Atmos. Chem. Phys., 11, 6639-6662, 2011
www.atmos-chem-phys.net/11/6639/2011/
doi:10.5194/acp-11-6639-2011
© Author(s) 2011. This work is distributed
under the Creative Commons Attribution 3.0 License.
Modeling organic aerosols in a megacity: comparison of simple and complex representations of the volatility basis set approach
M. Shrivastava1, J. Fast1, R. Easter1, W. I. Gustafson Jr.1, R. A. Zaveri1, J. L. Jimenez2, P. Saide3, and A. Hodzic4
1Atmospheric Sciences & Global Change Division, Pacific Northwest National Laboratory, Richland, WA 99352, USA
2University of Colorado, Boulder, CO, USA
3Center for Global and Regional Environmental Research, University of Iowa, Iowa City, Iowa, USA
4National Center for Atmospheric Research, Boulder, CO, USA

Abstract. The Weather Research and Forecasting model coupled with chemistry (WRF-Chem) is modified to include a volatility basis set (VBS) treatment of secondary organic aerosol formation. The VBS approach, coupled with SAPRC-99 gas-phase chemistry mechanism, is used to model gas-particle partitioning and multiple generations of gas-phase oxidation of organic vapors. In addition to the detailed 9-species VBS, a simplified mechanism using 2 volatility species (2-species VBS) is developed and tested for similarity to the 9-species VBS in terms of both mass and oxygen-to-carbon ratios of organic aerosols in the atmosphere. WRF-Chem results are evaluated against field measurements of organic aerosols collected during the MILAGRO 2006 campaign in the vicinity of Mexico City. The simplified 2-species mechanism reduces the computational cost by a factor of 2 as compared to 9-species VBS. Both ground site and aircraft measurements suggest that the 9-species and 2-species VBS predictions of total organic aerosol mass as well as individual organic aerosol components including primary, secondary, and biomass burning are comparable in magnitude. In addition, oxygen-to-carbon ratio predictions from both approaches agree within 25 %, providing evidence that the 2-species VBS is well suited to represent the complex evolution of organic aerosols. Model sensitivity to amount of anthropogenic semi-volatile and intermediate volatility (S/IVOC) precursor emissions is also examined by doubling the default emissions. Both the emission cases significantly under-predict primary organic aerosols in the city center and along aircraft flight transects. Secondary organic aerosols are predicted reasonably well along flight tracks surrounding the city, but are consistently over-predicted downwind of the city. Also, oxygen-to-carbon ratio predictions are significantly improved compared to prior studies by adding 15 % oxygen mass per generation of oxidation; however, all modeling cases still under-predict these ratios downwind as compared to measurements, suggesting a need to further improve chemistry parameterizations of secondary organic aerosol formation.

Citation: Shrivastava, M., Fast, J., Easter, R., Gustafson Jr., W. I., Zaveri, R. A., Jimenez, J. L., Saide, P., and Hodzic, A.: Modeling organic aerosols in a megacity: comparison of simple and complex representations of the volatility basis set approach, Atmos. Chem. Phys., 11, 6639-6662, doi:10.5194/acp-11-6639-2011, 2011.
 
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