The Chemical Composition of PM2.5to support PM ImplementationNeil FrankAQAG/AQAD USEPAFor Presentation atEPA State / Local / Tribal Training Workshop: PM2.5 Final Rule Implementation and 2006 PM 2.5Designation ProcessJune20-212Topics• How do we derive FRM PM2.5composition• How does avg composition vary by region, byseason and over time• Variation within urban areas• What are the local vs regional components andhow does this relate to potential emissionsources• Differences between peak day and averagecomposition3What is the composition of PM2.5and where does it come from?Major components• Ammonium Sulfate• Ammonium Nitrate• OrganicCarbonaceous Mass• Elemental Carbon• Crustal MaterialSO2NOXDirect PMVOC+NH3The chemistry is complicated and particle formationis dependent on other pollutants and atmospheric conditionsFrom:The Particle Pollution Report:Current Understanding of Air Quality and Emissions through 20034To estimate urban PM2.5 composition• Use measurements from routinemonitoring networks– STN, SLAMS (=CSN)• Make adjustments to represent FRM mass•FRM mass does notequal the simple sum ofthe measured components[i.e. PM2.5 = AmmSul + AmmNitr + OCM +EC + Crustal]5Cleveland, OH

NO3 Concentration0.02.04.06.08.0J FMAMJ J ASONDannavgBirmingham, ALJ FMAMJ J ASONDannavg6 Nitrate Study Sites, 2003FRM doesn’t retain all ambient nitratesMonthly and AnnualAverage NO3, 2003STN (total bar)FRM (red barand black line)Sulfate Nitrate TCM Crustal PassiveReconstructed Fine MassRCFM(reflects ambient)SANDWICH(reflects FRM PM2.5)FRM Compared to SpeciationNetwork Measurements• Less Nitrate• Includes particle bound water• Carbon achieves mass balanceand reflects all needed adjustmentsPM2.5 mass alsoincludesparticle bound water(at mass weighing conditions)6SANDWICHmore than a cute acronym• What is theSANDWICHApproach?–Sulfate,AdjustedNitrate,DerivedWater,InferredCarbonHybrid materialbalance approach• for estimating PM2.5 mass composition asif it was measured by the PM2.5 FRM.– The approach uses a combination ofspeciation measurements and modeledspeciation estimates to represent FRM PM2.5.• Why is it needed?– The FRM defines the regulatory indicatorof PM2.5.– FRM mass may not retain all nitrate,and includes particle bound water and othercomponents not estimated directly with STN measurements.– To estimate FRM PM2.5composition including FRM carbonaceous mass without“fudge” factors.– To help QC speciation measurements• SANDWICH is the default method in EPA modeling guidance to definebaseline PM2.5– for SMAT (speciated modeled attainment test)– “FRM” composition with the peer-reviewed “SANDWICH” technique used in CAIRand PM2.5RIAFrank, N. Retained Nitrate, Hydrated Sulfates, and Carbonaceous Massin Federal Reference Method Fine Particulate Matter for Six Eastern U.S. Cities,J. Air & Waste Manage. Assoc.56:500–5117(a) W. Reduced Nitrates(b) With added waterSO4UnknownCrustalpassiveTCMNO3(c) Plus filter contamination(= FRM “blank”)(d) Remaining unknown massis assigned to carbon(1) Approachusing measurementsand calculated valuesConceptual Overview of Mass Balance Approaches*Distributeunknown(or scale alldown) equally* Default SANDWICH can be modified to considerother components, like salt. This reduces estimate of TCM.(2) SANDWICHSulfate mass increases8RCFMSANDWICHAnnual Average Composition (2002-04) in East NA areasLess nitrate and more sulfate mass with SANDWICHNA area without STN data (02-04)Black outlined pieshad collocatedFRM and speciationarea area_annual_dvNA area: Johnstown, PA 15.3NA area: Martinsburg, WV-Hagerstown, MD 16.1NA area: Parkersburg-Marietta, WV-OH 15.2NA area: Reading, PA 16.1NA area: Steubenville-Weirton, OH-WV 17NA area: Wheeling, WV-OH 15.19RCFMSANDWICHAnnual Average Composition (2002-04) in West NA areasLess nitrate and more carbon mass with SANDWICHBlack outlined pies have collocated FRM and speciation102 3 4 5 6 7 8 9 10 11 12Riverside-San Bernardino,CA site= 060658001 (2005)2 3 4 5 6 7 8 9 10 11 12

