Multi-Metals CEMS: A Review ofMetals CEMS: A Review ofCurrentlyAvailable TechnologygyKrag A. PettersonJh ACon.ooperCooperEnvironmentalServices, LLCS mposi m on AirSymposiumonAirQuality MeasurementMethods andTechnologyNovember 3, 2010Cooper Environmental Services1November3,2010Why Measure Metals?zSignificant adverse human health effects (cardiacarrhythmia neurotoxic elevated cancer risks)arrhythmia,neurotoxic,elevatedcancerrisks)zDeveloping fetus & children especially susceptiblezMetals represent 8 of US EPA’top 33 pollutants ofMetalsrepresent8ofUSEPA stop33pollutantsofhighest concernzArsenic is one of US EPA’s top three priority pollutantsof concernzGlobal concern for metals – As, Cd, Cr, Pb and Hg -RoHS, WEEE and ELVRoHS,WEEEandELV•US EPA. Framework for Inorganic MetalsRisk Assessment. EPA 120/R-07/001. March 2007.•US EPA. Health Effects Notebook for Hazardous Air Pollutants. EPA Technology Transfer Network Air Toxics Website.Accessed November 2007.•Agencyfor Toxic Substances and Disease Registry. Toxic Substances Portal. Accessed November 2007.Cooper Environmental Services2g y gyExamples of Contemporary Researchy1997, Costa and Dreher: “The lung dose of bioavailable transition metals,notinstilled PM mass, was the primary determinant of the acute inflammatory responsefor both the combustion source and ambient PM samples.”forboththecombustionsourceandambientPMsamples.y2002, Magari et al.:“...Results of this study suggest an association betweenexposure to airborne metals (vanadium, nickel, chromium, lead, copper, andmanganese) and significant alterations in cardiac autonomic function.”manganese)andsignificantalterationsincardiacautonomicfunction.y2009, Chen and Lippmann: “...Concentrations of nickel and vanadium in ambientair PM were associated with significant differences in mortality rates,while othermeasured PM components were not.”measuredPMcomponentswerenoty2010, Maciejczyk et al.: “Three metals (nickel, barium, and manganese)... appearto be much more influential on lung cell responses than black carbon and sulfateionsthatarepresentat much higher massconcentrations.”s a a e p ese a uc g e ass co ce a o syMetals Are A Significant Contributor to the Health EffectsAssociated With PMCooper Environmental Services3Multi-Metals CEMSMetals CEMS –A Brief HistoryA Brief Historyz1995 to 1997 EPA/DOE conducts testing of Multi-metalsCEMSz1996–EPA Proposes Hazardous Waste CombustorMACT – Multi-metals CEMS would be preferred methodfor Monitoring MetalsforMonitoringMetalsz1997 Lilly Begins Funding of Xactz1997 – EPA Proposes Performance Specification 10z1997 – Third in series of EPA Tests Concludes that nocurrently available multi-metals CEMS can meetperformance specification 10performancespecification10z1997 -2004 – Continued interest in MM CEMS from Lillyand Army because of potential HWC MACT requirementsCooper Environmental Services4Multi-Metals CEMSMetals CEMS –A Brief HistoryA Brief Historyz2001 and 2002 CES’ XCEM is Tested at Army DemilFurnacesz2004 – Army and Lilly Purchase Xactz2005 CES X t i M th d 301 V lid t d2005CESXactisMethod301Validatedz2006 – Lilly’s Alternative Monitoring Petition IncludesXact for Metals Compliancez2004 to Present - Lilly Xact Operates Passing all AnnualRATAsCooper Environmental Services5Overview of Measurement Approaches1997 Evaluation Included Eight different MM-CEMS at variousstages of developmentzInductively Coupled Plasma Atomic Emission Spectrometry (ICPAES) – 2 participants (Thermo Jerrell Ash)zLaser Induced Breakdown Spectroscopy (LIBS)2 participantsLaserInducedBreakdownSpectroscopy(LIBS)–2participantszSpark Induced Breakdown Spectroscopy - 1 vendorzMicrowave Induced Breakdown Spectroscopy–1participantpypzHigh Resolution Interferometric Spectrometer – VendorzHazardous Element Sampling Train (HEST) + XRF analysis –CES Precursor to XactzOnly CES’ XRF Approach is Currently AvailableCooper Environmental Services6XactReview1.How the instrument works2.M301 Validation3.QA Procedures and InstrumentPerformance4Compliance Performance Specifications.and Procedures5.Results from other testingCooper Environmental Services7Xact-CEMSConnect to Probe andTransport LineSamplingandMain Flow From Stack100 to 800 LpmDilutionModulep gAnalysis ModuleSub sample onto Tape ~1 LPMControlModuleFlow ModuleCooper Environmental Services8XACT SAMPLING AND ANALYSISX-Ray TubeRay TubeAerosol DepositSample FlowAnalysis AreaAnalysisAreaFilter TapeFilter TapeCooper Environmental Services9Determination of Stack ConcentrationMass(XRF)CONC (μg/m3)VOLUME=(MFM)Cooper Environmental Services10XACT DETECTION LIMITS (μg/m3)*Element15 Min.*60 Min.Meth. 29**Cr 0.2 0.03 0.3As 0.1 0.02 0.4Cd24 030 03...Hg 0.3 0.04 0.6Pb 0.4 0.06 0.3M0 30 040 3n...Co 0.3 0.04 0.3Ni 0.3 0.04 5.4Se 0.1 0.02 0.8Ag 4.6 0.6 2.6Sb6 10 71 1...*95% confidence based on3899blanksCooper Environmental Services11**120 minute samplesXact Method 301Xact Method 301 -ValidationValidationMethod 301 is a procedure or guideline fordetermining the precision and accuracydeterminingtheprecisionandaccuracyof candidate methodsThe Xact was validated using CES’Q tit ti A l G t QAGQuantitativeAerosolGenerator orQAGas a Reference MethodThink Cal Gas for MetalsThinkCalGasforMetalsCooper Environmental Services12QUANTITATIVE AEROSOL GENERATOR (QAG)(Previous Generation Used During M301 Testing)

