Polar stratospheric chlorine kinetics from a self-match flight during SOLVE-II/EUPLEX

Abstract

In-situ measurements of ClO made onboard the Geophysica aircraft on 30 January 2003 in the Arctic afford a novel approach to constrain the kinetic parameters governing polar stratospheric chlorine chemistry using atmospheric observations. The self-match flight pattern, i.e. sampling individual air masses twice at different zenith angles, was utilized by simulating the evolution of ClO mixing ratios between two 'matching' points using a photochemical model and optimizing the model parameters to fit the observations within a retrieval framework. Our results suggest a ClO/ClOOCl thermal equilibrium constant Keq a factor of 5 smaller and a ratio J/kf a factor of 2 larger than the values based on..