PM2.5 and Components, ug/m3 0 60Rubidoux, CA (2005)RCFMSANDWICHFRM PM2.5 massLess nitrate massMore sulfate and carbonGray line shows {OCMmb - OCM14}Chem Sulfate_mass Nitrate_mass ECOCMmb Crustal PassiveOver-estimates FRM massFRM composition can be very different thanconstructed mass from speciation measurements110.05.010152025303540455055601 2 3 4 5 6 7 8 9 10 11 121 2 3 4 5 6 7 8 9 10 11 12RCFMSANDWICHFRM PM2.5 mass

PM2.5 and Components, ug/m3 0 60Less nitrate massMore sulfate and carbonBirmingham, AL (2005)Under-estimates FRM massBirmingham,AL site=010732003 (2005)Gray line shows {OCMmb - OCM14}Chem Sulfate_mass Nitrate_mass ECOCMmb Crustal PassiveFRM composition can be very different thanconstructed mass from speciation measurements12Q1Q3Q2Q4Sulfate_mass Nitrate_mass TCMUnknown_at_DV_site Crustal PassiveQuarterly PM2.5 Compositionin Eastern NA areas, 2002-04Note: Many areas do not have speciation data and some at a different siteNospeciationdata in2002-0413Q1Q3Q2Q4Sulfate_mass Nitrate_mass TCMUnknown_at_DV_site Crustal PassiveQuarterly PM2.5 Composition in NA areas, 2002-04Many areas do not have speciation data and some at a different siteZOOM14Q1Q3Q2 Q4Sulfate_mass Nitrate_mass TCMUnknown_at_DV_site Crustal PassiveQuarterly PM2.5 Composition in Western NA areas, 2002-041stand 4thquarters have higher concentrations (except LA)15Composition Can Vary Within the NA Area“Generally” the extra component is carbonAllen Park airs_site_code=261630001 year=2003Sulfate_mass Nitrate_mass TCMCrustal Passive0.42.350.505.485.49Dearborn airs_site_code=261630033 year=20032.682.870.507.377.14Allen Pk DearbornSulfate Mass 5.5 7.4Carbonaceous Mass 5.5 7.1Nitrate 2.4 2.9Crustal Material 0.4 2.7PM2.5 14.22 20.56More sulfate, carbon and crustalFor some cities, there are gradients in non-C components16Carbon, NO3 or Crustal?Baltimore (Essex speciation site) is not at DV site, 2002 speciation dataWhen DV site does not have speciation data, the unknown mass may or may not be TCMIt could be crustal material (as we observe inBirmingham and Detroit) or possibly NitrateWhat to do if speciation is not at the DV site?Accounting for differences in within-area speciation profilesSpeciation location (Ann Avg=14.9 ug/m3)NA area: Baltimore, MD - 240053001(2002-04)Sulfate_mass Nitrate_mass TCMUnknown_at_DV_site Crustal PassiveSANDWICH7.981.115.600.710.49SANDWICH_PacMan7.981.115.601.400.710.49DV site (16.3 ug/m3)1.4 ug/m3 is unknown17

PM2.5 and component mass, ug/m30.02.04.06.08.01012141618202224

PM2.5 and component mass, ug/m30.02.04.06.08.01012141618202224 PM2.5 and component mass, ug/m30.02.04.06.08.01012141618202224 PM2.5 and component mass, ug/m30.02.04.06.08.01012141618202224

PM2.5 and component mass, ug/m30.02.04.06.08.01012141618202224

PM2.5 and component mass, ug/m30.02.04.06.08.01012141618202224Regional Trends in PM2.5 Composition, 2002-2006Compositional changes in some regionsLower nitratesand sulfates.Increasing CarbonReduced Nitrates,Sulfates & CarbonNo change Sulfates.Decreasing NitratesIncreasing CarbonLower nitratesand sulfatesLower nitratesand sulfatesLower nitratesand sulfates02 03 04 05 0602 03 04 05 0602 03 04 05 0602 03 04 05 0602 03 04 05 0602 03 04 05 06Sulfate_mass Nitrate_mass ECOCMmb Crustal PassiveDRAFT18SANDWICH data are now available on Air Explorerhttp://www.epa.gov/airexplorer/19The Urban Excess20Urban Composition,PM2.5 ~17ug/m3SulfateEstimated AmmoniumNitrateTCMCrustal+Urban Increment~6ug/m3Regional Contribution~11ug/m3Urban PM2.5 is Composed of Urban and Regional Components36%26%54%47%10%33%12%21%17%5%11%16%Baltimore PM2.5 compared toUpwind rural site illustratesurban/rural contributionsBased on constructedmass (not SANDWICH),March 01 – Feb 0221From Particle Pollution Report, 2003Comparing single urban and rural locationsSulfates•Most from regional sourcesUrban PM2.5 is Composed of Urban and Regional ComponentsCarbon• Large PM2.5 component• Local contribution (40-70%)Nitrates• 10-30% of PM2.5• Some east avg. ambient nitrates~4 ug/m3• Local contribution >50%22Carbon and Nitrates dominate the average local urban excessComposition of Eastern PM2.5 Non-Attainment AreasEstimated PM2.5 CompositionEstimated Urban Excess*Indicates areas with > 30% UE nitrates0% 20% 40% 60% 80% 100%York, ; Harrisb, PAWashington, DCSt, Louis, MO-IL* Reading, LancasterPA;Pittsb, WheelingPhiladelphia,New