Sources of organic aerosol: Positive matrix factorization of molecular marker data and comparison of results from different source apportionment models

This paper presents results from positive matrix factorization (PMF) of organic molecular marker data to investigate the sources of organic carbon (OC) in Pittsburgh, Pennsylvania. PMF analysis of 21 different combinations of input species found essentially the same seven factors with distinctive source-class-specific groupings of molecular markers. To link factors with source classes we directly compare PMF factor profiles with actual source profiles. Six of the PMF factors appear related to primary emissions from sources such as motor vehicles, biomass combustion, and food cooking. Each primary factor contributed between 5% and 10% of the annual-average OC with the exception of the cooking related factor which contributed 20% of the OC. However, the contribution of the cooking factor was sensitive to the specific combinations of input species. PMF could not differentiate between gasoline and diesel emissions, but the aggregate contribution of primary emissions from these two source classes is estimated to be less than 10% of the annual-average OC. One factor appears related to secondary organic aerosol based on its substantial contribution to biogenic oxidation products. This secondary factor contributed more than 50% of the summertime average OC. Reasonable agreement was observed between the PMF results and those of a previously published chemical mass balance (CMB) analysis of the same molecular marker dataset. Individual PMF factors are correlated with specific CMB sources, but systematic biases exist between the two estimates. These biases were generally within the uncertainty of the two estimates, but there is also evidence that PMF is not cleanly differentiating between source classes.

[1]  M. Kleeman,et al.  Open burning of agricultural biomass: Physical and chemical properties of particle-phase emissions , 2005 .

[2]  Michael J Kleeman,et al.  Measurement of emissions from air pollution sources. 5. C1-C32 organic compounds from gasoline-powered motor vehicles. , 2002, Environmental science & technology.

[3]  Allen L. Robinson,et al.  Photochemical oxidation and changes in molecular composition of organic aerosol in the regional context , 2006 .

[4]  J. Schauer,et al.  Molecular composition of PM2.5 organic aerosol measured at an urban site of Korea during the ACE-Asia campaign , 2006 .

[5]  P. Hopke,et al.  Major Source Categories for PM2.5 in Pittsburgh using PMF and UNMIX , 2006 .

[6]  A. Duarte,et al.  Composition of extractable organic matter of air particles from rural and urban Portuguese areas , 2001 .

[7]  P. Hopke,et al.  Atmospheric aerosol over Vermont: chemical composition and sources. , 2001, Environmental science & technology.

[8]  B. Simoneit.  A review of biomarker compounds as source indicators and tracers for air pollution , 1999, Environmental science and pollution research international.

[9]  J. Fick,et al.  Effect of OH radicals, relative humidity, and time on the composition of the products formed in the ozonolysis of α-pinene , 2003 .

[10]  G. Cass,et al.  Sources of Fine Organic Aerosol. 7. Hot Asphalt Roofing Tar Pot Fumes , 1997 .

[11]  S. Koch,et al.  Formation of new particles in the gas phase ozonolysis of monoterpenes , 2000 .

[12]  John H. Seinfeld,et al.  Gas-Phase Ozone Oxidation of Monoterpenes: Gaseous and Particulate Products , 1999 .

[13]  A. Robinson,et al.  Mass balance closure and the federal reference method for PM2.5 in Pittsburgh, Pennsylvania , 2004 .

[14]  J. Schauer,et al.  Source apportionment of PM2.5 in the Southeastern United States using solvent-extractable organic compounds as tracers. , 2002, Environmental science & technology.

[15]  B. Simoneit,et al.  Characterization of Organic Constituents in Aerosols in Relation to Their rigin and Transport: A Review , 1986 .

[16]  G. Cass,et al.  Chemical Characterization of Fine Particle Emissions from the Wood Stove Combustion of Prevalent United States Tree Species , 2004 .

[17]  Matthew P. Fraser,et al.  Air Quality Model Evaluation Data for Organics. 5. C6−C22 Nonpolar and Semipolar Aromatic Compounds , 1998 .

[18]  Glen R. Cass,et al.  Sources of fine organic aerosol. 4. Particulate abrasion products from leaf surfaces of urban plants , 1993 .

[19]  G R Cass,et al.  Measurement of emissions from air pollution sources. 3. C1-C29 organic compounds from fireplace combustion of wood. , 2001, Environmental science & technology.

[20]  J. C. Cabada,et al.  Positive and Negative Artifacts in Particulate Organic Carbon Measurements with Denuded and Undenuded Sampler Configurations Special Issue of Aerosol Science and Technology on Findings from the Fine Particulate Matter Supersites Program , 2004 .

[21]  Michael D Hays,et al.  Speciation of gas-phase and fine particle emissions from burning of foliar fuels. , 2002, Environmental science & technology.

[22]  A. Robinson,et al.  Source apportionment of molecular markers and organic aerosol--1. Polycyclic aromatic hydrocarbons and methodology for data visualization. , 2006, Environmental science & technology.

[23]  Christopher G. Nolte,et al.  Levoglucosan, a tracer for cellulose in biomass burning and atmospheric particles , 1999 .

[24]  Michael J. Kleeman,et al.  MEASUREMENT OF EMISSIONS FROM AIR POLLUTION SOURCES. 2. C1 THROUGH C30 ORGANIC COMPOUNDS FROM MEDIUM DUTY DIESEL TRUCKS , 1999 .

[25]  Michael J. Kleeman,et al.  Measurement of Emissions from Air Pollution Sources. 1. C1 through C29 Organic Compounds from Meat Charbroiling , 1999 .