e d )NISTTraceableAerosol TypesHeatedDrying Air n g A i r C h a m b e r ( h e a t eTraceableAerosolyp-Metals-PMTime

D r y i nPressuregauge-PMVRTCCQi/)(=Solution loss rateM lS lCarrier airvolume

l izerFlowMeterPeristalticPumpSolutionlossrateMetalSol. conc.IceNIST TraceableM t l l ti Nebu lCooper Environmental Services13BathMetals solutionM301 Arrangement(March 2005)Stack GasX tEntersXactQAGCooper Environmental Services14Xact Method 301Xact Method 301 -PrecisionPrecision4M301 R i d P i i 10%3

DM301 Required Precision=10%Passed 301 for Precision2

% RS D10AsCdCrPbHgCooper Environmental Services15AsCdCrPbHgXact-LinearityLinearityy= 0.952x - 1.10120140

m ) ayr = 0.995n = 96080100

o n (μg/dsc mCrA4060

o ncentrati oAsHgPbAll RESULTS INCLUDED02040

Xact C oPbCd00 20 40 60 80 100 120QAG Reference Concentration (μg/dscm)Cooper Environmental Services16Method 301Method 301 XactValidation SummaryzNumber of Runs 9 192 PasszP i i (RSD)10%3%PGoalTest ResultPass?zPrecision(RSD)<10%<3%PasszBias <20% <7% PasszCorr Coeff (R)>0 85>0 99PassCorr.Coeff.(R)..zNIST traceable Yes Yes PasszSlope ND 0.95 NDzIntercept ND 1.10 NDAll measurement results includedCooper Environmental Services17ND: Not DefinedAllmeasurementresultsincludedAutomated Quality Assurance1. Every Sample•Calibration stabilitycheck2. Daily•Upscale error check•Flow calibration checkcheck•Reactant level Check•Leak test•Flowcalibrationcheck•Zero level check3. Quarterly and annual audits•Linearity•Annual RATAcheck of the whole systemAnnualRATA-checkofthewholesystem4.OptionalOptionalindependent analytical audit ofarchived SamplesarchivedSamples18XRF QADaily Upscale RodPd Rod – FixedPosition – checksevery sampleCooper Environmental Services1912 Month Daily Calibration Error CheckXact Upscale March 2006 - March 200725002000

g/dsc mCd10001500

n tration (μCrHgRe-calibration was not requiredduring this 12 month period5001000

