Kinetics Study of Heterogeneous Bromine Release from the Reaction between Gaseous Ozone and Aqueous Bromide Solution

The heterogeneous release of molecular bromine, Br₂, from the reaction between gaseous ozone and aqueous bromide ion in seawater ice and sea salt aerosols is considered to be an initial source of reactive bromine species in the troposphere. Recent studies have demonstrated that the uptake of ozone by aqueous bromide solution is promoted by reactions at the gas-liquid interface. The present work investigated the heterogeneous reaction between gaseous ozone and aqueous bromide solution at atmospheric pressure and room temperature using a wetted wall flow reactor combined with a chemical ionization mass spectrometer. The emission rate of Br₂ was measured as a function of gaseous ozone concentration, aqueous bromide concentration, and pH. In addition, we conducted a simple kinetics model simulation that included only bulk aqueous-phase reactions and compared the theoretical values with the experimentally determined values. The Br₂ emission rates measured experimentally differ from the simulated rates at relatively high bromide concentration, as well as in the pH region of 6-9. These differences might be explained by different Br^- concentration and/or deprotonation efficiency near the interface region and those in the bulk solution.