Atmos. Chem. Phys. Discuss., 11, 7189-7233, 2011
© Author(s) 2011. This work is distributed
under the Creative Commons Attribution 3.0 License.
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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.
Ozone-driven photochemical formation of carboxylic acid groups from alkane groups
S. Liu1, D. A. Day1,*, J. E. Shields1, and L. M. Russell1
1Scripps Institution of Oceanography, Univ. of California, San Diego, La Jolla, California, USA
*now at: Cooperative Institute for Research in the Environmental Sciences, University of Colorado, Boulder, Colorado, USA

Abstract. Carboxylic acids are ubiquitous in atmospheric particles, and they play an important role in the physical and chemical properties of aerosol particles. During measurements in coastal California in the summer of 2009, carboxylic acid functional groups were highly associated with trajectories from an industrial region with high organic mass (OM), likely from fossil fuel combustion emissions. The concentration of carboxylic acid groups peaked during daytime, suggesting a photochemical secondary formation mechanism. This daytime increase in concentration was tightly correlated with O3 mixing ratio, indicating O3 was the likely driver in acid formation. Based on the diurnal cycles of carboxylic acid and alkane groups, the covariation of carboxylic acid groups with O3, and the composition of the Combustion factor resulted from the factor analyses, gas-phase alkane oxidation by OH radicals to form dihyfrofuran followed by further oxidation of dihydrofuran by O3 is the likely acid formation mechanism. Using the multi-day average of the daytime increase of carboxylic acid group concentrations and m/z 44-based Aged Combustion factor, we estimated the lower-bound contributions of secondary organic aerosol (SOA) formed in 12-h daytime of processing in a single day to be 30% of the carboxylic acid groups and 25–45% of the Combustion factor concentration. These unique ambient observations of photochemically-driven acid formation suggest that gas-phase alkanes might be important sources of SOA formation in this coastal region.

Citation: Liu, S., Day, D. A., Shields, J. E., and Russell, L. M.: Ozone-driven photochemical formation of carboxylic acid groups from alkane groups, Atmos. Chem. Phys. Discuss., 11, 7189-7233, doi:10.5194/acpd-11-7189-2011, 2011.
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