeÏrepeating€the€run.Ìà  à9.2.4.2€€If€the€post„run€sampling€system€bias€for€both€theÏzero€and€upscale€calibration€gas€are€within€the€sampling€systemÏbias€specification,€then€construct€two€2„point€straight€lines,Ïone€using€the€pre„run€zero€and€upscale€check€values€and€the€otherÏusing€the€post„run€zero€and€upscale€check€values.€€Use€the€slopesÏand€y„intercepts€of€the€two€lines€to€calculate€the€gasÏconcentration€for€the€run€in€accordance€with€equation€1€of€thisÏmethod.€Ìà  à9.3€€Analyte€Spikingð"ðSelf„Validating€Procedure.€€Use€analyteÏspiking€to€verify€the€effectiveness€of€the€sampling€system€forÏthe€target€compounds€in€the€actual€kiln€gas€matrix.€€QualityÏassurance€(QA)€spiking€should€be€performed€before€and€after€eachÏsample€run.€€The€spikes€may€be€performed€following€the€samplingÏsystem€bias€checks€(zero€and€mid„range€system€calibrations)Ïbefore€each€run€in€a€series€and€also€after€the€last€run.€€The€HClÏspike€recovery€should€be€within€ðð30percent€as€calculated€usingÏequations€1€and€2€of€this€method.€€Two€general€approaches€areÏapplicable€for€the€use€of€analyte€spiking€to€validate€a€GFC€HClÏmeasurement€system:€€(1)€two€independent€measurement€systems€canÏbe€operated€concurrently€with€analyte€spikes€introduced€to€one€ofÏthe€systems,€or€(2)€a€single€measurement€system€can€be€used€toÏanalyze€consecutively,€spiked€and€unspiked€samples€in€anÏalternating€fashion.€€The€two„system€approach€is€similar€toÏMethod€301€of€this€appendix€and€the€measurement€bias€isÏdetermined€from€the€difference€in€the€paired€concurrentÏmeasurements€relative€to€the€amount€of€HCl€spike€added€to€theÏspiked€system.€€The€two„system€approach€must€employ€identicalÏsampling€systems€and€analyzers€and€both€measurement€systemsÏshould€be€calibrated€using€the€same€mid„€and€high„rangeÏcalibration€standards.€€The€two„system€approach€should€be€largelyÏunaffected€by€temporal€variations€in€the€effluent€concentrationsÐ .h)5 Ðif€both€measurement€systems€achieve€the€same€calibrationÏresponses€and€both€systems€have€the€same€response€times.€€(SeeÏMethod€301€of€this€appendix€for€appropriate€calculationÏprocedures.)€€The€single€measurement€system€approach€isÏapplicable€when€the€concentration€of€HCl€in€the€source€does€notÏvary€substantially€during€the€period€of€the€test.€€Since€theÏapproach€depends€on€the€comparison€of€consecutive€spiked€andÏunspiked€samples,€temporal€variations€in€the€effluent€HClÏconcentrations€will€introduce€errors€in€determining€the€expectedÏconcentration€of€the€spiked€samples.€€If€the€effluent€HClÏconcentrations€vary€by€more€than€ðð10€percent€(or€ðð5€ppm,Ïwhichever€is€greater)€during€the€time€required€to€obtain€andÏequilibrate€a€new€sample€(system€response€time),€it€may€beÏnecessary€to:€€(1)€use€a€dual€sampling€system€approach,Ï(2)postpone€testing€until€stable€emission€concentrations€areÏachieved,€(3)€switch€to€the€two„system€approach€[if€possible]€or,Ï(4)€rely€on€alternative€QA/QC€procedures.€€The€dual„samplingÏsystem€alternative€uses€two€sampling€lines€to€convey€sample€toÏthe€gas€distribution€manifold.€€One€of€the€sample€lines€is€usedÏto€continuously€extract€unspiked€kiln€gas€from€the€source.