Modelling the impact of possible snowpack emissions of O(3P) and NO2 on photochemistry in the South Pole boundary layer

P. D. Hamer; D. E. Shallcross; A. Yabushita; M. Kawasaki

doi:10.1071/EN08022

RESEARCH ARTICLE

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Modelling the impact of possible snowpack emissions of O(³P) and NO₂ on photochemistry in the South Pole boundary layer

P. D. Hamer ^A ^B ^D , D. E. Shallcross ^A , A. Yabushita ^C and M. Kawasaki ^C

+ Author Affiliations

- Author Affiliations

^A School of Chemistry, University of Bristol, Cantock’s Close, Bristol, BS8 1TS, United Kingdom.

^B Present address: Jet Propulsion Laboratory – NASA, 4800 Oak Grove Drive, MS 183-601, Pasadena, CA 91109, USA.

^C Department of Molecular Engineering, Kyoto University, Kyoto, 615-8510, Japan.

^D Corresponding author. Email: paul.d.hamer@jpl.nasa.gov

Environmental Chemistry 5(4) 268-273 https://doi.org/10.1071/EN08022
Submitted: 6 March 2008 Accepted: 27 June 2008 Published: 19 August 2008

Environmental context. The study of surface photochemical ozone production on the Antarctic continent has direct relevance to climate change and general air quality and is scientifically noteworthy given the otherwise pristine nature of this environmental region. The identification of possible direct ozone emissions from snow surfaces and their contribution to the already active photochemical pollution present there represents a unique physical phenomenon. This process could have wider global significance for other snow-covered regions and therefore for global climate change.

Abstract. O(³P) emissions due to photolysis of nitrate were recently identified from ice surfaces doped with nitric acid. O(³P) atoms react directly with molecular oxygen to yield ozone. Therefore, these results may have direct bearing on photochemical activity monitored at the South Pole, a site already noted for elevated summertime surface ozone concentrations. NO₂ is also produced via the photolysis of nitrate and the firn air contains elevated levels of NO₂, which will lead to direct emission of NO₂. A photochemical box model was used to probe what effect O(³P) and NO₂ emissions have on ozone concentrations within the South Pole boundary layer. The results suggest that these emissions could account for a portion of the observed ozone production at the South Pole and may explain the observed upward fluxes of ozone identified there.

Additional keywords: nitrate and ice chemistry, oxygen atoms, ozone, reaction dynamics.

Acknowledgements

P. D. Hamer would like to thank National Environment Research Council (NERC) and BAS for funding, and Will Harris, Betty Hamer and Laura Watson for special assistance. Special thanks to Greg Huey for allowing access to the ISCAT 2000 dataset and to Doug Davis for extremely helpful discussion. D. E. Shallcross and M. Kawasaki thank the Daiwa Anglo-Japanese Foundation for a Daiwa-Adrian award that supported the current work. A. Yabushita and M. Kawasaki thank the Ministry of Education of Japan for financial support.

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