VISTAS Special Monitoring StudiesCarbon Analyses for PM2.5 and HazePatricia Brewer1,Johann Engelbrecht2, Roger Tanner3,Scott Reynolds4,John Calcagni51VISTAS2Desert Research Institute3Tennessee Valley Authority4South Carolina Department of Health and Environmental Control15Environmental Protection AgencybPresentation Ojectives•VISTAS Data Analysis•Special Monitoring StudiesSpecialMonitoringStudies• Carbon Studies: C14isotope, Positive MatrixFactorization,and Chemical Mass Balance2Areas with Poorest Visibility are similar to PM2.5 Non-attainment AreasBRIG1DOSO1JARI1MACA1SHEN1CADI1COHU1GRSM1HEGL1LIGO1MACA1MING1SHRO1SWAN1UPBU1CACR1ROMA1SIPS1FederalTribalClass I AreasCHAS1OKEF1SAMA1IMPROVE SiteBRET1EVER1Average Extinction for 20% Haziest DaysN IMPROVE Al ith2000-2004NewIMPROVEAlgorithm250300200

( Mm -1 )Sea SaltCoarse100150

Extinction (SoilECPOMNH4NO3(NH4)2SO450100Rayleigh0 SWAN ROMA OKEF EVER CHAS SAMA DOSO SHEN JARI LIGO SHRO GRSM COHU SIPS MACA BRIG BRET MING HEGL UPBU CACRVISTAS coastalVISTAS inlandnon-VISTASSulfate dominates the 20% Haziest Days at VISTAS Class I areasAverage Extinction for 20% Best Days2000-2004New IMPROVE Algorithm604050

M m

-1 )Sea SaltCM30

Extinction ( MSoilECPOMNH4NO3(NH4)2SO41020Rayleigh0 SWAN ROMA OKEF EVER CHAS SAMA DOSO SHEN JARI LIGO SHRO GRSM COHU SIPS MACA BRIG BRET MING HEGL UPBU CACRVISTAS coastalVISTAS inlandnon-VISTASSulfate also dominates the 20% Clearest Days at VISTAS Class I areasNatural Conditions -- New IMPROVE Algorithm -Left = B20%; Center = Average; Right = W20%4050*Breton based on 2001Q2-2002Q1 & 2002Q4-2003Q3

)Sea SaltCM2030

x t (Mm-1 )CMSoilECPOM010

be xNH4NO3(NH4)2SO4R lih0ayeighMonitoring ObjectivesMonitoringObjectivesIdentify sources of organic carbonIdentifysourcesoforganiccarbonUse high volume samplers with PM2.5 head andquartz filters at 5 sitesS l ll t d A il 2004M 2005Samples collectedApril2004–ay2005Analyses by Desert Research InstituteSelect 250 samples for carbon analysis (5 sitesSelect250samplesforcarbonanalysis(5sites,50 samples per site including field and lab blanks)Define carbon mass of each sampleCh t i i iti (GC/MS)Characterize organic composition(GC/MS)Identify tracers of primary sources of carbon(Chemical Mass Balance and Positive Matrix8Factorization)Monitoring ObjectivesMonitoringObjectivesIdentify sources of organic carbonIdentifysourcesoforganiccarbonFor same samples, characterize C14isotope and ratio of modern to fossil carbonAnalyses by Woods Hole OceanographicInstitute’s National Oceanographic SciencesAccelerator Mass Spectrometry (NOSAMS)AcceleratorMassSpectrometry(NOSAMS)Sources of modern carbon: vegetativeemissions, wood burning, agriculturalburning, cookingSources of fossil carbon: gasoline, diesel,oil9VISTAS Carbon Study SitesShenandoahMammoth CaveGreat Smoky Mtns.RaleighCape RomainURBANCLASS 110Sources of Organic Carbon:L LdessonsLearnedModern carbon fraction seldom <0 60Moderncarbonfractionseldom<0.60,usually >0.70Higher modern carbon at forested sitesHighermoderncarbonatforestedsites(GRSM and MACA) than coastal (ROMA) orurban(MILL)sites)Higher total carbon and higher total PM2.5aturban site correspond to lower modern carbonNo clear seasonal trends in modern carbonHypothesize that greater wood burning in wintermonths and greater vegetative emissions in11monthsandgreatervegetativeemissionsinspring/summer12Apr 2004 May 2005Fraction Modern Carbon vs. Aerosol CarbonCape Romain, All Seasons1.00

m0.800.90

n Carbon, f0.600.70

c tion Modery = 0.045x + 0.556R2= 0.4220.400.50

Fra c0.300.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.013Aerosol C,μg/m314Fraction Modern Carbon vs. Aerosol CarbonGreat Smoky Mtns, All Seasons1.10y = 0.038x + 0.609R2= 0.13620.901.00