York, NY-NJ-CTLouisville, KY-INKnoxville, KY* Indianapolis, INHickory, NCGreensboro, NC* Evansville, IN-KY* Detroit, MIColumbus, OH;* Cleveland, OHCincinnati, OH-KY-INChicago,IL-IN-WI;Chattanooga, TN-GACharleston, Hngtn,WV;* Canton, Steuben OH/WVBirmingham, ALBaltimore, MDAtlanta, GA; Macon, GACarbonSulfatesNitratesCrustal0% 20% 40% 60% 80% 100%York, ; Harrisb, PAWashington, DCSt, Louis, MO-ILReading, LancasterPA;Pittsb, WheelingPhiladelphia,New York, NY-NJ-CTLouisville, KY-INKnoxville, KYIndianapolis, INHickory, NCGreensboro, NCEvansville, IN-KYDetroit, MIColumbus, OH;Cleveland, OHCincinnati, OH-KY-INChicago,IL-IN-WI;Chattanooga, TN-GACharleston, Hngtn,WV;Canton, Steuben OH/WVBirmingham, ALBaltimore, MDAtlanta, GA; Macon, GACarbonSulfatesNitratesCrustal23High Day vs. Average CompositionAverage Concentration is based on alldays but is strongly influenced by thehighest concentration days24Composition on Annual Average andHigh PM2.5 DaysSome source categories and regional influences may bemore important for high concentration days• Comparing average of 5 highest daysduring 2003, regional sources ofsulfates and nitrates are largercontributors to peak dayconcentrations than to annualaverage (selected city analysis)• Composition can vary from high dayto high day• Carbon can be smaller as % -- butstill larger in absolute concentrationvalues -- compared to the averageSMWCANEFrom PM Staff Paper (Rao et al)BirmAtlantaNYCClevelandChicagoSt .LouisSLCFresnoUT More Sulfate More NitrateHigh PM2.5days have:NitrateTCMSulfateCrustalThis analysis showsPM2.5 Composition ofthe ambient aerosol(notadjusted to represent FRM mass)25yg gPLOTGT35ug/m3atFRMsitesPvX01020304050J F MA MJ J A S OND%50250yg gPLOTGT35ug/m3atFRMsitesPvX01020304050J F MA MJ J A S ONDyg gPLOTGT35ug/m3atFRMsitesPvXJ F MA MJ J A S ONDyg g01020304050J F MA MJ J A S ONDyg gPLOTGT35ug/m3atFRMsitesPvX0102030405060J F MA MJ J A S OND01020304050J F MA MJ J A S ONDNW UT IMWMid CAS.CA SEMidAtlPercent of 2003-05 FRM Days > 35 ug/m3 by MonthBased on all sites which violate 24-hr NAAQSJ F M A M J J A S O N DJ F M A M J J A S O N DJ F M A M J J A S O NDLa Cruces, NMyg g01020304050J F MA MJ J A S OND%50250J F M A M J J A S O N D26yg g01020304050J F MA MJ J A S ONDyg gPLOTGT35ug/m3atFRMsitesPvX01020304050J F MA MJ J A S ONDof 2003-05 Days > 35 ug/m3, by Month (N.Eng-MidAtl)Based on all FRM Site-days throughout the Regional DomainJFMAMJJASONDyg g01020304050J F MA MJ J A S ONDyg gPLOTGT35ug/m3atFRMsitesPvX01020304050J F MA MJ J A S ONDyg gPLOTGT35ug/m3atFRMsitesPvX01020304050J F MA MJ J A S ONDPercent of 2003-05 Days > 35 ug/m3, by Month (Mid. Cal)Based on all FRM Site-days throughout the Regional DomainPLOTGT35ug/m3atFRMsitesPvX0102030405060J F MA MJ J A S ONDyg g01020304050J F MA MJ J A S ONDNW UT IMWMid CAS.CA La CrucesNMSEMidAtlAvg High 3 ColdAvg High 3 WarmAvg High 3 ColdAvg High 3 WarmAvg High 3 ColdAvg High 3 WarmAvg High 3 Cold“Example” Composition for High Days[“Warm” Season (May-Sept) &“Cold”]But sites can be different within each “domain”ColdCold WarmCold WarmWarmCold WarmColdColdColdEl Paso STNorJ F M A M J J A S O N DJ F M A M J J A S O N D%50250%50250Pies represent average of3 highest days per yearper season, using SANDWICHor27IMW - 180970078 Indiana Indianapolis24-hr DV= 38 ug/m3 Annual DV= 15.4 ug/m3 Existing NA area= Indianapolis, INTotal 3 yr obs = 280 "cold" days > 30 = 3 "warm" days > 30 = 15Avg conc. - top 3 values/yr: 36.9 ug/m3 37.9 ug/m3Sulfate_mass Nitrate_mass EC OCMmbCrustal Passive NoneAVGAvg High 3 ColdAvg High 3 WarmPercent of 2003-05 Days > 35 ug/m3, by Month (IMW)Based on all FRM Site-days throughout the Regional DomainPLOTGT35ug/m3atFRMsitesPvX01020304050J F MA MJ J A S ONDJ F M A M J J A S O N DIMW - 260810020 Michigan Grand Rapids-Muskegon-Holland,MI24-hr DV= 37 ug/m3 Annual DV= 13.1 ug/m3Total 3 yr obs = 171 "cold" days > 30 = 5 "warm" days > 30 = 5Avg conc. - top 3 values/yr: 42.5 ug/m3 38.2 ug/m3Sulfate_mass Nitrate_mass ECOCMmb Crustal PassiveAVGAvg High 3 ColdAvg High 3 WarmIndustrial Midwest• Generally nitrate dominated winter-time valuesin northern areas• Sulfate dominated episodes in summer (region-wide)Note: Passive is PM2.5 unrelated to emissionsIMWNorthern Site (Grand Rapids, MI)AnnAvg of top 3 days/yrAvgColdWarmNumber inside pie is the “top3” average concentration, ug/m343ug/m338ug/m338ug/m324hr DV= 37 ug/m324hr DV= 38 ug/m3More Details about PM2.5Chemical Composition for the IMW13.1ug/m3Southern Site (Indianapolis, IN )15.4ug/m337ug/m328IMW - 180970078 Indiana Indianapolis24-hr DV= 38 ug/m3 Annual DV= 15.4 ug/m3 Existing NA area= Indianapolis, INTotal 3 yr obs = 280 "cold" days > 30 = 3 "warm" days > 30 = 15Avg conc. - top 3 values/yr: 36.9 ug/m3 37.9 ug/m3Sulfate_mass Nitrate_mass EC OCMmbCrustal Passive NoneAVGAvg High 3 ColdAvg High 3 WarmIMW - 540391005 West Virginia South Charleston24-hr DV= 36 ug/m3 Annual DV= 16.6 ug/m3 Existing NA area= Charleston, WVTotal 3 yr obs = 49 "cold" days > 30 = 0 "warm" days > 30 = 9Avg conc. - top 3 values/yr: 0.0 ug/m3 35.9 ug/m3Sulfate_mass Nitrate_mass EC OCMmbCrustal Passive NoneAVGAvg High 3 ColdAvg High 3 WarmIMW - 180390003 Indiana Elkhart24-hr DV= 36 ug/m3 Annual DV= 14.6 ug/m3 Existing NA area=Total 3 yr obs = 47 "cold" days > 30 = 2 "warm" days > 30 = 1Avg conc. - top 3 values/yr: 41.8 ug/m3 40.8 ug/m3Sulfate_mass Nitrate_mass EC OCMmbCrustal Passive NoneAVGAvg High 3 ColdAvg High 3 WarmIMW - 260810020 Michigan Grand Rapids-Muskegon-Holland,MI24-hr DV= 37 ug/m3 Annual DV= 13.1 ug/m3Total 3 yr obs = 171 "cold" days > 30 = 5 "warm" days > 30 = 5Avg conc. - top 3 values/yr: 42.5 ug/m3 38.2 ug/m3Sulfate_mass Nitrate_mass ECOCMmb Crustal PassiveAVGAvg High 3 ColdAvg High 3 WarmIMW - 261630033 Michigan Detroit,MI24-hr DV= 44 ug/m3 Annual DV= 18.2 ug/m3Total 3 yr obs = 139 "cold" days > 30 = 12 "warm" days > 30 = 9Avg conc. - top 3 values/yr: 38.0 ug/m3 43.2 ug/m3Sulfate_mass Nitrate_mass ECOCMmb Crustal PassiveAVGAvg High 3 ColdAvg High 3 WarmIMW - 261630001 Michigan Detroit,MI24-hr DV= 40 ug/m3 Annual DV= 15.1 ug/m3Total 3 yr obs = 327 "cold" days > 30 = 8 "warm" days > 30 = 11Avg conc. - top 3 values/yr: 44.2 ug/m3 38.5 ug/m3Sulfate_mass Nitrate_mass ECOCMmb Crustal PassiveAVGAvg High 3 ColdAvg High 3 WarmIMW - 360290005 New York Buffalo-Niagara Falls,NY24-hr DV= 37 ug/m3 Annual DV= 13.8 ug/m3Total 3 yr obs = 135 "cold" days > 30 = 3 "warm" days > 30 = 5Avg conc. - top 3 values/yr: 37.3 ug/m3 36.7 ug/m3Sulfate_mass Nitrate_mass ECOCMmb Crustal PassiveAVGAvg High 3 ColdAvg High 3 WarmIMW - 551330027 Wisconsin Milwaukee-Waukesha,WI24-hr DV= 36 ug/m3 Annual DV= 13.5 ug/m3Total 3 yr obs = 161 "cold" days > 30 = 5 "warm" days > 30 = 1Avg conc. - top 3 values/yr: 39.0 ug/m3 41.1 ug/m3Sulfate_mass Nitrate_mass ECOCMmb Crustal PassiveAVGAvg High 3 ColdAvg High 3 WarmMilwaukee, WIGrand Rapids, MIDetroit (Dearborn), MIDetr (Allen Park), MIBuffalo, NYCharleston, WVIndianapolis, INElkhart, INIMW - 420030008 Pennsylvania Pittsburgh24-hr DV= 39 ug/m3 Annual DV= 15.5 ug/m3 Existing NA area= Pittsburgh-Beaver Valley, PATotal 3 yr obs = 291 "cold" days > 30 = 2 "warm" days > 30 = 10Avg conc. - top 3 values/yr: 31.6 ug/m3 40.8 ug/m3Sulfate_mass Nitrate_mass ECOCMmb Crustal PassiveAVGAvg High 3 ColdAvg High 3 WarmPittsburgh, PAIMW - 420030064 Pennsylvania Liberty24-hr DV= 68 ug/m3 Annual DV= 20.8 ug/m3 Existing NA area= Pittsburgh-Beaver Valley, PATotal 3 yr obs = 109 "cold" days > 30 = 7 "warm" days > 30 = 11Avg conc. - top 3 values/yr: 50.5 ug/m3 55.7 ug/m3Sulfate_mass Nitrate_mass ECOCMmb Crustal PassiveAVGAvg High 3 ColdAvg High 3 WarmLiberty, PASulfate_mass Nitrate_mass ECOCMmb Crustal PassiveNote: Map show existing NA areas& new violation sitesNitrates - important in the N. sub-RegionSulfates and warm season in S. portion24hr DV= 44ug/m324hr DV= 40ug/m329Percent of 2003-05 Days > 35 ug/m3, by Month (N.Eng-MidAtl)Based on all FRM Site-days throughout the Regional DomainPLOTGT35ug/m3atFRMsitesPvX01020304050J F MA MJ J A S ONDJ F M A M J JA S O N DMid_Atlantic RegionGenerally Sulfate dominated episodeseverywhere in summerFewer Nitrate contributed winter-time values(except in SE. PA)N.Eng-MidAtl - 420270100 Pennsylvania State College24-hr DV= 38 ug/m3 Annual DV= 13.4 ug/m3 Existing NA area=Total 3 yr obs = 165 "cold" days > 30 = 1 "warm" days > 30 = 7Avg conc. - top 3 values/yr: 32.7 ug/m3 42.0 ug/m3Sulfate_mass Nitrate_mass ECOCMmb Crustal PassiveAVGAvg High 3 ColdAvg High 3 WarmN.Eng-MidAtl - 100032004 Delaware Wilmington-Newark,DE-MD24-hr DV= 37 ug/m3 Annual DV= 15.1 ug/m3Total 3 yr obs = 94 "cold" days > 30 = 3 "warm" days > 30 = 2Avg conc. - top 3 values/yr: 31.7 ug/m3 35.5 ug/m3Sulfate_mass Nitrate_mass ECOCMmb Crustal PassiveAVGAvg High 3 ColdAvg High 3 WarmMidAtlWestern Mid-Atl site: State College, PAEastern Mid-Atl site: Wilmington, DE33423624hr DV= 37 ug/m324hr DV= 37 ug/m33230N.Eng-MidAtl - 340390004 New Jersey Elizabeth24-hr DV= 46 ug/m3 Annual DV= 15.5 ug/m3 Existing NA area= New York-N.New Jersey-Long Island, NY-NJ-CTTotal 3 yr obs = 245 "cold" days > 30 = 9 "warm" days > 30 = 11Avg conc. - top 3 values/yr: 41.1 ug/m3 41.9 ug/m3Sulfate_mass Nitrate_mass EC OCMmbCrustal Passive NoneAVGAvg High 3 ColdAvg High 3 WarmN.Eng-MidAtl - 100032004 Delaware Wilmington-Newark,DE-MD24-hr DV= 37 ug/m3 Annual DV= 15.1 ug/m3Total 3 yr obs = 94 "cold" days > 30 = 3 "warm" days > 30 = 2Avg conc. - top 3 values/yr: 31.7 ug/m3 35.5 ug/m3Sulfate_mass Nitrate_mass ECOCMmb Crustal PassiveAVGAvg High 3 ColdAvg High 3 WarmN.Eng-MidAtl - 110010042 District Of Columbia Washington,DC-MD-VA-WV24-hr DV= 37 ug/m3 Annual DV= 14.5 ug/m3Total 3 yr obs = 135 "cold" days > 30 = 3 "warm" days > 30 = 10Avg conc. - top 3 values/yr: 33.5 ug/m3 35.9 ug/m3Sulfate_mass Nitrate_mass ECOCMmb Crustal PassiveAVGAvg High 3 ColdAvg High 3 WarmN.Eng-MidAtl - 360610062 New York New York,NY24-hr DV= 42 ug/m3 Annual DV= 15.3 ug/m3Total 3 yr obs = 202 "cold" days > 30 = 3 "warm" days > 30 = 7Avg conc. - top 3 values/yr: 42.8 ug/m3 43.3 ug/m3Sulfate_mass Nitrate_mass ECOCMmb Crustal PassiveAVGAvg High 3 ColdAvg High 3 WarmN.Eng-MidAtl - 420270100 Pennsylvania State College,PA24-hr DV= 38 ug/m3 Annual DV= 13.4 ug/m3Total 3 yr obs = 165 "cold" days > 30 = 1 "warm" days > 30 = 7Avg conc. - top 3 values/yr: 32.7 ug/m3 42.0 ug/m3Sulfate_mass Nitrate_mass ECOCMmb Crustal PassiveAVGAvg High 3 ColdAvg High 3 WarmN.Eng-MidAtl - 421010004 Pennsylvania Philadelphia,PA-NJ24-hr DV= 37 ug/m3 Annual DV= 14.3 ug/m3Total 3 yr obs = 208 "cold" days > 30 = 5 "warm" days > 30 = 10Avg conc. - top 3 values/yr: 32.1 ug/m3 40.9 ug/m3Sulfate_mass Nitrate_mass ECOCMmb Crustal PassiveAVGAvg High 3 ColdAvg High 3 WarmN.Eng-MidAtl - 420710007 Pennsylvania Lancaster,PA24-hr DV= 44 ug/m3 Annual DV= 17.5 ug/m3Total 3 yr obs = 172 "cold" days > 30 = 12 "warm" days > 30 = 6Avg conc. - top 3 values/yr: 42.1 ug/m3 42.9 ug/m3Sulfate_mass Nitrate_mass ECOCMmb Crustal PassiveAVGAvg High 3 ColdAvg High 3 WarmLancaster, PAPhiladelphia, PAElizabeth, NJNew York, NYWilmington, DEWashington, DCState College, PASulfates dominate high Summer daysNitrates - important on fewer cold days31SE - 011130001 Alabama Phenix City24-hr DV= 37 ug/m3 Annual DV=15.7 ug/m3 Existing NA area=Total 3 yr obs = 39 "cold" days > 30 = 1 "warm" days > 30 = 3Avg conc. - top 3 values/yr: 31.8 ug/m3 39.3 ug/m3Sulfate_mass Nitrate_mass EC OCMmbCrustal Passive NoneAVGAvg High 3 ColdAvg High 3 WarmPercent of 2003-05 Days > 35 ug/m3, by Month (SE)Based on all FRM Site-days throughout the Regional Domain01020304050J F MA MJ J A S ONDSEJ F M A M J JA S O N DSE - 010732003 Alabama Birmingham24-hr DV= 39 ug/m3 Annual DV= 16.5 ug/m3 Existing NA area= Birmingham,ALTotal 3 yr obs = 173 "cold" days > 30 = 3 "warm" days > 30 = 9Avg conc. - top 3 values/yr: 34.1 ug/m3 39.9 ug/m3Sulfate_mass Nitrate_mass ECOCMmb Crustal PassiveAVGAvg High 3 ColdAvg High 3 WarmInsufficientData forAnn AvgSouth East RegionMostly sulfate dominated + OC episodes, in summer-- shows influence of biogenics and other SOAFewer cold-season exceedances (& are driven by carbon)Existing NA: Birmingham, ALNew 24hr Violation: Phenix City, AL(Columbus, GA area)34403924hr DV= 39 ug/m324hr DV= 37 ug/m33232SE - 370350004 North Carolina Hickory24-hr DV= 36 ug/m3 Annual DV= 15.3 ug/m3 Existing NA area= Hickory-Morganton-Lenoir, NCTotal 3 yr obs = 69 "cold" days > 30 = 0 "warm" days > 30 = 7Avg conc. - top 3 values/yr: 0.0 ug/m3 35.7 ug/m3Sulfate_mass Nitrate_mass EC OCMmbCrustal