Heterogeneous reactions in sulfuric acid aerosols: A framework for model calculations

Abstract

A framework for applying rates of heterogeneous chemical reactions measured in the laboratory to small sulfuric acid aerosols found in the stratosphere is presented. The procedure for calculating the applicable reactive uptake coefficients using laboratory‐measured parameters is developed, the necessary laboratory‐measured quantities are discussed, and a set of equations for use in models are presented. This approach is demonstrated to be essential for obtaining uptake coefficients for the HOCl + HCl and ClONO2 + HCl reactions applicable to the stratosphere. In these cases the laboratory‐measured uptake coefficients have to be substantially corrected for the small size of the atmospheric aerosol droplets. The measured uptake coefficients for N2O5 + H2O and ClONO2 + H2O as well as those for other heterogeneous reactions are discussed in the context of this model. Finally, the derived uptake coefficients were incorporated in a two‐dimensional dynamical and photochemical model thus for the first time the HCl reactions in sulfuric acid have been included. Substantial direct chlorine activation and consequent ozone destruction is shown to occur due to heterogeneous reactions involving HCl for volcanically perturbed aerosol conditions at high latitudes. Smaller but significant chlorine activation also is predicted for background aerosol loadings at extreme high latitudes, suggesting chlorine activation can occur on background sulfuric acid aerosol in these regions. The coupling between homogeneous and heterogeneous chemistry is shown to lead to important changes in the concentrations of various reactive species. The basic physical and chemical quantities needed to better constrain the model input parameters are identified.