C arbon, f m0.700.80

o n Modern C0.500.60

Fracti o0.300.400.00 1.00 2.00 3.00 4.00 5.00 6.00 7.0015Aerosol Carbon,μg/m316Fraction Modern Carbon vs. Aerosol CarbonMammoth Cave, All Seasons1 100.901.001.10

C arbon, f m0.700.80

o n Modern C0.500.60

Fracti o0.300.400.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.017Aerosol Carbon,μg/m318Fraction Modern Carbon vs. Aerosol CarbonMillbrook, All Seasons0 901.001.10

arbon, f m0.700.800.90

o n Modern C0.500.60

Fracti0.300.400.00 2.00 4.00 6.00 8.00 10.00 12.0019Aerosol Carbon,μg/m320Fraction Modern Carbon vs. Aerosol CarbonShenadoah, All Seasons1.100.901.00

arbon, f m0.700.80

o n Modern Cy=0.054x+0.5140.500.60

Fracti oy0.054x0.514R2= 0.4340.300.400 001 002 003 004 005 006 007 008 009 0010 00210.001.002.003.004.005.006.007.008.009.0010.00Aerosol Carbon,μg/m3Monitoring ObjectivesMonitoringObjectivesPositive Matrix Factorization applied toPositiveMatrixFactorizationappliedtocluster organic compounds.Tracers identified forBiogenic EmissionsVegetative BurnGasoline emissionsDiesel emissionsCrude Oil (Commercial Marine seen at ROMA)CrudeOil(CommercialMarine,seenatROMA)Analyses incomplete: tracers still need to berelated back to total carbon to understand22relative importanceVegetative burnBiogenic Emissions23BiogenicEmissionsDiesel CrudeMotor vehicles24252627Monitoring ObjectivesMonitoringObjectivesChemical Mass Balance analysesresults to date from few samples analyzed by MeiZheng, Ga TechCh i l k ( fil ) f iChemicalmarkers(profiles)for primarycarbon sources:Wood CombustionWoodCombustionGasoline emissionsDiesel emissionsMeat CookingMeatCookingVegetative detritusOther Organic Matter (unidentified primary sourcesl d i)28plus secondary organics)GTCMB R lt-CMBResults6.004.005.002 003.00

μ g/m31.002.000.0029DieselGasolineWood CombustionMeat CookingVegetative DetritusOther OMCarbon Source Attribution:Lessons LearnedCMB Results from samples analyzed byCMBResultsfromsamplesanalyzedbyMei Zheng, Ga TechIn April samples from all sites, unidentifiedpcomponent is largest fraction (>70%)Likely secondary, likely biogenicW d b ti i l t id tifi dWoodcombustionislargestidentifiedcomponent in Jan samples, all sitesGasoline higher in Jan than Apr samples?GasolinehigherinJanthanAprsamples?Diesel at all sites in Apr, not Jan samples?30Carbon Source Attribution:Lessons LearnedCMB analyses together with C14resultsCMBanalysestogetherwithCresultsindicate that modern carbon is moreimportant than fossil carbon at Class Iareas and urban area sampled.Little seasonal variability in modern carbonwood burning vs biogenicStill need integration to understand sourcecontributions31Next StepsNextStepsRelate organic tracers used as PMF factors tolarger population of organic compoundsComplete CMB organic analyses all samplesRelate organic profiles to measured carbonIntegrate results with C14 analysesInterpret source attribution for organic carbonIntegrate results with SOA production inCMAQ/CAMx air quality modelsCMAQ/CAMxairqualitymodelsFinalize project reportsSubmit manucript for publication32Submitmanucriptforpublication