Tropospheric Chemistry of Halogen Compounds

Sea salt contains (by weight) 55.7% Cl, 0.19% Br, and 0.00002% I. Depletion of the Cl and Br content of marine aerosol relative to bulk seawater, as measured by Cl/Na and Br/Na ratios, indicates that there is some net flux of these two halogens to the gas phase. Interestingly, the ratio I/Na in marine aerosol is typically much greater than that in seawater, often by a factor of 1000. The large enrichment for iodine in seasalt aerosols relative to seawater has been attributed, in part, to the enhanced level of organic I compounds in the surface organic layer on the ocean that become incorporated in the aerosol formation mechanism. 

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Platt, U. (1995) The chemistry of halogen compounds in the Arctic troposphere, in Tropospheric Oxidation Mechanisms, K. H. Becker, ed., European Commission, Report EUR 16171 EN, Luxembourg, pp. 9-20. 

Barbara J. Finlayson-Pitts is Professor of Chemistry at the University of California, Irvine. Her research program focuses on laboratory studies of the kinetics and mechanisms of reactions in the atmosphere, especially those involving gases with liquids or solids of relevance in the troposphere. Reactions of sea salt particles to produce photochemically active halogen compounds and the subsequent fates of halogen atoms in the troposphere are particular areas of interest, as are reactions of oxides of nitrogen at aqueous and solid interfaces. Her research is currently supported by the National Science Foundation, the Department of Energy, the California Air Resources Board, the Dreyfus Foundation, and NATO. She has authored or coauthored more than 80 publications in this area, as well as a previous book, Atmospheric Chemistry Fundamentals and Experimental Techniques. 

Platt U. and Moortgat G. K. (1999) Heterogeneous and homogeneous chemistry of reactive halogen compounds in the lower troposphere. J. Atmos. Chem. 34, 1-8. 

The stratospheric ozone-depleting potential of a compound emitted at the Earth s surface depends on how much of it is destroyed in the troposphere before it gets to the stratosphere, the altitude at which it is broken down in the stratosphere, and chemistry subsequent to its dissociation. Halocarbons containing hydrogen in place of halogens or containing double bonds are susceptible to attack by OH in the troposphere. (We will consider the mechanisms of such reactions in Chapter 6.) The more effective the tropospheric removal processes, the less of the compound that will survive to reach the stratosphere. Once halocarbons reach the stratosphere their relative importance in ozone depletion depends on the altitude at which they are photolyzed and the distribution of halogen atoms, Cl, Br, and F, contained within the molecule. 

Sander, R. Vogt, R. Harris, G.W. Crutzen, P.J., 1997 Modeling the Chemistry of Ozone, Halogen Compounds, and Hydrocarbons in the Arctic Troposphere During Spring , in Tellus, 49B 522-532. 

Other secondary chlorine species (atomic Cl, CIO, ClOOCl etc.) have been made responsible for Arctic ozone depletion, whereas the sources of the chlorine atoms are poorly understood (Keil and Shepson 2006). The Cl atom reacts similarly to OH (e. g. in oxidation of volatile organic compounds Cai and Griffin 2006). However, the photolysis of HCl is too slow (even in the stratosphere) to provide atomic Cl. Thus, the only direct Cl source from HCl is due to its reaction with OH, but with a fairly low reaction rate constant (Rossi 2003). There are several chemical means of production of elemental Cl (and other halogens) from heterogeneous chemistry (see Chapter 5.8.2) in the troposphere the photolysis of chloroorganic is not very important, with a few exceptions (see Chapter 5.8.1). 

In the tropospheric halogen chemistry, CIONO2 is a quasi-stable compound formed in the chain termination reaction of CIO in the urban coastal area where NO concentration is relatively high. The reaction of CIONO2 with sea salt results in photochemically active CI2 as in the process. 

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