Conce nPb0Feb-06 May-06 Aug-06 Nov-06 Mar-0720DateXact Mercury Upscale Results12 Month Daily Calibration Error CheckMarch 2006 - March 2007500300400

( μg/dsc m± 5% errorPassedRATAPassedQuarterly Audit200300

e ntration (RATAQuarterlyAuditDifferenceAs – 2.2%Cd2 8%100

Conc e–2.8%Cr – 1.5%Pb – 2.3%Hg– 1.8%0Feb-06 May-06 Aug-06 Nov-06 Mar-07Date21MicromatterMicromatter StandardsStandardszUsed to calibrate the XactzUsed to perform XRFaudits on the Xact(Quarterly)zRecommended by IO 3 3RecommendedbyIO3.3for calibration of XRFinstrumentszGravimetrically NISTtraceableCooper Environmental Services22Daily Flow QA/QC Check-Percent Difference10.005 000 000 005.00

D ifferenc e0.003000

Percent D-5.00±3%23-10.00DateMarch 06 March 07Independent VerificationIndependent Verification of Xactof XactResultsM29 vs. Xact Prototypey = 1.09x - 9.602140160180

c m)72 Xact spots cutfrom tape and reR2= 0.986080100120140

t Pb (μg/ds c72 Xact Runspanalyzed in the lab020400 50 100 150 200M29 Pb ( /d )

Xac ty = 0.9727x + 3.42592140160180

2 00212 Method 29 RunsM29Pb(μg/dscm)R2= 0.96856080100120140

c. (μg/m3) July, 272 Lab. Anal.0204060

Lab Con72 Xact RunsIndependent Verification240 50 100 150 200Xact Conc. (μg/m3); May, 2002Lilly HWI Alternative Monitoring PlanzXact Used for CompliancezPass Performance SpecificationPassPerformanceSpecificationzOn-going QA RequirementsD il–ay–QuarterlyAnnually–Cooper Environmental Services25Lilly HWI Alternative Monitoring PlanPerformance Specificationsz7 Day Stability Test– Meet Criteria Every Day for 7 Days–Upscale Drift < 15% Drift – Checks XRF Drift–Zero Drift < 20% Drift – Checks XRF Drift in Background–Flow Drift < 20% Drift – Checks Stability of Xact FlowMeasurementzXRF Calibration Audit– <10% Error–Checks Calibration Against NIST Traceable StandardszFlow Calibration Audit<10% ErrorFlowCalibrationAudit-<10%Error–Flow Audit with NIST Traceable flow meterzLinearityRATA–Spiking with the QAG – Three Concentration Levels–Slope between 0.80 and 1.20Intercept less than 20% of emission limitCooper Environmental Services26–Interceptlessthan20%ofemissionlimit–Correlation Coefficient > 0.90Lilly HWI Alternative Monitoring PlanOn-GoingQA RequirementsqzDaily–Upscale–Zero–FlowzQuarterly–XRF–FlowA llznnuay–QAG LinearityCooper Environmental Services27Lilly QAG Audit Results Since 2006Cr As Cd Hg Pb AverageSlopeYear2006 0.83 0.90 0.85 0.82 0.85 0.852006(Quarterly) 0.91 0.77 0.95 0.92 0.93 0.892007 0.84 0.82 0.88 0.84 0.81 0.842008 0.96 0.71 0.98 0.99 0.97 0.922009 0.96 0.99 0.99 1.10 1.00 1.0120100.971.061.111.021.041.04Average 0.91 0.87 0.96 0.95 0.93 0.93HAS Passed All Required AnnualHASPassedAllRequiredAnnualand Quarterly Audits Since Startof AMPCooper Environmental Services28ofAMPXact CEMSEPA Method 301ValidatedAMP EPAApprovedEPA SiteC tifi d~6 Years OnSt k O tiCertifiedStackOperationsM 2007EPA Cl Ai29May2007–EPACleanAirExcellence AwardOver View of Other TestingzXCEM (Xact Predecessor) Comparison with M29 onArmy IncineratorzArmy Xact Comparison with M29 for As and Hg on aCoal Fired BoilerzSmall Business Innovative Research Grant–SpikingSmallBusinessInnovativeResearchGrantSpikingwith QAG on Coal Fired Test FurnacezHg Measurement on Coal-fired Power Plant –Comparison with Method 30B and Thermo HgFreedomCooper Environmental Services30XCEM Tests (2002)zComparison of XCEM to Method 29zMetals Spike at Army Munitions IncineratorzSpiked Concentration Measured by M29 and XactzSponsored by US Army Engineer Research andD l t C t C t ti E i iDevelopmentCenterConstructionEngineeringResearch Laboratory (EDRC/CERL)zM29gathered and analyzed byindependent laboratoryy yp ygroupCooper Environmental Services312002 XCEM Testing ResultsElement % RelativeAccuracyMet PS-10CriteriaPb4.4%Yes%Cd 17% YesCr15%YesBa 4% YesCooper Environmental Services32Army Xact Comparison to M29zLater Version of XactzHg and As spiked into a subsample of Coal fired boilerEffluentzHg and As Measured by M29 and XactR lt % R l ti AzResults%RelativeAccuracy–Hg – 17%–As 16%Cooper Environmental Services33EPA Sponsored Small BusinessInnovative Research GrantzCoal Fired furnace - EPA’s Multi-Pollutant ControlResearch FacilityXactvsQAGforAllElementszSpike a subsample of effluent with the QAG at 3concentration levelszCompare Xact to QAGy=1.1041x‐1.3829300.00350.00

