Atmos. Chem. Phys. Discuss., 12, 33127-33163, 2012
© Author(s) 2012. This work is distributed
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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.
Weak sensitivity of cloud condensation nuclei and the aerosol indirect effect to Criegee + SO2 chemistry
J. R. Pierce1,2, M. J. Evans3, C. E. Scott4, S. D. D'Andrea1,2, D. K. Farmer5, E. Swietlicki6, and D. V. Spracklen4
1Department of Atmospheric Science, Colorado State University, Ft. Collins, CO, USA
2Department of Physics and Atmospheric Science, Dalhousie University, Halifax, NS, Canada
3Department of Chemistry, University of York, York, UK
4School of Earth and Environment, University of Leeds, Leeds, UK
5Department of Chemistry, Colorado State University, Ft. Collins, CO, USA
6Division of Nuclear Physics, Lund University, Lund, Sweden

Abstract. H2SO4 vapor is important for the nucleation of atmospheric aerosols and the growth of ultrafine particles to cloud condensation nuclei (CCN) sizes. Recent studies have found that reactions of stabilized Criegee intermediates (CIs, formed from the ozonolysis of alkenes) with SO2 may be an important source of H2SO4 that has been missing from atmospheric aerosol models. In this paper, we use the chemical transport model, GEOS-Chem, with the online aerosol microphysics module, TOMAS, to estimate the possible impact of CIs on present-day H2SO4, CCN, and the cloud-albedo aerosol indirect effect (AIE). We extend the standard GEOS-Chem chemistry with CI-forming reactions (ozonolysis of isoprene, methyl vinyl ketone, methacrolein, propene, and monoterpenes) from the Master Chemical Mechanism. Using a fast rate constant for CI+SO2, we find that the addition of this chemistry increases the global production of H2SO4 by 4%. H2SO4 concentrations increase by over 100% in forested tropical boundary layers and by over 10–25% in forested NH boundary layers (up to 100% in July) due to CI + SO2 chemistry, but the change is generally negligible elsewhere. The predicted changed in CCN were strongly dampened to the CI + SO2 changes in H2SO4 in these regions: less than 15% in tropical forests and less than 2% in most mid-latitude locations. The global-mean CCN change was less than 1% both in the boundary layer and the free troposphere. The associated cloud-albedo AIE change was less than 0.03 W m−2. The model global sensitivity of CCN and the AIE to CI + SO2 chemistry is significantly (approximately one order-of-magnitude) smaller than the sensitivity of CCN and AIE to other uncertain model inputs, such as nucleation mechanisms, primary emissions, SOA and deposition. Similarly, comparisons to size-distribution measurements show that uncertainties in other model parameters dominate model biases in the model-predicted size distributions. We conclude that improvement in the modeled CI + SO2 chemistry would not likely to lead to significant improvements in present-day CCN and AIE predictions.

Citation: Pierce, J. R., Evans, M. J., Scott, C. E., D'Andrea, S. D., Farmer, D. K., Swietlicki, E., and Spracklen, D. V.: Weak sensitivity of cloud condensation nuclei and the aerosol indirect effect to Criegee + SO2 chemistry, Atmos. Chem. Phys. Discuss., 12, 33127-33163, doi:10.5194/acpd-12-33127-2012, 2012.
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