€€TheÏother€sample€line€serves€as€the€analyte€spike€line.€€One€GFCÏanalyzer€can€be€used€to€alternately€measure€the€HCl€concentrationÏfrom€the€two€sampling€systems€with€the€need€to€purge€only€theÏcomponents€between€the€common€manifold€and€the€analyzer.€€ThisÏminimizes€the€time€required€to€acquire€an€equilibrated€sample€ofÏspiked€or€unspiked€kiln€gas.€€If€the€source€varies€by€more€thanÏðð10€percent€or€ðð5ppm,€(whichever€is€greater)€during€the€time€itÏtakes€to€switch€from€the€unspiked€sample€line€to€the€spikedÏsample€line,€then€the€dual„sampling€system€alternative€approachÏis€not€applicable.€€As€a€last€option,€(where€no€otherÏalternatives€can€be€used)€a€humidified€nitrogen€stream€may€beÏgenerated€in€the€field€which€approximates€the€moisture€content€ofÏthe€kiln€gas.€€Analyte€spiking€into€this€humidified€stream€can€beÏemployed€to€assure€that€the€sampling€system€is€adequate€forÏtransporting€the€HCl€to€the€GFC€analyzer€and€that€the€analyzer'sÏwater€interference€rejection€is€adequate.Ìà  à9.3.1€€Spike€Gas€Concentration€and€Spike€Ratio.€€The€volumeÏof€HCl€spike€gas€should€not€exceed€10percent€of€the€total€sampleÏvolume€(i.e.,€spike€to€total€sample€ratio€of€1:10)€to€ensure€thatÏthe€sample€matrix€is€relatively€unaffected.€€An€ideal€spikeÏconcentration€should€approximate€the€native€effluentÏconcentration,€thus€the€spiked€sample€concentrations€wouldÏrepresent€approximately€twice€the€native€effluent€concentrations.€ÏThe€ideal€spike€concentration€may€not€be€achieved€because€theÏnative€HCl€concentration€cannot€be€accurately€predicted€prior€toÏthe€field€test,€and€limited€calibration€gas€standards€will€beÏavailable€during€the€field€test.€€Some€flexibility€is€availableÏby€varying€the€spike€ratio€over€the€range€from€1:10€to€1:20.€ÏPractical€constraints€must€be€applied€to€allow€the€tester€toÏspike€at€an€anticipated€concentration.€€Thus,€the€tester€may€useÏa€100€ppm€calibration€gas€and€a€spike€ratio€of€1:10€as€defaultÏvalues€where€information€regarding€the€expected€HCl€effluentÏconcentration€is€not€available€prior€to€the€tests.€ÏAlternatively,€the€tester€may€select€another€calibration€gasÐ .h)5 Ðstandard€and/or€lower€spike€ratio€(e.g.,€1:20)€to€more€closelyÏapproximate€the€effluent€HCl€concentration.Ìà  à9.3.2€€Spike€Procedure.€€Introduce€the€HCl€spike€gas€mixtureÏat€a€constant€flow€rate€(ðð2€percent)€at€less€than€10€percent€ofÏthe€total€sample€flow€rate.€€(For€example,€introduce€the€HClÏspike€gas€at€1€L/min€(ðð20€cc/min)€into€a€total€sample€flow€rateÏof€10L/min).€€The€spike€gas€must€be€preheated€beforeÏintroduction€into€the€sample€matrix€to€prevent€a€localizedÏcondensation€of€the€gas€stream€at€the€spike€introduction€point.€ÏA€heated€sample€transport€line(s)€containing€multiple€transportÏtubes€within€the€heated€bundle€may€be€used€to€spike€gas€upÏthrough€the€sampling€system€to€the€spike€introduction€point.€€UseÏa€calibrated€flow€device€(e.g.,€mass€flow€meter/controller)€toÏmonitor€the€spike€flow€rate.€€Use€a€calibrated€flow€device€(e.g.,Ïrotameter,€mass€flow€meter,€orifice€meter,€or€other€method)€toÏmonitor€the€total€sample€flow€rate.€€Calculate€the€spike€ratioÏfrom€the€measurements€of€spike€flow€and€total€flow.