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Regional and global impacts of Criegee intermediates on atmospheric sulphuric acid concentrations and first steps of aerosol formation

Regional and global impacts of Criegee intermediates on atmospheric sulphuric acid concentrations and first steps of aerosol formation
Regional and global impacts of Criegee intermediates on atmospheric sulphuric acid concentrations and first steps of aerosol formation
Carbonyl oxides (“Criegee intermediates”), formed in the ozonolysis of alkenes, are key species in tropospheric oxidation of organic molecules and their decomposition provides a non-photolytic source of OH in the atmosphere (Johnson and Marston, Chem. Soc. Rev., 2008, 37, 699, Harrison et al., Sci. Total Environ., 2006, 360, 5, Gäb et al., Nature, 1985, 316, 535,). Recently it was shown that small Criegee intermediates, C.I.’s, react far more rapidly with SO2 than typically represented in tropospheric models, (Welz, Science, 2012, 335, 204,) which suggested that carbonyl oxides could have a substantial influence on the atmospheric oxidation of SO2. Oxidation of SO2 is the main atmospheric source of sulphuric acid (H2SO4), which is a critical contributor to aerosol formation, although questions remain about the fundamental nucleation mechanism (Sipilä et al., Science, 2010, 327, 1243, Metzger et al., Proc. Natl. Acad. Sci. U.S.A., 2010 107, 6646, Kirkby et al., Nature, 2011, 476, 429,). Non-absorbing atmospheric aerosols, by scattering incoming solar radiation and acting as cloud condensation nuclei, have a cooling effect on climate (Intergovernmental Panel on Climate Change (IPCC), Climate Change 2007: The Physical Science Basis, Cambridge University Press, 2007). Here we explore the effect of the Criegees on atmospheric chemistry, and demonstrate that ozonolysis of alkenes via the reaction of Criegee intermediates potentially has a large impact on atmospheric sulphuric acid concentrations and consequently the first steps in aerosol production. Reactions of Criegee intermediates with SO2 will compete with and in places dominate over the reaction of OH with SO2 (the only other known gas-phase source of H2SO4) in many areas of the Earth's surface. In the case that the products of Criegee intermediate reactions predominantly result in H2SO4 formation, modelled particle nucleation rates can be substantially increased by the improved experimentally obtained estimates of the rate coefficients of Criegee intermediate reactions. Using both regional and global scale modelling, we show that this enhancement is likely to be highly variable spatially with local hot-spots in e.g. urban outflows. This conclusion is however contingent on a number of remaining uncertainties in Criegee intermediate chemistry.
0301-7249
1-29
Percival, Carl J.
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Welz, Oliver
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Eskola, Arkke J.
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Savee, John D.
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Osborn, David L.
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Topping, David O.
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Lowe, Douglas
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Utembe, Steven R.
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Bacak, Asan
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McFiggans, Gordon
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Cooke, Michael C.
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Xiao, Ping
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Archibald, Alexander T.
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Jenkin, Michael E.
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Derwent, Richard G.
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Riipinen, Ilona
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Mok, Daniel W. K.
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Lee, Edmond P.F.
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Dyke, John M.
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Taatjes, Craig A.
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Shallcross, Dudley E.
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Percival, Carl J.
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Welz, Oliver
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Eskola, Arkke J.
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Savee, John D.
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Osborn, David L.
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Topping, David O.
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Lowe, Douglas
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Utembe, Steven R.
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Bacak, Asan
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McFiggans, Gordon
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Cooke, Michael C.
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Xiao, Ping
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Archibald, Alexander T.
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Jenkin, Michael E.
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Derwent, Richard G.
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Riipinen, Ilona
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Mok, Daniel W. K.
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Lee, Edmond P.F.
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Dyke, John M.
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Taatjes, Craig A.
381610dc-019b-4dd3-bbf0-3cccb63b13dd
Shallcross, Dudley E.
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Percival, Carl J., Welz, Oliver, Eskola, Arkke J., Savee, John D., Osborn, David L., Topping, David O., Lowe, Douglas, Utembe, Steven R., Bacak, Asan, McFiggans, Gordon, Cooke, Michael C., Xiao, Ping, Archibald, Alexander T., Jenkin, Michael E., Derwent, Richard G., Riipinen, Ilona, Mok, Daniel W. K., Lee, Edmond P.F., Dyke, John M., Taatjes, Craig A. and Shallcross, Dudley E. (2013) Regional and global impacts of Criegee intermediates on atmospheric sulphuric acid concentrations and first steps of aerosol formation Faraday Discussions, pp. 1-29. (doi:10.1039/C3FD00048F).

