ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-11-4209-2011 Global and regional effects of the photochemistry of CH<sub>3</sub>O<sub>2</sub>NO<sub>2</sub>: evidence from ARCTAS Browne E. C. 1 Perring A. E. 1 9 10 Wooldridge P. J. 1 Apel E. 2 Hall S. R. 2 Huey L. G. 3 Mao J. 4 Spencer K. M. 5 Clair J. M. St. 6 Weinheimer A. J. 2 Wisthaler A. 7 Cohen R. C. 1 8 Department of Chemistry, University of California Berkeley, Berkeley, CA, USA Atmospheric Chemistry Division, National Center for Atmospheric Research, Boulder, CO, USA School of Earth and Atmospheric Sciences, Georgia Institute of Technology, Atlanta, GA, USA School of Engineering and Applied Science, Harvard University, Cambridge, MA, USA Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, USA Division of Geology and Planetary Sciences, California Institute of Technology, Pasadena, CA, USA Institut für Ionenphysik & Angewandte Physik, University of Innsbruck, Innsbruck, Austria Department of Earth and Planetary Sciences, University of California Berkeley, Berkeley, CA, USA now at: Chemical Sciences Division, Earth Systems Research Laboratory, National Oceanic and Atmospheric Administration, Boulder, CO, USA now at: Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO, USA 06 05 2011 11 9 4209 4219 This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. This article is available from http://www.atmos-chem-phys.net/11/4209/2011/acp-11-4209-2011.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/11/4209/2011/acp-11-4209-2011.pdf

Using measurements from the NASA Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) experiment, we show that methyl peroxy nitrate (CH<sub>3</sub>O<sub>2</sub>NO<sub>2</sub>) is present in concentrations of ~5–15 pptv in the springtime arctic upper troposphere. We investigate the regional and global effects of CH<sub>3</sub>O<sub>2</sub>NO<sub>2</sub> by including its chemistry in the GEOS-Chem 3-D global chemical transport model. We find that at temperatures below 240 K inclusion of CH<sub>3</sub>O<sub>2</sub>NO<sub>2</sub> chemistry results in decreases of up to ~20 % in NO<sub>x</sub>, ~20 % in N<sub>2</sub>O<sub>5</sub>, ~5 % in HNO<sub>3</sub>, ~2 % in ozone, and increases in methyl hydrogen peroxide of up to ~14 %. Larger changes are observed in biomass burning plumes lofted to high altitude. Additionally, by sequestering NO<sub>x</sub> at low temperatures, CH<sub>3</sub>O<sub>2</sub>NO<sub>2</sub> decreases the cycling of HO<sub>2</sub> to OH, resulting in a larger upper tropospheric HO<sub>2</sub> to OH ratio. These results may impact some estimates of lightning NO<sub>x</sub> sources as well as help explain differences between models and measurements of upper tropospheric composition.

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