ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-10-9551-2010 Laboratory simulation for the aqueous OH-oxidation of methyl vinyl ketone and methacrolein: significance to the in-cloud SOA production Zhang X. 1 Chen Z. M. 1 Zhao Y. 1 State Key Laboratory of Environmental Simulation and Pollution Control, College of Environmental Sciences and Engineering, Peking University, Beijing 100871, China 08 10 2010 10 19 9551 9561 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/10/9551/2010/acp-10-9551-2010.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/10/9551/2010/acp-10-9551-2010.pdf

Increasing evidence suggests that secondary organic aerosol (SOA) is formed through aqueous phase reactions in atmospheric clouds. In the present study, the aqueous oxidation of methyl vinyl ketone (MVK) and methacrolein (MACR) via OH radical were investigated, with an emphasis on the composition and variation of small-molecular-weight organic products. In addition, high-molecular-weight compounds (HMWs) were found, interpreted as the ion abundance and time evolution. Our results provide, for the first time to our knowledge, experimental evidence that aqueous OH-oxidation of MVK contributes to SOA formation. Further, a mechanism primarily involving radical processes was proposed to gain a basic understanding of these two reactions. Based on the assumed mechanism, a kinetic model was developed for comparison with the experimental results. The model reproduced the observed profiles of first-generation intermediates, but failed to simulate the kinetics of most organic acids mainly due to the lack of chemical kinetics parameters for HMWs. A sensitivity analysis was performed in terms of the effect of stoichiometric coefficients for precursors on oxalic acid yields and the result indicates that additional pathways involving HMWs chemistry might play an important role in the formation of oxalic acid. We suggest that further study is needed for better understanding the behavior of multi-functional products and their contribution to the oxalic acid formation.

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