Atmos. Chem. Phys. Discuss., 10, 3547-3604, 2010
www.atmos-chem-phys-discuss.net/10/3547/2010/
doi:10.5194/acpd-10-3547-2010
© Author(s) 2010. This work is distributed
under the Creative Commons Attribution 3.0 License.
Review Status
This discussion paper has been under review for the journal Atmospheric Chemistry and Physics (ACP). Please refer to the corresponding final paper in ACP.
Investigation of the correlation between odd oxygen and secondary organic aerosol in Mexico City and Houston
E. C. Wood1, M. R. Canagaratna1, S. C. Herndon1, J. H. Kroll1,*, T. B. Onasch1, C. E. Kolb1, D. R. Worsnop1, W. B. Knighton2, R. Seila3, M. Zavala4, L. T. Molina4, P. F. DeCarlo5,6,**, J. L. Jimenez5,6,7, A. J. Weinheimer8, D. J. Knapp8, B. T. Jobson9, J. Stutz10, W. C. Kuster11, and E. J. Williams11
1Aerodyne Research, Inc., Billerica, Massachusetts, USA
2Department of Chemistry, Montana State University, Bozeman, Montana, USA
3United States Environmental Protection Agency, Research Triangle Park, North Carolina, USA
4Molina Center for Energy and the Environment, La Jolla, California, USA
5Department of Atmospheric and Oceanic Sciences, University of Colorado, Boulder, Colorado, USA
6Cooperative Institute for Research in the Environmental Sciences (CIRES), University of Colorado, Boulder, Colorado, USA
7Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado, USA
8National Center for Atmospheric Research, Boulder, Colorado, USA
9Department of Civil and Environmental Engineering, Washington State University, Pullman, Washington, USA
10Department of Atmospheric and Oceanic Sciences, University of California, Los Angeles, California, USA
11NOAA Earth System Research Laboratory, Boulder, Colorado, USA
*now at: Department of Civil and Environmental Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts, USA
**now at: Laboratory of Atmospheric Chemistry, Paul Scherrer Institute, Switzerland

Abstract. Many recent models underpredict secondary organic aerosol (SOA) particulate matter (PM) concentrations in polluted regions, indicating serious deficiencies in the models' chemical mechanisms and/or missing SOA precursors. Since tropospheric photochemical ozone production is much better understood, we investigate the correlation of odd-oxygen ([Ox]≡[O3]+[NO2]) and the oxygenated component of organic aerosol (OOA), which is interpreted as a surrogate for SOA. OOA and Ox measured in Mexico City in 2006 and Houston in 2000 were well correlated in air masses where both species were formed on similar timescales (less than 8 h) and not well correlated when their formation timescales or location differed greatly. When correlated, the ratio of these two species ranged from 30 μg m−3 ppm−1 (STP) in Houston during time periods affected by large petrochemical plant emissions to as high as 160 μg m−3 ppm−1 in Mexico City, where typical values were near 120 μg m−3 ppm−1. On several days in Mexico City, the [OOA]/[Ox] ratio decreased by a factor of ~2 between 08:00 and 13:00 LT. This decrease is only partially attributable to evaporation of the least oxidized and most volatile components of OOA; differences in the diurnal emission trends and timescales for photochemical processing of SOA precursors compared to ozone precursors also likely contribute to the observed decrease. The extent of OOA oxidation increased with photochemical aging. Calculations of the ratio of the SOA formation rate to the Ox production rate using ambient VOC measurements and traditional laboratory SOA yields are lower than the observed [OOA]/[Ox] ratios by factors of 5 to 15, consistent with several other models' underestimates of SOA. Calculations of this ratio using emission factors for organic compounds from gasoline and diesel exhaust do not reproduce the observed ratio. Although not succesful in reproducing the atmospheric observations presented, modeling P(SOA)/P(Ox) can serve as a useful test of photochemical models using improved formulation mechanisms for SOA.

Citation: Wood, E. C., Canagaratna, M. R., Herndon, S. C., Kroll, J. H., Onasch, T. B., Kolb, C. E., Worsnop, D. R., Knighton, W. B., Seila, R., Zavala, M., Molina, L. T., DeCarlo, P. F., Jimenez, J. L., Weinheimer, A. J., Knapp, D. J., Jobson, B. T., Stutz, J., Kuster, W. C., and Williams, E. J.: Investigation of the correlation between odd oxygen and secondary organic aerosol in Mexico City and Houston, Atmos. Chem. Phys. Discuss., 10, 3547-3604, doi:10.5194/acpd-10-3547-2010, 2010.
 
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