Investigating the Halogen Chemistry From High-Latitude Nighttime Stratospheric Measurements of OClO and NO2

Two cases of simultaneous nighttime measurements of NO2 and OClO in the winter polar stratosphere are analyzed in order to test our present knowledge of halogen chemistry in the presence of high amount of NO2 at low temperature. Comparisons with Lagrangian model calculations using several hypotheses are performed. First simulations, using the admitted constant rates of chemical reaction, strongly underestimate the measured OClO while the NO2 profiles are correctly reproduced. If uncertainties in actinic fluxes calculations are taken into account, simulation results do not show a significant reduction of the underestimation. A better agreement can be achieved if the formation of unstable isomers of ClONO2 and of BrONO2 occurs in the cold conditions of the polar stratosphere. An approximate value of the branching ratios of the channels leading to ClONO2 and ClOONO, and to BrONO2 and BrOONO, necessary to reproduce both OClO and NO2 is given and discussed.