Chemical Analysis for SourceAttribution of Fine and CoarseParticulate Matter in Pinal County, AZAndrea L. Clements1, Yuling Jia1,Matthew P. Fraser1,2, Pierre Herckes3,Michael Sundblom4, and Paul A. Solomon51Rice University – Civil and Environmental Engineering2Arizona State University – Global Institute of Sustainability3Arizona State University – Chemistry4Pinal County Air Quality Control District5USEPA Region 9Casa GrandeInfluenced by the small cityof Casa Grande – populationroughly 50,000.CowtownImpacted by cattle feed lots,agricultural fields, a grainprocessing plant, railroadtraffic, and unpaved andpaved roads all in theimmediate vicinity.Pinal County HousingImpacted by native desert,agricultural fields and paved andunpaved roads.More distantly, it is influencedby a dairy, cotton gins, theCounty fairgrounds, and miningand smeltering operations.Ambient Field Sampling PlanAmbient Field Sampling PlanCGCOWPCH3 samplingsites4 monitorsper siteTeflonTeflonQuartzBlanks +Co-locatedMeasurementsMass and IonSpeciationMass and MetalSpeciationBulk OC/EC andOrganic SpeciationEach SamplerCollects TwoFiltersFineCoarseSierra-Anderson, Model 241Dichotomous SamplersFine FractionFine Fraction––MassConcentration Time SeriesConcentration Time Series0510152025302/6/09 2/24/09 3/14/09 4/1/09 4/19/09 5/7/09 5/25/09 6/12/09 6/30/09Sampling Date

Ambient Mass Concentration (ug/m3)PCHCowCGCoarse FractionCoarse Fraction–MassConcentration Time SeriesConcentration Time Series0204060801001201401601802/6/09 2/24/09 3/14/09 4/1/09 4/19/09 5/7/09 5/25/09 6/12/09 6/30/09Sampling Date

Ambient Mass Concentration (ug/m3)PCHCowCG150 ug/m3Daily Average StandardBulk Organic CarbonBulk Organic CarbonConcentration Time SeriesConcentration Time Series0510152025302/6/09 2/24/09 3/14/09 4/1/09 4/19/09 5/7/09 5/25/09 6/12/09 6/30/09 7/18/09Sampling Date

Ambient Organic Carbon Concentration (ug/m3)CG - CoarseCow - CoarsePCH - CoarseCG - FineCow - FinePCH - FineBulk Carbon ThermographBulk Carbon Thermograph–4/19051015202530CG COW PCH

Carbon Concentration (ug/m3)OC1OC2OC3OC4Pyrol CEC0.00.51.01.52.02.53.03.54.04.55.0CG COW PCH

Carbon Concentration (ug/m3)OC1OC2OC3OC4Pyrol CECCoarse FractionFine FractionSulfateSulfateConcentration Time SeriesConcentration Time Series0.00.51.01.52.02.52/6/09 2/24/09 3/14/09 4/1/09 4/19/09 5/7/09 5/25/09Sampling Date

Ion Concentration (ug/m3)CG-C-SO4COW-C-SO4PCH-C-SO4CG-F-SO4COW-F-SO4PCH-F-SO4PhosphatePhosphateConcentration Time SeriesConcentration Time Series0.00.51.01.52.02.53.02/6/09 2/24/09 3/14/09 4/1/09 4/19/09 5/7/09 5/25/09Sampling Date

Ion Concentration (ug/m3)CG-C-PO4COW-C-PO4PCH-C-PO4CG-F-PO4COW-F-PO4PCH-F-PO4CationConcentrationConcentrationTime SeriesTime Series-CowtownCowtown0.00.51.01.52.02.52/6/09 2/24/09 3/14/09 4/1/09 4/19/09 5/7/09 5/25/09Sampling Date

Ion Concentration (ug/m3)Sodium-CAmmonium-CP otassium-CM agnesium-CCalcium-CSodium-FAmmonium-FP otassium-FM agnesium-FCalcium-FMajor Metal ConcentrationMajor Metal ConcentrationTime SeriesTime Series--CowtownCowtown01000200030004000500060007000800090002/6/09 2/24/09 3/14/09 4/1/09 4/19/09 5/7/09 5/25/09 6/12/09Sampling Date

