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Atmospheric Peroxides in a Polluted Subtropical Environment: Seasonal Variation, Sources and Sinks, and Importance of Heterogeneous Processes

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Department of Civil and Environmental Engineering, The Hong Kong Polytechnic University, Hong Kong, China
Chemistry Department, Leibniz Institute for Tropospheric Research (TROPOS), 04318 Leipzig, Germany
§ Environmental Protection Department, the Government of the Hong Kong Special Administrative Region, Hong Kong, China
Environment Research Institute of Shandong University, Shandong University, Jinan, Shandong 250100, China
*Phone: (0852)27666059. Fax: (852) 2334 6389. E-mail: [email protected]
Cite this: Environ. Sci. Technol. 2014, 48, 3, 1443–1450
Publication Date (Web):December 20, 2013
Copyright © 2013 American Chemical Society

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    Hydrogen peroxide (H2O2) and organic peroxides play an important role in atmospheric chemistry, but knowledge of their abundances, sources, and sinks from heterogeneous processes remains incomplete. Here we report the measurement results obtained in four seasons during 2011–2012 at a suburban site and a background site in Hong Kong. Organic peroxides were found to be more abundant than H2O2, which is in contrast to most previous observations. Model calculations with a multiphase chemical mechanism suggest important contributions from heterogeneous processes (primarily transition metal ion [TMI]-HOx reactions) to the H2O2 budget, accounting for about one-third and more than half of total production rate and loss rate, respectively. In comparison, they contribute much less to organic peroxides. The fast removal of H2O2 by these heterogeneous reactions explains the observed high organic peroxide fractions. Sensitivity analysis reveals that the role of heterogeneous processes depends on the abundance of soluble metals in aerosol, serving as a net H2O2 source at low metal concentrations, but as a net sink with high metal loading. The findings of this study suggest the need to consider the chemical processes in the aerosol aqueous phase when examining the chemical budget of gas-phase H2O2.

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    Detailed description of the measurements and modeling settings, a table summarizing average H2O2 and organic peroxide concentrations in different seasons, two figures describing the location of the observation sites and 24-h backward trajectories ending in Hong Kong for the case study. This material is available free of charge via the Internet at

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