€€(SeeÏequation€2€and€3€in€section10.2€of€this€method.)Ìà  à9.3.3€€Analyte€Spiking.€€Determine€the€approximate€effluentÏHCl€concentrations€by€examination€of€preliminary€samples.€€ForÏsingle„system€approaches,€determine€whether€the€HCl€concentrationÏvaries€significantly€with€time€by€comparing€consecutive€samplesÏfor€the€period€of€time€corresponding€to€at€least€twice€the€systemÏresponse€time.€€(For€analyzers€without€sample€averaging,€estimateÏaverage€values€for€two€to€five€minute€periods€by€observing€theÏinstrument€display€or€data€recorder€output.)€If€the€concentrationÏof€the€individual€samples€varies€by€more€than€ðð10€percentÏrelative€to€the€mean€value€or€ðð5€ppm,€(whichever€is€greater),€anÏalternate€approach€may€be€needed.Ìà  à9.3.3.1€€Adjust€the€spike€flow€rate€to€the€appropriate€levelÏrelative€to€the€total€flow€by€metering€spike€gas€through€aÏcalibrated€mass€flow€meter€or€controller.€€Allow€spike€flow€toÏequilibrate€within€the€sampling€system€for€at€least€theÏmeasurement€system€response€time€and€a€steady€response€to€theÏspike€gas€is€observed€before€recording€response€to€the€spiked€gasÏsample.€€Next,€terminate€the€spike€gas€flow€and€allow€theÏmeasurement€system€to€sample€only€the€effluent.€€After€theÏmeasurement€system€response€time€has€elapsed€and€representativeÏeffluent€measurements€are€obtained,€record€the€effluent€unspikedÏconcentration.€€Immediately€calculate€the€spike€recovery.Ìà  à9.3.3.2€€If€the€spike€recovery€is€not€within€acceptableÏlimits€and€a€change€in€the€effluent€concentration€is€suspected€asÏthe€cause€for€exceeding€the€recovery€limit,€repeat€the€analyteÏspike€procedure€without€making€any€adjustments€to€the€analyzer€orÏsampling€system.€€If€the€second€spike€recovery€falls€within€theÏrecovery€limits,€disregard€the€first€attempt€and€record€theÏresults€of€the€second€spike.€€Ìà  à9.3.3.3€€Analyte€spikes€must€be€performed€before€and€afterÏeach€test€run.€€Sampling€system€bias€checks€must€also€beÏperformed€before€and€after€each€test€run.€€Depending€on€theÏparticular€sampling€strategy€and€other€constraints,€it€may€beÏnecessary€to€compare€effluent€data€either€immediately€before€orÏimmediately€after€the€spike€sample€to€determine€the€spikeÏrecovery.€€Either€method€is€acceptable€provided€a€consistentÐ .h)5 Ðapproach€is€used€for€the€test€program.€€The€average€spikeÏrecovery€for€the€pre„€and€post„run€spikes€shall€be€used€toÏdetermine€if€spike€recovery€is€between€70and€130€percent.€€ÌÌ10.0€€Data€Analysis€and€Emission€CalculationsÌà  àThe€average€gas€effluent€concentration€is€determined€fromÏthe€average€gas€concentration€displayed€by€the€gas€analyzer€andÏis€adjusted€for€the€zero€and€upscale€sampling€system€bias€checks,Ïas€determined€in€accordance€with€section9.2.3€of€this€method.€ÏThe€average€gas€concentration€displayed€by€the€analyzer€may€beÏdetermined€by€integration€of€the€area€under€the€curve€for€chartÏrecorders,€or€by€averaging€all€of€the€effluent€measurements.€ÏAlternatively,€the€average€may€be€calculated€from€measurementsÏrecorded€at€equally€spaced€intervals€over€the€entire€duration€ofÏthe€run.