Atmospheric Chemistry and Physics www.atmos-chem-phys.net 1680-7316 1680-7324 8 8 2008 10.5194/acp-8-2255-2008 http://www.atmos-chem-phys.net/8/2255/2008/ http://www.atmos-chem-phys.net/8/2255/2008/acp-8-2255-2008.html http://www.atmos-chem-phys.net/8/2255/2008/acp-8-2255-2008.pdf 2255 2265 2008-04-24 Aqueous-phase ozonolysis of methacrolein and methyl vinyl ketone: a potentially important source of atmospheric aqueous oxidants Z. M. Chen zmchen@pku.edu.cn H. L. Wang L. H. Zhu C. X. Wang C. Y. Jie W. Hua State Key Laboratory of Environmental Simulation and Pollution Control, College of Environmental Sciences and Engineering, Peking University, Beijing 100871, China Recent studies indicate that isoprene and its gas-phase oxidation products could contribute a considerable amount of aerosol through aqueous-phase acid-catalyzed oxidation with hydrogen peroxide (H₂O₂), although the source of H₂O₂ is unclear. The present study revealed a potentially important route to the formation of aqueous oxidants, including H₂O₂, from the aqueous-phase ozonolysis of methacrolein (MAC) and methyl vinyl ketone (MVK). Laboratory simulation was used to perform the atmospheric aqueous-phase ozonolysis at different pHs and temperatures. Unexpectedly high molar yields of the products, including hydroxylmethyl hydroperoxide (HMHP), formaldehyde (HCHO) and methylglyoxal (MG), of both of these reaction systems have been seen. Moreover, these yields are almost independent of pH and temperature and are as follows: (i) for MAC–O₃, 70.3±6.3% HMHP, 32.3±5.8% HCHO and 98.6±5.4% MG; and (ii) for MVK–O₃, 68.9±9.7% HMHP, 13.3±5.8% HCHO and 75.4±7.9% MG. A yield of 24.2±3.6% pyruvic acid has been detected for MVK–O₃. HMHP is unstable in the aqueous phase and can transform into H₂O₂ and HCHO with a yield of 100%. 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