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Weak global sensitivity of cloud condensation nuclei and the aerosol indirect effect to Criegee + SO2 chemistry

Pierce, J. R. ; Evans, M. J. ; Scott, C. E. ; D'Andrea, S. D. ; Farmer, D. K. ; Swietlicki, Erik LU and Spracklen, D. V. (2013) In Atmospheric Chemistry and Physics 13(6). p.3163-3176
Abstract
H2SO4 vapor is important for the nucleation of atmospheric aerosols and the growth of ultrafine particles to cloud condensation nuclei (CCN) sizes with important roles in the global aerosol budget and hence planetary radiative forcing. 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. For the first time in a global model, we investigate the impact of this new source of H2SO4 in the atmosphere. 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... (More)
H2SO4 vapor is important for the nucleation of atmospheric aerosols and the growth of ultrafine particles to cloud condensation nuclei (CCN) sizes with important roles in the global aerosol budget and hence planetary radiative forcing. 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. For the first time in a global model, we investigate the impact of this new source of H2SO4 in the atmosphere. 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 changes in CCN were strongly dampened to the CI+ SO2 changes in H2SO4 in some 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 (secondary organic aerosol) 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 lead to significant improvements in present-day CCN and AIE predictions. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Atmospheric Chemistry and Physics
volume
13
issue
6
pages
3163 - 3176
publisher
Copernicus Gesellschaft mbH
external identifiers
  • wos:000316961000015
  • scopus:84901346317
ISSN
1680-7324
DOI
10.5194/acp-13-3163-2013
language
English
LU publication?
yes
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The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Nuclear Physics (Faculty of Technology) (011013007)
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32ee5898-3b68-4048-a25e-0f48e8f64bdc (old id 3853404)
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2016-04-01 10:12:33
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2020-01-05 05:14:32
@article{32ee5898-3b68-4048-a25e-0f48e8f64bdc,
  abstract     = {H2SO4 vapor is important for the nucleation of atmospheric aerosols and the growth of ultrafine particles to cloud condensation nuclei (CCN) sizes with important roles in the global aerosol budget and hence planetary radiative forcing. 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. For the first time in a global model, we investigate the impact of this new source of H2SO4 in the atmosphere. 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 changes in CCN were strongly dampened to the CI+ SO2 changes in H2SO4 in some 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 (secondary organic aerosol) 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 lead to significant improvements in present-day CCN and AIE predictions.},
  author       = {Pierce, J. R. and Evans, M. J. and Scott, C. E. and D'Andrea, S. D. and Farmer, D. K. and Swietlicki, Erik and Spracklen, D. V.},
  issn         = {1680-7324},
  language     = {eng},
  number       = {6},
  pages        = {3163--3176},
  publisher    = {Copernicus Gesellschaft mbH},
  series       = {Atmospheric Chemistry and Physics},
  title        = {Weak global sensitivity of cloud condensation nuclei and the aerosol indirect effect to Criegee + SO2 chemistry},
  url          = {http://dx.doi.org/10.5194/acp-13-3163-2013},
  doi          = {10.5194/acp-13-3163-2013},
  volume       = {13},
  year         = {2013},
}