€€For€sampling€run€durations€of€less€than€1„hour,€averageÏmeasurements€at€2„minute€intervals€or€less,€shall€be€used.€€ForÏsampling€run€durations€greater€than€1„hour,€measurements€at€2„¼minute€intervals€or€a€minimum€of€96measurements,€whichever€isÏless€restrictive,€shall€be€used.€€Calculate€the€effluent€gasÏconcentration€using€equation€1.Ì߉€}ÛÚQA=z ,¹ 0  €@ Pdddd@E°P¹Û›aƒèP¨‰ßâ (#(#°(#°(#âÌà è àà ˜ à(Eq.€1)ÌÌwhere:ÌÓ~[X°` ¸ / hÀpÈ xÐ (#€%Ø'0*ˆ,à.813è5@8˜:ð<H? AøC` ƒX£p†X¬&~Óà0 è àà0@è(#è(#àà è àbòòcóóà @ à=€€Y„Ð pÀ Ðintercept€ofÏtheÏcalibrationÏâ °(#@(#(#@(#âleast„¼squares€à @! àà @! à¼line.Ð @(#@(# Ðà  àbòòfóóà0 ` à=€€Y„intercept€of€the€final€bias€check€2„point€à Ð àà @Ð àline.Ðè8` (#` (# Ðà  àbòòióóà ` à=€€Y„intercept€of€the€initial€bias€check€2„point€à Ð àÐ °  Ðà  àà ` àà × àline.Ìà0  àCòògasóóà0` (#(#à=€€Effluent€gas€concentration,€as€measured,€ppm.Ð@"` (#` (# Ðà  àCòòavgóóà0 ` à=€€Average€gas€concentration€indicated€by€gas€à Ð àà @Ð àÐ  X# Ðanalyzer,€as€measured,€ppm.Ð ` (#` (# Ðà  àmòòcóóà ` à=€€Slope€of€the€calibration€least„squares€line.Ð ˜!è% Ðà  àmòòfóóà ` à=€€Slope€of€theòò€óófinal€bias€check€2„point€line.Ð `"°& Ðà  àmòòià ` à=à × àóóSlope€of€theòò€óóinitial€bias€check€2„point€line.Ð (#x' ÐÌThe€following€equations€are€used€to€determine€the€percentÏrecovery€(%R)€for€analyte€spiking:Ì€€€€€€€€€€€€€€€€€òò%R€=€(SòòMóó/CòòEóó)€x€100à€88D(#à(Eq.€2)óóˆÐ H&˜!+ Ðwhere:ÌÓx[X°`  / hÀpÈ xÐ (#€%Ø'0*ˆ,à.813è5@8˜:ð<H? AøCX„X/ h–XxÓà0  àà0« (#(#àà  àSòòMóó€=€€Mean€concentration€of€duplicate€analyte€spiked€à Ð àà @Ð àÐ 0(€#- Ðsamples€(observed).Ð « (#« (# Ðà0  àà0« (#(#àà  àCòòEóó€=€€Expected€concentration€of€analyte€spiked€samples€à @  àà @  àà @  àÐ À)%/ Ð(theoretical).Ð « (#« (# Ѐ€€€€€€€€€€òòCòòEóó€=€CòòSóó(QòòSóó/QòòTóó)€+€SòòUóó(1„QòòSóó/QòòTóó)€à€88D(#à(Eq.€3)óóˆÐ P+ &1 Ðwhere:Ìà0  àà0« (#(#àà  àCòòSóó€=€€Concentration€of€HCl€spike€gas€(cylinder€tag€à Ð àà @Ð àÐ 8-ˆ(3 Ðvalue).Ð.P)4« (#« (# Ðà0  àQòòSóó€=à0« (#(#àSpike€gas€flow€rate.а« (#« (# Ðà0  àQòòTóó€=à0« (#(#àTotal€sample€flow€rate€(effluent€sample€flow€plusÐ xÈ Ðspike€flow).Ð « (#« (# Ðà0  àSòòUóó€=à0« (#(#àNative€concentration€of€HCl€in€unspiked€effluentÐ X Ðsamples.Ð « (#« (# ÐAcceptable€recoveries€for€analyte€spiking€are€ðð30€percent.Ì11.0€€Pollution€PreventionÌà  àGas€extracted€from€the€source€and€analyzed€or€vented€fromÏthe€system€manifold€shall€be€either€scrubbed,€exhausted€back€intoÏthe€stack,€or€discharged€into€the€atmosphere€where€suitableÏdilution€can€occur€to€prevent€harm€to€personnel€health€andÏwelfare€or€plant€or€personal€property.Ì12.0€€Waste€ManagementÌà  àGas€standards€of€HCl€are€handled€as€according€to€theÏinstructions€enclosed€with€the€materials€safety€data€sheets.Ì13.0€€ReferencesÌà  à1.€€Peeler,€J.W.,€Summary€Letter€Report€to€Ann€Dougherty,ÏPortland€Cement€Association,€June€20,€1996.Ìà  à2.€€Test€Protocol,€Determination€of€Hydrogen€ChlorideÏEmissions€from€Cement€Kilns€(Instrumental€Analyzer€Procedure)ÏRevision€4;€June€20,€1996.Ìà  à3.€€Westlin,€Peter€R.€and€John€W.€Brown.€€Methods€forÏCollecting€and€Analyzing€Gas€Cylinder€Samples.€€Source€EvaluationÏSociety€Newsletter.€€òò3óó(3):5„15.€€September€1978.Ô#†XܺXXX6# #ÔÔ‡X6#XXXܺÔÐ ¨ø ÐÔ#†XܺXXX6#X®#Ôññ