3 )Xactvs.QAGforAllElementsCrLinearityzCompareXacttoQAGyR2=0.9912150.00200.00250.00

C onc. ( μ g/mAsCdHgExperimental Criteria ExperimentalSlopeLinearityCorrelation Coefficient0.0050.00100.00

Xact CPbCriteria Result Met? Criteria Average Criteria Met?Cr1.09 yes >0.99 yesAs1.14 yes >0.99 yesCd1.11yes>0.99yesElement>0.900.85 to1 150.00 50.00 100.00 150.00 200.00 250.00 300.00QAGConc.(μg/m)Cd1.11yes0.99yesHg1.14 yes >0.99 yesPb1.00 yes >0.99 yes0.901.15Cooper Environmental Services34Hg Measurement on Coal Fired PowerPlantz585 Mwatt Coal Fired Power PlantzDownstream of Electrostatic PrecipitatorzMeasurement of Stack Concentrations of HgzComparison with Method 30B and an on-site operatingTh M F d U itThermoMercuryFreedomUnitzXact was installed and operating within 2 daysCooper Environmental Services35Hg Measurement on a Coal FiredPower Plant8910

m )5678

c . ( μ g/dsc m3.53% RELATIVE2345

e rcury Con cCESXactMethod30BThermoCMMTh QA P i dACCURACY FOR CESXACT012

M eThermoQAPeriod0 1 2 3 4 5 6 7 8 9 10 11 12 13RATANumberCooper Environmental Services36Applicable Sources?zIncinerators(Tested and installed)zCoalfired Boilers(Tested)-firedBoilers(Tested)zWet and Dry Stacks(Tested)z50 PPM Acid Gases(Tested)zSmelters and MillsSmeltersandMillszCement and Lime KilnszMineral ProcessingzPlatingand WeldingCooper Environmental Services37g gWhat Next?zEPA Asked for Comment on the use of multi-metalsCEMS as a part of CISWI MACT (August 2010)zEPA Asked for Comment on the use of multi-metalsCEMS for Sewage Sludge Incinerators (September2010).zWhy is EPA regulating with Surrogate (PM) instead ofMM-CEMS?zMM-CEMS as an alternative to Hg CEMS + PMCEMS for PC MACT, Boiler MACT, CISWI MACTand Utility MACT?andUtilityMACT?Cooper Environmental Services38QUESTIONS?Krag Pettersonkragp@cooperenvironmental.comCooper Environmental Services39