[26]  Allen L Robinson,et al.  Source apportionment of molecular markers and organic aerosol. 3. Food cooking emissions. , 2006, Environmental science & technology.

[27]  P. Paatero,et al.  Atmospheric aerosol over Alaska: 2. Elemental composition and sources , 1998 .

[28]  B. Turpin,et al.  Fine particle emission profile for a large coke production facility based on highly time-resolved fence line measurements , 2005 .

[29]  Allen L. Robinson,et al.  Contribution of motor vehicle emissions to organic carbon and fine particle mass in Pittsburgh, Pennsylvania: Effects of varying source profiles and seasonal trends in ambient marker concentrations , 2006 .

[30]  M. Claeys,et al.  Formation of 2-methyl tetrols and 2-methylglyceric acid in secondary organic aerosol from laboratory irradiated isoprene/NOX/SO2/air mixtures and their detection in ambient PM2.5 samples collected in the eastern United States , 2005 .

[31]  G R Cass,et al.  Sources of fine organic aerosol. 6. Cigaret smoke in the urban atmosphere. , 1994, Environmental science & technology.

[32]  G. Cass,et al.  Sources of Fine Organic Aerosol. 9. Pine, Oak, and Synthetic Log Combustion in Residential Fireplaces , 1998 .

[33]  G R Cass,et al.  Chemical characterization of fine particle emissions from fireplace combustion of woods grown in the northeastern United States. , 2001, Environmental science & technology.

[34]  B. Simoneit,et al.  Biomass burning — a review of organic tracers for smoke from incomplete combustion , 2002 .

[35]  B. Simoneit,et al.  Combustion products of plastics as indicators for refuse burning in the atmosphere. , 2005, Environmental science & technology.

[36]  Glen R. Cass,et al.  Sources of fine organic aerosol. 1. Charbroilers and meat cooking operations , 1991 .

[37]  Qi Zhang,et al.  Ubiquity and dominance of oxygenated species in organic aerosols in anthropogenically‐influenced Northern Hemisphere midlatitudes , 2007 .

[38]  Barbara Zielinska,et al.  Emission Rates and Comparative Chemical Composition from Selected In-Use Diesel and Gasoline-Fueled Vehicles , 2004, Journal of the Air & Waste Management Association.

[39]  A. Robinson,et al.  Source apportionment of molecular markers and organic aerosol. 2. Biomass smoke. , 2006, Environmental science & technology.

[40]  Glen R. Cass,et al.  SOURCES OF FINE ORGANIC AEROSOL. 3. ROAD DUST, TIRE DEBRIS, AND ORGANOMETALLIC BRAKE LINING DUST: ROADS AS SOURCES AND SINKS , 1993 .

[41]  J. Yu,et al.  Atmospheric photooxidation of alkylbenzenes-I. Carbonyl product analyses , 1997 .

[42]  Allen L. Robinson,et al.  Positive and Negative Artifacts in Particulate Organic Carbon Measurements with Denuded and Undenuded Sampler Configurations Special Issue of Aerosol Science and Technology on Findings from the Fine Particulate Matter Supersites Program , 2004 .

[43]  D. R. Worsnop,et al.  Hydrocarbon-like and oxygenated organic aerosols in Pittsburgh: insights into sources and processes of organic aerosols , 2005 .

[44]  B. Simoneit,et al.  Organic Matter of the Troposphere-II. Natural Background of biogenic lipid matter in aerosols over the rural western United States ††Contribution No. 2088: Institute of Geophysics and Planetary Physics, University of California at Los Angeles. , 2007 .

[45]  B. Simoneit,et al.  Application of Molecular Marker Analysis to Vehicular Exhaust for Source Reconciliations , 1985 .

[46]  Cliff I. Davidson,et al.  Pittsburgh air quality study overview , 2004 .

[47]  J. Schauer,et al.  Trends in secondary organic aerosol at a remote site in Michigan's upper peninsula. , 2004, Environmental science & technology.

[48]  J. Schauer,et al.  Source reconciliation of atmospheric gas-phase and particle-phase pollutants during a severe photochemical smog episode. , 2002, Environmental science & technology.

[49]  P. Paatero,et al.  Positive matrix factorization: A non-negative factor model with optimal utilization of error estimates of data values† , 1994 .

[50]  B. Simoneit.  Organic matter of the troposphere—III. Characterization and sources of petroleum and pyrogenic residues in aerosols over the western united states , 1984 .

[51]  A. Robinson,et al.  Local and Regional Secondary Organic Aerosol: Insights from a Year of Semi-Continuous Carbon Measurements at Pittsburgh , 2006 .

[52]  A. Robinson,et al.  Insights into the primary–secondary and regional–local contributions to organic aerosol and PM2.5 mass in Pittsburgh, Pennsylvania , 2007 .

[53]  Glen R. Cass,et al.  Sources of fine organic aerosol. 2. Noncatalyst and catalyst-equipped automobiles and heavy-duty diesel trucks , 1993 .

[54]  G. Cass,et al.  Air quality model evaluation data for organics. 6. C3-C24 organic acids. , 2003, Environmental science & technology.

[55]  B. Turpin,et al.  Identification of secondary organic aerosol episodes and quantitation of primary and secondary organic aerosol concentrations during SCAQS , 1995 .

[56]  James J. Schauer,et al.  Source apportionment of airborne particulate matter using organic compounds as tracers , 1996 .

[57]  Armistead G Russell,et al.  Source Apportionment of Daily Fine Particulate Matter at Jefferson Street, Atlanta, GA, during Summer and Winter , 2007, Journal of the Air & Waste Management Association.