Record type: Article

Abstract

Carbonyl oxides (“Criegee intermediates”), formed in the ozonolysis of alkenes, are key species in tropospheric oxidation of organic molecules and their decomposition provides a non-photolytic source of OH in the atmosphere (Johnson and Marston, Chem. Soc. Rev., 2008, 37, 699, Harrison et al., Sci. Total Environ., 2006, 360, 5, Gäb et al., Nature, 1985, 316, 535,). Recently it was shown that small Criegee intermediates, C.I.’s, react far more rapidly with SO2 than typically represented in tropospheric models, (Welz, Science, 2012, 335, 204,) which suggested that carbonyl oxides could have a substantial influence on the atmospheric oxidation of SO2. Oxidation of SO2 is the main atmospheric source of sulphuric acid (H2SO4), which is a critical contributor to aerosol formation, although questions remain about the fundamental nucleation mechanism (Sipilä et al., Science, 2010, 327, 1243, Metzger et al., Proc. Natl. Acad. Sci. U.S.A., 2010 107, 6646, Kirkby et al., Nature, 2011, 476, 429,). Non-absorbing atmospheric aerosols, by scattering incoming solar radiation and acting as cloud condensation nuclei, have a cooling effect on climate (Intergovernmental Panel on Climate Change (IPCC), Climate Change 2007: The Physical Science Basis, Cambridge University Press, 2007). Here we explore the effect of the Criegees on atmospheric chemistry, and demonstrate that ozonolysis of alkenes via the reaction of Criegee intermediates potentially has a large impact on atmospheric sulphuric acid concentrations and consequently the first steps in aerosol production. Reactions of Criegee intermediates with SO2 will compete with and in places dominate over the reaction of OH with SO2 (the only other known gas-phase source of H2SO4) in many areas of the Earth's surface. In the case that the products of Criegee intermediate reactions predominantly result in H2SO4 formation, modelled particle nucleation rates can be substantially increased by the improved experimentally obtained estimates of the rate coefficients of Criegee intermediate reactions. Using both regional and global scale modelling, we show that this enhancement is likely to be highly variable spatially with local hot-spots in e.g. urban outflows. This conclusion is however contingent on a number of remaining uncertainties in Criegee intermediate chemistry.

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Published date: 1 May 2013
Organisations: Computational Systems Chemistry

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Local EPrints ID: 359958
URI: http://eprints.soton.ac.uk/id/eprint/359958
ISSN: 0301-7249
PURE UUID: 2cc755b9-1ad3-43de-acb3-49d71b3e6076
ORCID for John M. Dyke: ORCID iD orcid.org/0000-0002-9808-303X

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Date deposited: 18 Nov 2013 16:22
Last modified: 18 Jul 2017 03:16

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Contributors

Author: Carl J. Percival
Author: Oliver Welz
Author: Arkke J. Eskola
Author: John D. Savee
Author: David L. Osborn
Author: David O. Topping
Author: Douglas Lowe
Author: Steven R. Utembe
Author: Asan Bacak
Author: Gordon McFiggans
Author: Michael C. Cooke
Author: Ping Xiao
Author: Alexander T. Archibald
Author: Michael E. Jenkin
Author: Richard G. Derwent
Author: Ilona Riipinen
Author: Daniel W. K. Mok
Author: Edmond P.F. Lee
Author: John M. Dyke ORCID iD
Author: Craig A. Taatjes
Author: Dudley E. Shallcross

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