Chlorine chemistry in urban atmospheres: a review
C. B. Faxon A B and D. T. Allen A
+ Author Affiliations
- Author Affiliations
A Center for Energy and Environmental Resources, University of Texas, M/C 27100, 10100 Burnet Road, Austin, TX 78758, USA.
B Corresponding author. Email: cfax@utexas.edu
Cameron Faxon is currently a doctoral candidate in Chemical Engineering at the University of Texas at Austin. His research efforts involve the investigation of atmospheric chlorine chemistry with a focus on the impacts on local and regional air quality. Current research projects include the development and implementation of chlorine chemistry mechanisms for use in regional photochemical models as well as environmental chamber studies of heterogeneous processes. |
Dr David Allen is the Gertz Regents Professor of Chemical Engineering at the University of Texas at Austin. He also serves as the Director of the Center for Energy and Environmental Resources and was recently appointed as chair of the Environmental Protection Agency's Science Advisory Board (SAB). He is the author of six books and over 170 papers in areas ranging from coal liquefaction and heavy oil chemistry to the chemistry of urban atmospheres. |
Environmental Chemistry 10(3) 221-233 https://doi.org/10.1071/EN13026
Submitted: 1 February 2013 Accepted: 18 April 2013 Published: 19 June 2013
Journal Compilation © CSIRO Publishing 2013 Open Access CC BY-NC-ND
Environmental context. Atmospheric chlorine radicals can affect the chemical composition of the atmosphere through numerous reactions with trace species. In urban atmospheres, the reactions of chlorine radicals can lead to effects such as increases in ozone production, thus degrading local and regional air quality. This review summarises the current understanding of atmospheric chlorine chemistry in urban environments and identifies key unresolved issues.
Abstract. Gas phase chlorine radicals (Cl•), when present in the atmosphere, react by mechanisms analogous to those of the hydroxyl radical (OH•). However, the rates of the Cl•-initiated reactions are often much faster than the corresponding OH• reactions. The effects of the atmospheric reactions of Cl• within urban environments include the oxidation of volatile organic compounds and increases in ozone production rates. Although concentrations of chlorine radicals are typically low compared to other atmospheric radicals, the relatively rapid rates of the reactions associated with this species lead to observable changes in air quality. This is particularly evident in the case of chlorine radical-induced localised increases in ozone concentrations. This review covers five aspects of atmospheric chlorine chemistry: (1) gas phase reactions; (2) heterogeneous and multi-phase reactions; (3) observational evidence of chlorine species in urban atmospheres; (4) regional modelling studies and (5) areas of uncertainty in the current state of knowledge.
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