Atmos. Chem. Phys. Discuss., 5, 8421-8471, 2005
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This discussion paper has been under review for the journal Atmospheric Chemistry and Physics (ACP). Please refer to the corresponding final paper in ACP.
Hydrocarbon-like and oxygenated organic aerosols in Pittsburgh: insights into sources and processes of organic aerosols
Q. Zhang1, D. R. Worsnop3, M. R. Canagaratna3, and J.-L. Jimenez1,2
1Cooperative Institute for Research in Environmental Sciences (CIRES), 216 UCB, University of Colorado-Boulder, Boulder, Colorado 80309-0216, USA
2Department of Chemistry and Biochemistry, 216 UCB, University of Colorado-Boulder, Boulder, Colorado 80309-0216, USA
3Aerodyne Research Inc., Billerica, Massachusetts 01821-3976, USA

Abstract. A recently developed algorithm (Zhang et al., 2005) has been applied to deconvolve the mass spectra of organic aerosols acquired with the Aerosol Mass Spectrometer (AMS) in Pittsburgh during September 2002. The results are used here to characterize the mass concentrations, size distributions, and mass spectra of hydrocarbon-like and oxygenated organic aerosol (HOA and OOA, respectively). HOA accounts for 34% of the measured organic aerosol mass and OOA accounts for 66%. The mass concentrations of HOA demonstrate a prominent diurnal profile that peaks in the morning during the rush hour and decreases with the rise of the boundary layer. The diurnal profile of OOA is relatively flat and resembles those of SO42− and NH4+. The size distribution of HOA shows a distinct ultrafine mode that is commonly associated with fresh emissions while OOA is generally concentrated in the accumulation mode and appears to be mostly internally mixed with the inorganic ions, such as SO42− and NH4+. These observations suggest that HOA is likely primary aerosol from local, combustion-related emissions and that OOA is secondary organic aerosol (SOA) influenced by regional contributions. There is strong evidence of the direct correspondence of OOA to SOA during an intense new particle formation and growth event, when condensational growth of OOA was observed. The mass spectrum of OOA of this new particle formation event is very similar to the OOA spectrum of the entire study, which strongly suggests that most OOA during this study is SOA. O3 appears to be a poor indicator for SOA concentration while SO42− is a relatively good surrogate for this dataset. Since the diurnal averages of HOA tightly track those of CO during day time, oxidation/aging of HOA appears to be very small on the time scale of several hours. Based on extracted mass spectra and the likely elemental compositions of major m/z's, the organic mass to organic carbon ratios (OM:OC) of HOA and OOA are estimated at 1.2 and 2.2 μg/μg C, respectively, leading to an average OM:OC ratio of 1.8 for submicron OA in Pittsburgh during September. The C:O ratio of OOA is estimated at 1:0.8. The carbon contents in HOA and OOA calculated accordingly correlate well to primary and secondary organic carbon, respectively, estimated by the OC/EC tracer technique (assuming POC-to-EC ratio=1). In addition, the total carbon concentrations calculated from the AMS data agree well with those measured by the Sunset Laboratory Carbon analyzer (r2=0.87; slope=1.01±0.11).

Citation: Zhang, Q., Worsnop, D. R., Canagaratna, M. R., and Jimenez, J.-L.: Hydrocarbon-like and oxygenated organic aerosols in Pittsburgh: insights into sources and processes of organic aerosols, Atmos. Chem. Phys. Discuss., 5, 8421-8471, doi:10.5194/acpd-5-8421-2005, 2005.
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