ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-11-1243-2011 Substrate effects in the photoenhanced ozonation of pyrene Styler S. A. 1 Loiseaux M.-E. 1 Donaldson D. J. 1 2 Department of Chemistry, University of Toronto, Toronto, Ontario, Canada Department of Physical and Environmental Sciences, University of Toronto Scarborough, Toronto, Ontario, Canada 14 02 2011 11 3 1243 1253 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/11/1243/2011/acp-11-1243-2011.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/11/1243/2011/acp-11-1243-2011.pdf

We report the effects of actinic illumination on the heterogeneous ozonation kinetics of solid pyrene films and pyrene adsorbed at air-octanol and air-aqueous interfaces. Upon illumination, the ozonation of solid pyrene films and pyrene at the air-aqueous interface proceeds more quickly than in darkness; no such enhancement is observed for pyrene at the air-octanol interface. Under dark conditions, the reaction of pyrene at all three interfaces proceeds via a Langmuir-Hinshelwood-type surface mechanism. In the presence of light, Langmuir-Hinshelwood kinetics are observed for solid pyrene films but a linear dependence upon gas-phase ozone concentration is observed at the air-aqueous interface. We interpret these results as evidence of the importance of charge-transfer pathways for the ozonation of excited-state pyrene. The dramatically different behaviour of pyrene at the surface of these three simple reaction environments highlights the difficulties inherent in representing complex reactive surfaces in the laboratory, and suggests caution in extrapolating laboratory results to environmental surfaces.

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