Metal Concentration ng/m3Fe-coarseAl-coarseK-coarseCa-coarseFe-fineAl-fineK-fineCa-fineFine FractionFine Fraction-AlkaneandHopaneConcentrationsConcentrations0510152025E-F-1 E-F-2 E-F-3 H-F-1 H-F-2 H-F-3 L-F-1 L-F-2 L-F-3

Concentration (ng/m 3)C25C26C27C28C29C30C31C32C33C34C3515202505101520Casa GrandeCowtownPC HousingSum ofHopaneSpeciesCoarse FractionCoarse Fraction--AlkaneandHopaneConcentrationsConcentrations0510152025303540E-C-1 E-C-2 E-C-3 H-C-1 H-C-2 H-C-3 L-C-1 L-C-2 L-C-3

Concentration (ng/m 3)C25C26C27C28C29C30C31C32C33C34C350246Casa GrandeCowtownPC HousingSum ofHopaneSpeciesTreheloseTreheloseConcentrationConcentration0510152025E-1 E-2 E-3 H-1 H-2 H-3 L-1 L-2 L-3

Sugar Concentration (ng/m3)FineCoarseCasa GrandeCowtownPC HousingLead ConcentrationsLead Concentrations0123456789102/6/09 2/24/09 3/14/09 4/1/09 4/19/09 5/7/09 5/25/09 6/12/09Sampling Date

Metal Concentration ng/m3Pb-coarse-CGPb-coarse-COWPb-coarse-PCHPb-fine-CGPb-fine-COWPb-fine-PCHConclusionsConclusionsMeasurements from the Casa Grande and Pinal CountyMeasurements from the Casa Grande and Pinal CountyHousing Monitors are highly correlated reflecting more ofHousing Monitors are highly correlated reflecting more ofa regional signature, especially in fine particles.a regional signature, especially in fine particles.Measurements from theMeasurements from theCowtownCowtownsite are generally notsite are generally notwell correlated with the other monitoring sites reflectingwell correlated with the other monitoring sites reflectingthe influence of more local sources.the influence of more local sources.The composition and behavior of fine and coarseThe composition and behavior of fine and coarseparticles are fundamentally different.particles are fundamentally different.The organic carbon concentrations in the coarse fractionThe organic carbon concentrations in the coarse fractioncollected atcollected atCowtownCowtownare almost 10x higher than theare almost 10x higher than thefine fraction and measurements taken elsewhere, andfine fraction and measurements taken elsewhere, anddominated by OC2 and OC3 anddominated by OC2 and OC3 andpyrrolizedpyrrolizedcarbon.carbon.Elevated coarse carbon concentrations are oftenElevated coarse carbon concentrations are oftenaccompanied by elevated metal measurements whichaccompanied by elevated metal measurements whichsuggests that they are cosuggests that they are co-emitted or that organicemitted or that organiccompounds are condensed on crustal materials.compounds are condensed on crustal materials.Alkane, ion, and sugar data at, ion, and sugar data atCowtownCowtownsuggest that thesuggest that thecoarse particles may come from at least two distinctcoarse particles may come from at least two distinctsources including a plantsources including a plant-rich agricultural soil and anrich agricultural soil and anorganicorganic-rich feed lot soil.rich feed lot soil.Ongoing work on source apportionment and a full annualOngoing work on source apportionment and a full annualdataset will yield a unique understanding of PM sourcesdataset will yield a unique understanding of PM sourcesin the desert Southwest and is applicable to otherin the desert Southwest and is applicable to otheragricultural regions.agricultural regions.ConclusionsConclusionsAcknowledgementsAcknowledgementsFunding from EPA Region 9Funding from EPA Region 9Disclaimer:Disclaimer:Although this work was reviewed by EPAAlthough this work was reviewed by EPAand approved for publication, it may not necessarilyand approved for publication, it may not necessarilyreflect official Agency policy.reflect official Agency policy.Filter collection and site operations by Pinal AirFilter collection and site operations by Pinal AirQuality Control District personnelQuality Control District personnelICP-MS analysis conducted byMS analysis conducted byNabinUpadhyayUpadhyay