Passive NoneAVGAvg High 3 ColdAvg High 3 WarmSE - 011130001 Alabama Phenix City24-hr DV= 37 ug/m3 Annual DV= 15.7 ug/m3 Existing NA area=Total 3 yr obs = 39 "cold" days > 30 = 1 "warm" days > 30 = 3Avg conc. - top 3 values/yr: 31.8 ug/m3 39.3 ug/m3Sulfate_mass Nitrate_mass EC OCMmbCrustal Passive NoneAVGAvg High 3 ColdAvg High 3 WarmSE - 010730023 Alabama Birmingham,AL24-hr DV= 44 ug/m3 Annual DV= 18.2 ug/m3Total 3 yr obs = 353 "cold" days > 30 = 11 "warm" days > 30 = 34Avg conc. - top 3 values/yr: 37.9 ug/m3 45.3 ug/m3Sulfate_mass Nitrate_mass ECOCMmb Crustal PassiveAVGAvg High 3 ColdAvg High 3 WarmSE - 131150005 Georgia Not in a MSA24-hr DV= 36 ug/m3 Annual DV= 16.2 ug/m3Total 3 yr obs = 92 "cold" days > 30 = 1 "warm" days > 30 = 2Avg conc. - top 3 values/yr: 33.8 ug/m3 34.8 ug/m3Sulfate_mass Nitrate_mass ECOCMmb Crustal PassiveAVGAvg High 3 ColdAvg High 3 WarmSE - 010732003 Alabama Birmingham,AL24-hr DV= 39 ug/m3 Annual DV= 16.5 ug/m3Total 3 yr obs = 173 "cold" days > 30 = 3 "warm" days > 30 = 9Avg conc. - top 3 values/yr: 34.1 ug/m3 39.9 ug/m3Sulfate_mass Nitrate_mass ECOCMmb Crustal PassiveAVGAvg High 3 ColdAvg High 3 WarmBirmingham, ALBirmingham, ALRome, GAHickory, NCPhenix City, AL(Columbus, GA area)Sulfates and carbon during summerCarbon more important on fewer cold daysNote: Columbus area designated Attainmentin 2005 on basis ofspatial averaging.33SW Texas - 481410053 Texas El Paso24-hr DV= 42 ug/m3 Annual DV= 17.7 ug/m3 Existing NA area=Total 3 yr obs = 19 "cold" days > 30 = 3 "warm" days > 30 = 0Avg conc. - top 3 values/yr: 35.7 ug/m3 0.0 ug/m3Sulfate_mass Nitrate_mass EC OCMmbCrustal Passive NoneAVGAvg High 3 ColdAvg High 3 WarmPM2.5 speciation - 02/02/2003Southwestern US•Speciation data (from El Paso) suggest emissionsources creating crustal and carbon•Shows effect of aridity and wind24hr DV=42(not pop- oriented?)Ann DV=17.3Las Cruces,NM24hr DV=36Ann DV=10.4Nitrate data was not available for this siteInsufficientData forAnn AvgNo summerdays> 30 ug/m3Percent of 2003-05 Days > 35 ug/m3, by Month (Las Cruces)Based on all FRM Site-days throughout the Regional DomainPLOTGT35ug/m3atFRMsitesPvX01020304050J F MA MJ J A S ONDLas Cruces, NMEl Paso, TX34Percent of 2003-05 Days > 35 ug/m3, by Month (S. Cal)Based on all FRM Site-days throughout the Regional Domain01020304050J F MA MJ J A S ONDS.CAS. Cal - 060658001 California Riverside-San Bernardino,CA24-hr DV= 65 ug/m3 Annual DV= 22.6 ug/m3Total 3 yr obs = 326 "cold" days > 30 = 43 "warm" days > 30 = 29Avg conc. - top 3 values/yr: 69.9 ug/m3 44.8 ug/m3Sulfate_mass Nitrate_mass ECOCMmb Crustal PassiveAVGAvg High 3 ColdAvg High 3 WarmSouthern California• Nitrates dominate High PM2.5 in LA.• Carbon (summer) and also nitrates (winter) in Calexico• Lower % crustal on high daysS. Cal - 060250005 California Calexico24-hr DV= 39 ug/m3 Annual DV= 12.7 ug/m3 Existing NA area=Total 3 yr obs = 66 "cold" days > 30 = 2 "warm" days > 30 = 1Avg conc. - top 3 values/yr: 31.9 ug/m3 34.2 ug/m3Sulfate_mass Nitrate_mass ECOCMmb Crustal PassiveAVGAvg High 3 ColdAvg High 3 WarmDownwind of LA: Rubidoux, CABorder Site: Calexico, CA70453424hr DV= 65 ug/m324hr DV= 39 ug/m33235S. Cal - 060371103 California Los Angeles-Long Beach,CA24-hr DV= 56 ug/m3 Annual DV= 19.6 ug/m3Total 3 yr obs = 172 "cold" days > 30 = 17 "warm" days > 30 = 7Avg conc. - top 3 values/yr: 53.5 ug/m3 45.8 ug/m3Sulfate_mass Nitrate_mass ECOCMmb Crustal PassiveAVGAvg High 3 ColdAvg High 3 WarmS. Cal - 060250005 California Not in a MSA24-hr DV= 39 ug/m3 Annual DV= 12.7 ug/m3Total 3 yr obs = 66 "cold" days > 30 = 2 "warm" days > 30 = 1Avg conc. - top 3 values/yr: 31.9 ug/m3 34.2 ug/m3Sulfate_mass Nitrate_mass ECOCMmb Crustal PassiveAVGAvg High 3 ColdAvg High 3 WarmS. Cal - 060658001 California Riverside-San Bernardino,CA24-hr DV= 65 ug/m3 Annual DV= 22.6 ug/m3Total 3 yr obs = 326 "cold" days > 30 = 43 "warm" days > 30 = 29Avg conc. - top 3 values/yr: 69.9 ug/m3 44.8 ug/m3Sulfate_mass Nitrate_mass ECOCMmb Crustal PassiveAVGAvg High 3 ColdAvg High 3 WarmLos Angeles, CARubidoux, CACalexico, CAComposition Varies Across this Diverse CA Domain24hr DV= 56 ug/m3 24hr DV= 65 ug/m336Mid. Cal - 