ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-12-10257-2012 Chamber simulation of photooxidation of dimethyl sulfide and isoprene in the presence of NO<sub>x</sub> Chen T. 1 Jang M. 1 Department of Environmental Engineering Sciences, P.O. Box 116450, University of Florida, Gainesville, FL, 32611, USA 06 11 2012 12 21 10257 10269 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/12/10257/2012/acp-12-10257-2012.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/12/10257/2012/acp-12-10257-2012.pdf

To improve the model prediction for the formation of H<sub>2</sub>SO<sub>4</sub> and methanesulfonic acid (MSA), aerosol-phase reactions of gaseous dimethyl sulfide (DMS) oxidation products [e.g., dimethyl sulfoxide (DMSO)] in aerosol have been included in the DMS kinetic model with the recently reported gas-phase reactions and their rate constants. To determine the rate constants of aerosol-phase reactions of both DMSO and its major gaseous products [e.g., dimethyl sulfone (DMSO<sub>2</sub>) and methanesulfinic acid (MSIA)], DMSO was photooxidized in the presence of NO<sub>x</sub> using a 2 m<sup>3</sup> Teflon film chamber. The rate constants tested in the DMSO kinetic mechanisms were then incorporated into the DMS photooxidation mechanism. The model simulation using the newly constructed DMS oxidation mechanims was compared to chamber data obtained from the phototoxiation of DMS in the presence of NO<sub>x</sub>. Within 120-min simulation, the predicted concentrations of MSA increase by 200–400% and those of H<sub>2</sub>SO<sub>4</sub>, by 50–200% due to aerosol-phase chemistry. This was well substantiated with experimental data. To study the effect of coexisting volatile organic compounds, the photooxidation of DMS in the presence of isoprene and NO<sub>x</sub> has been simulated using the newly constructed DMS kinetic model integrated with the Master Chemical Mechanism (MCM) for isoprene oxidation, and compared to chamber data. With the high concentrations of DMS (250 ppb) and isoprene (560–2248 ppb), both the model simulation and experimental data showed an increase in the yields of MSA and H<sub>2</sub>SO<sub>4</sub> as the isoprene concentration increased.

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