ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-12-7187-2012 Understanding the aqueous phase ozonolysis of isoprene: distinct product distribution and mechanism from the gas phase reaction Wang H. L. 1 Huang D. 1 Zhang X. 1 2 Zhao Y. 1 Chen Z. M. 1 State Key Laboratory of Environmental Simulation and Pollution Control, College of Environmental Sciences and Engineering, Peking University, Beijing 100871, China now at: Department of Environmental Science and Engineering, California Institute of Technology, Pasadena, CA 91125, USA 07 08 2012 12 15 7187 7198 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/12/7187/2012/acp-12-7187-2012.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/12/7187/2012/acp-12-7187-2012.pdf

The aqueous phase reaction of volatile organic compounds (VOCs) has not been considered in most analyses of atmospheric chemical processes. However, some experimental evidence has shown that, compared to the corresponding gas phase reaction, the aqueous chemical processes of VOCs in the bulk solutions and surfaces of ambient wet particles (cloud, fog, and wet aerosols) may potentially contribute to the products and formation of secondary organic aerosol (SOA). In the present study, we performed a laboratory experiment of the aqueous ozonolysis of isoprene at different pHs (3–7) and temperatures (4–25 °C). We detected three important kinds of products, including carbonyl compounds, peroxide compounds, and organic acids. Our results showed that the molar yields of these products were nearly independent of the investigated pHs and temperatures, those were (1) carbonyls: 56.7 ± 3.7 % formaldehyde, 42.8 ± 2.5 % methacrolein (MAC), and 57.7 ± 3.4 % methyl vinyl ketone (MVK); (2) peroxides: 53.4 ± 4.1 % hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) and 15.1 ± 3.1 % hydroxylmethyl hydroperoxide (HMHP); and (3) organic acids: undetectable (<1 % estimated by the detection limit). Based on the amounts of products formed and the isoprene consumed, the total carbon yield was estimated to be 94.8 ± 4.1 %. This implied that most of the products in the reaction system were detected. The combined yields of both MAC + MVK and H<sub>2</sub>O<sub>2</sub> + HMHP in the aqueous isoprene ozonolysis were much higher than those observed in the corresponding gas phase reaction. We suggest that these unexpected high yields of carbonyls and peroxides are related to the greater capability of condensed water, compared to water vapor, to stabilize energy-rich Criegee radicals. This aqueous ozonolysis of isoprene (and possibly other biogenic VOCs) could potentially occur on the surfaces of ambient wet particles and plants. Moreover, the high-yield carbonyl and peroxide products might provide a considerable source of aqueous phase oxidants and SOA precursors.

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