Source Apportionment forPM2.5at Houston Clinton DriveDavid W. SullivanThe University of Texas at AustinCenter for Energy & Environmental ResearchRichard TroppUniversity of Nevada RenoDesert Research InstitutePM2.5Issues• Clinton Drive, west end of Ship Channel,only site in Texas at risk of nonattainment.• 2004-2006 design value 15.4μg/m3exceeds 15.0 NAAQS.• Next highest DV in HGB:13μg/m3• Various methods show “soil” to besignificant factor in why this site is areamax.Methods of Data Analysis• Analyze PM2.5= f( rain, wind speed, direction ).• Analyze PM2.5= f( time, weekday, season )• Analyze PM10& PM10/PM2.5by wind direction.• Use Hysplit1trajectories to assess transport.• Use previous research results to describefactors.• Apply Positive Matrix Factorization to speciation.1. Draxler, R.R. and Rolph, G.D., 2003. HYSPLIT (HYbrid Single-ParticleLagrangian Integrated Trajectory)Model access via NOAA ARL READY Website (http://www.arl.noaa.gov/ready/hysplit4.html). NOAA AirResources Laboratory,Silver Spring, MD.Rolph, G.D., 2003. Real-time Environmental Applications and Display sYstem (READY) Website(http://www.arl.noaa.gov/ready/hysplit4.html). NOAA Air Resources Laboratory, Silver Spring, MD.Major Features ofMajor Features ofAtmospheric Particle Mass DistributionAtmospheric Particle Mass Distribution02468100.0010.010.1110100Particle Aerodynamic Diameter (μm)

Relative Mass ConcentrationAccumulationCoarsePM10PM2.5GeologicalMaterial, Pollen,Sea SaltSulfate, Nitrate,Ammonium,Organic Carbon,Elemental Carbon,Heavy Metals, FineGeologicalCondensedOrganicCarbon orSulfuric AcidVapors, CleanEnvironmentUltrafineCondensationModeDropletModeTSPPM0.1NucleationFresh HighTemperatureEmissions,OrganicCarbon,Sulfuric Acid,Metal VaporsData• Clinton PM2.5FRM mass, hourly TEOM mass• Clinton PM2.5special speciation for this study:– Quartz-filter: EC, OC,– Teflon-filter: ions, elements• Clinton PM10HiVol filter mass• PM2.5FRM and Speciation Network mass andfrom other HGB sites• PM2.5Speciation Network sample compositions• Clinton wind speed resultant, wind directionresultant, and precipitation data.Clinton and environsClinton PM2.5and meteorology• Look at effects of rain, wind direction, andwind speed.• Compare PM2.5and PM10directionalityPM2.5and rain• Using 24-hravg’d TEOMdata.• Found averageconcentration 2days after rainstatisticallysignificantlyhigher than alldays.PM2.5and wind direction• TEOM PM2.5concentrationby 10 deg. winddirection bin2002-2007• Relatively weakdirectionality,lowestconcentrationsto the northμg/m3PM10and wind direction• 24-hourfiltersamples whourlywinds• Clintonshowsdirectionality to SWDeer ParkWesthollowAldineClintonμg/m3μg/m3μg/m3μg/m30°= north, 90°= east, 180°= south, 270°= west, 360° =north% of PM2.5> 15μg/m3from eachwind direction in 2005, 2006 at Clinton0.0%1.0%2.0%3.0%4.0%5.0%6.0%7.0%8.0%9.0%10.0%0 30 60 90 120 150 180 210 240 270 300 330 3602005 % Excess2006 % ExcessCase studyCase Study - transportPM2.5 and wind speed• RegresshourlyPM2.5 onwind speedby 30-deg.winddirectionbin• Slopenegative allbut S & SWDirections 165-225degDirections 0-164, 226-360 degμg/m3μg/m3Meteorological evidence supports dust• Higher PM2.5after rain from dried roaddust• Strong directionality for PM10(crustalmaterial in PMcoarse)• Positive association with wind speed thatdislodges surface soil.Use speciation from past studies• As speciated data were collected:– Source profiles selected from EPS SPECIATEdatabase for comparison– Reconstruction formulas from published workused to calculate factors:Speciation data analysisSpeciation Analysis•Inventory of data validated to datePeriodSample typesNumber ofAmbient Samples1/4/05 – 4/7/06ions, elements (Teflon) 754/17/06 – 8/4/06ions, elements (Teflon) 545/27/06 – 8/4/06EC/OC (Quartz)408/6/06 – 12/31/06ions, elements (Teflon) 428/6/06 – 12/31/06EC/OC (Quartz)30Combined 5/27/06 – 12/31/06 EC/OC, ions, elements 63Teflon filters by XRF for elements and IC for ionsQuartz filters by thermal optical analysis for EC/OCFRM R&P 2025 sequential samplersTropp et al.’s (2006) Texas speciation•Soil= 1.89 * Al + 2.14 * Si + 1.40* Ca + 1.43 * Fe•Ammonium sulfate= 1.38 * SO4=•Ammonium nitrate= 1.29 * NO3-•Salt= 1.65 * Cl•Trace elements= sum of XRFspecies – (Al, Si, Ca, Fe, S, Cl,Na )•OC= 1.4 * OCTTC•EC= ECTTC•Other= theμg/m3from Teflonfilter minus seven constituentsabove.Al = AluminumS = SulfurSi = SiliconNa = SodiumCa = CalciumSO4= = Sulfate ionFe = ironNO3- = Nitrate ionCl = ChlorineOCTTC = OrganicCarbon by thermaltransmittanceECTTC = ElementalCarbon by thermaltransmittanceExample of PM2.5concentration factors by sitesJune 21, 2005 Reconstructed Species Comparison05101520253035Aldine Channelview Bayland Park EastClinton Deer Park