060670006 California Sacramento24-hr DV= 45 ug/m3 Annual DV= 11.8 ug/m3 Existing NA area=Total 3 yr obs = 196 "cold" days > 30 = 20 "warm" days > 30 = 0Avg conc. - top 3 values/yr: 41.4 ug/m3 0.0 ug/m3Sulfate_mass Nitrate_mass EC OCMmbCrustal Passive NoneAVGAvg High 3 ColdAvg High 3 WarmMid. Cal - 060290014 California Bakersfield24-hr DV= 58 ug/m3 Annual DV= 18 ug/m3 Existing NA area= San Joaquin Valley, CATotal 3 yr obs = 142 "cold" days > 30 = 37 "warm" days > 30 = 0Avg conc. - top 3 values/yr: 61.1 ug/m3 0.0 ug/m3Sulfate_mass Nitrate_mass EC OCMmbCrustal Passive NoneAVGAvg High 3 ColdAvg High 3 WarmPercent of 2003-05 Days > 35 ug/m3, by Month (Mid. Cal)Based on all FRM Site-days throughout the Regional DomainPLOTGT35ug/m3atFRMsitesPvX0102030405060J F MA MJ J A S ONDMid CAJ F M A M J J A S O N DMiddle California• Carbon in Northern Central Valley•from RWC?• Nitrates dominate High PM2.5 in lower SJVNo warmseasonexceedancesNo warmseasonexceedancesNorthern Central Valley (e.g. Sacramento)Southern SJV (e.g. Bakersfield, CA)4124hr DV= 45 ug/m324hr DV= 58 ug/m36137Mid. Cal - 060070002 California Chico24-hr DV= 47 ug/m3 Annual DV= 12.6 ug/m3 Existing NA area=Total 3 yr obs = 50 "cold" days > 30 = 6 "warm" days > 30 = 0Avg conc. - top 3 values/yr: 39.0 ug/m3 0.0 ug/m3Sulfate_mass Nitrate_mass EC OCMmbCrustal Passive NoneAVGAvg High 3 ColdAvg High 3 WarmMid. Cal - 060990005 California Modesto24-hr DV= 49 ug/m3 Annual DV= 14 ug/m3 Existing NA area= San Joaquin Valley, CATotal 3 yr obs = 56 "cold" days > 30 = 7 "warm" days > 30 = 0Avg conc. - top 3 values/yr: 38.8 ug/m3 0.0 ug/m3Sulfate_mass Nitrate_mass EC OCMmbCrustal Passive NoneAVGAvg High 3 ColdAvg High 3 WarmMid. Cal - 060850005 California San Jose24-hr DV= 39 ug/m3 Annual DV= 11.7 ug/m3 Existing NA area=Total 3 yr obs = 142 "cold" days > 30 = 16 "warm" days > 30 = 0Avg conc. - top 3 values/yr: 43.0 ug/m3 0.0 ug/m3Sulfate_mass Nitrate_mass EC OCMmbCrustal Passive NoneAVGAvg High 3 ColdAvg High 3 WarmMid. Cal - 060670006 California Sacramento24-hr DV= 45 ug/m3 Annual DV= 11.8 ug/m3 Existing NA area=Total 3 yr obs = 196 "cold" days > 30 = 20 "warm" days > 30 = 0Avg conc. - top 3 values/yr: 41.4 ug/m3 0.0 ug/m3Sulfate_mass Nitrate_mass EC OCMmbCrustal Passive NoneAVGAvg High 3 ColdAvg High 3 WarmMid. Cal - 060190008 California Fresno24-hr DV= 60 ug/m3 Annual DV= 16.9 ug/m3 Existing NA area= San Joaquin Valley, CATotal 3 yr obs = 166 "cold" days > 30 = 39 "warm" days > 30 = 0Avg conc. - top 3 values/yr: 59.3 ug/m3 0.0 ug/m3Sulfate_mass Nitrate_mass EC OCMmbCrustal Passive NoneAVGAvg High 3 ColdAvg High 3 WarmMid. Cal - 060290014 California Bakersfield24-hr DV= 58 ug/m3 Annual DV= 18 ug/m3 Existing NA area= San Joaquin Valley, CATotal 3 yr obs = 142 "cold" days > 30 = 37 "warm" days > 30 = 0Avg conc. - top 3 values/yr: 61.1 ug/m3 0.0 ug/m3Sulfate_mass Nitrate_mass EC OCMmbCrustal Passive NoneAVGAvg High 3 ColdAvg High 3 WarmChico, CASacramento, CAModesto, CAFresno, CABakersfield, CASan Jose, CANitrates dominate peak days in Southern SJVCarbon is big contributor in N. Central Valley (RWC)38NW - 300530018 Montana Libby24-hr DV= 44 ug/m3 Annual DV= 15.1 ug/m3 Existing NA area= Libby, MTTotal 3 yr obs = 88 "cold" days > 30 = 16 "warm" days > 30 = 0Avg conc. - top 3 values/yr: 41.6 ug/m3 0.0 ug/m3Sulfate_mass Nitrate_mass EC OCMmbCrustal Passive NoneAVGAvg High 3 ColdAvg High 3 WarmNW - 300630031 Montana Missoula24-hr DV= 41 ug/m3 Annual DV= 10.5 ug/m3 Existing NA area=Total 3 yr obs = 310 "cold" days > 30 = 11 "warm" days > 30 = 4Avg conc. - top 3 values/yr: 50.9 ug/m3 42.6 ug/m3Sulfate_mass Nitrate_mass ECOCMmb Crustal PassiveAVGAvg High 3 ColdAvg High 3 WarmPercent of 2003-05 Days > 35 ug/m3, by Month (NW)Based on all FRM Site-days throughout the Regional DomainPLOTGT35ug/m3atFRMsitesPvX01020304050J F MA MJ J A S ONDNWJ F M A M J J A S O N DNorth West• Carbon dominates Libby (from RWC?)• Nitrates are also found on high winter daysin Missoula (and elsewhere, e.g. Boise)-- mobile and valley influence or ?