ug/m3othertracesaltammonium_sulfateammonium_nitratesoilClinton,elevated“soil”Composite PM2.5 factors by siteSoil PM2.5agrees w directions for “excess PM2.5” and PM10– SE-WestThe data are from24-hour sampleson 30 “average”days and on 45high PM2.5days.SO4 at5 TCEQspec.sites,and atClintonAldine 2001-2005Channelview 2001Bayland 2002-2005East 2001-2006Deer Park 2001-2005Clinton 2006Positive matrix factorization• Given multivariate data and correspondinguncertainties, EPA PMF 1.1 estimatesfactors.• User selects desired number of factors,and must interpret output.• Results at Clinton w 63 62 samples in2006 similar to results on longer timeseries at other Houston area speciationsites.Positive matrix factorization• Solve matrix eq. X = G F + E where– X is n×m matrix of samples×species– G is n×p matrix of contribution of source tosample– F is p×m matrix of fixed source profiles– E is residual• Min Q = sumI(sumJ(eIJ2/ sIJ2))• Generally, good soln has Q* = n * m• This model n = 62, m = 17, Qtarget= 1054Results• Q* = 1091 (vs 1054)• 7 factors• However, reconstruction of total massfrom the factor contributions has largeresidual.• Hendler, 2006 has similar results• Buzcu, et al. 2003 have different resultsSea saltSea saltMotor vehiclesMotor vehiclesCalcium, ECCalcium, ECSulfateSulfateIndustrialcombustionIndustrialcombustionNitrateNitrateSOILSOILEnd comparison suggests need more data....Compare Reconstruct to Actual05101520253035400 5 10 15 20 25 30 35 40ug/m3

ug/m3Compare Hous. East (Hendler)FactorHouston EastClinton DrSulfate-rich secondaryaerosolSept. – Oct.fallNitrate-rich aerosol Nov. – Mar.winterMotor vehiclesAug. – Jan.fallSea saltMar., May-Jun.springSoil/crustal matterJul. – Aug.springIndustrial combustion Year-aroundsummerBiomass burning MayNot observed“Calcium”Not foundYear-aroundConclusion• Soil-like material provides some 2μg/m3add-on at Clinton.• Soil and dry bulk material samples havebeen taken for analysis and source profiledevelopment.• Additional projects to assess transport ofMex.-CenAm smoke and to assessregional trends apportionment ongoing.Photos of dusty nearby areasAt Clinton Gate – Facing EastValero AsphaltImmediately to the East of the GateAt Gate – Facing West towardsPTRA / A&L Loading YardAt Monitor – Across from UP,PTRA and A&L Loading YardA&L Trucking/Ranger SteelUse of Emulsified AsphaltEmulsified Asphalt...cont(tracking from outside roads?)Crushed Concrete Material