• Summer days are flagged fires• (not concurred?)No warmseasonexceedancesMissoula, MT (traffic influenced)Libby, MT (RWC)5124hr DV= 41 ug/m324hr DV= 44 ug/m34239NW - 300530018 Montana Libby24-hr DV= 44 ug/m3 Annual DV= 15.1 ug/m3 Existing NA area= Libby, MTTotal 3 yr obs = 88 "cold" days > 30 = 16 "warm" days > 30 = 0Avg conc. - top 3 values/yr: 41.6 ug/m3 0.0 ug/m3Sulfate_mass Nitrate_mass EC OCMmbCrustal Passive NoneAVGAvg High 3 ColdAvg High 3 WarmNW - 300630031 Montana Missoula24-hr DV= 41 ug/m3 Annual DV= 10.5 ug/m3 Existing NA area=Total 3 yr obs = 310 "cold" days > 30 = 11 "warm" days > 30 = 4Avg conc. - top 3 values/yr: 50.9 ug/m3 42.6 ug/m3Sulfate_mass Nitrate_mass ECOCMmb Crustal PassiveAVGAvg High 3 ColdAvg High 3 WarmDifficult to predict composition fromnearby locations(e.g. Missoula composition is similar to Boisebut different than Libby)Libby, MTMissoula, MTNew violation locationswithout STN dataComposition Varies. Only Carbon at some locations.Nitrate is evident at other sites. Many Viol sites wo STNTopographyEffects?40UT - 490353006 Utah Salt Lake City24-hr DV= 47 ug/m3 Annual DV= 11.6 ug/m3 Existing NA area=Total 3 yr obs = 194 "cold" days > 30 = 24 "warm" days > 30 = 0Avg conc. - top 3 values/yr: 52.3 ug/m3 0.0 ug/m3Sulfate_mass Nitrate_mass EC OCMmbCrustal Passive NoneAVGAvg High 3 ColdAvg High 3 WarmUT - 490494001 Utah Lindon24-hr DV= 43 ug/m3 Annual DV= 10.5 ug/m3 Existing NA area=Total 3 yr obs = 174 "cold" days > 30 = 6 "warm" days > 30 = 1Avg conc. - top 3 values/yr: 53.2 ug/m3 51.8 ug/m3Sulfate_mass Nitrate_mass ECOCMmb Crustal PassiveAVGAvg High 3 ColdAvg High 3 WarmPercent of 2003-05 Days > 35 ug/m3, by Month (UT)Based on all FRM Site-days throughout the Regional DomainPLOTGT35ug/m3atFRMsitesPvX01020304050J F MA MJ J A S ONDUTHigh PM2.5 in Utah• Consistently more Nitrates on high days• SLC has similar % Sulfates as ann avg• Lindon – one summer exceedance• unflagged fire?No warmseasonexceedancesSalt Lake City, UTLindon, UT5224hr DV= 47 ug/m324hr DV= 43 ug/m353PrescribedFire41UT - 490110004 Utah Bountiful24-hr DV= 40 ug/m3 Annual DV= 11 ug/m3 Existing NA area=Total 3 yr obs = 74 "cold" days > 30 = 9 "warm" days > 30 = 0Avg conc. - top 3 values/yr: 40.6 ug/m3 0.0 ug/m3Sulfate_mass Nitrate_mass EC OCMmbCrustal Passive NoneAVGAvg High 3 ColdAvg High 3 WarmUT - 490494001 Utah Lindon24-hr DV= 43 ug/m3 Annual DV= 10.5 ug/m3 Existing NA area=Total 3 yr obs = 174 "cold" days > 30 = 6 "warm" days > 30 = 1Avg conc. - top 3 values/yr: 53.2 ug/m3 51.8 ug/m3Sulfate_mass Nitrate_mass EC OCMmbCrustal Passive NoneAVGAvg High 3 ColdAvg High 3 WarmUT - 490353006 Utah Salt Lake City24-hr DV= 47 ug/m3 Annual DV= 11.6 ug/m3 Existing NA area=Total 3 yr obs = 194 "cold" days > 30 = 24 "warm" days > 30 = 0Avg conc. - top 3 values/yr: 52.3 ug/m3 0.0 ug/m3Sulfate_mass Nitrate_mass EC OCMmbCrustal Passive NoneAVGAvg High 3 ColdAvg High 3 WarmBountiful, UTSLC, UTLindon, UTMany Violating Locations in UTNitrates seems to dominate peaksLogan (Cache Co.)Ogden (Weber Co)Bountiful (Davis Co).SLCLindonProvoSpanish Fork CityOgden-ClearfieldCBSAProvo-OremCBSA42Alaska - 020900010 Alaska Fairbanks24-hr DV= 40 ug/m3 Annual DV= 11.9 ug/m3 Existing NA area=Total 3 yr obs = 35 "cold" days > 30 = 1 "warm" days > 30 = 2Avg conc. - top 3 values/yr: 32.8 ug/m3 32.8 ug/m3Sulfate_mass Nitrate_mass EC OCMmbCrustal Passive NoneAVGAvg High 3 ColdAvg High 3 WarmPercent of 2003-05 Days > 35 ug/m3, by Month (Alaska)Based on all FRM Site-days throughout the Regional DomainPLOTGT35ug/m3atFRMsitesPvX01020304050J F MA MJ J A S ONDAlaskaHigh PM2.5 in Alaska (Fairbanks)• 50% carbon on winter exceedance day• Two summer exceedances are flaggedfires (not concurred)InsufficientData toComputeAnn. avg333324hr DV= 40 ug/m33343Potential Source Influences by Season and Scale9**9999EGU (NOx)Ag (NH3)Mobile (NOx+NH3)NitrateCold• IMW• Mid-Atl• S. CA• UT• Mid CA• NM• AK*9EGU (SO2)Sulfate999Mobile, Area/RWC, IndustryCarbon9Industry, MobileCrustal*9EGU (SO2)SulfateWarm• IMW• Mid-Atl• SE• S. CACrustalCarbonMajor PM2.5Components9RegionalTypical Scales ofInfluence9*Mobile, Area, Industry99Mobile, Area, Industry,Biogenics and SmokeMicroUrbanSource categorySeason&AffectedDomainsUnderlined text indicates dominant season for the domain Carbonincludes OC and EC*Sometimes occurs