Modeling halogen chemistry in the marine boundary layer. 1. Cloud-free MBL

A numerical one-dimensional model of the marine boundary layer (MBL) is presented. It includes chemical reactions in the gas phase and aerosol particles, focusing on the reaction cycles of halogen compounds. Results of earlier box model studies were confirmed. They showed the acid-catalyzed activation of bromine from sea salt aerosol, and the role of halogen radicals in the destruction of O3. A distinct diurnal variation in BrO mixing ratios with maxima at sunrise and sunset was found which might be the cause of the recently published “sunrise ozone destruction.” Maxima of BrO and sea salt acidity are predicted at the top of the MBL and not close to the sea surface where sea salt spray is produced. The presence of sulfate aerosol was found to be important for the recycling of less reactive to photolyzable bromine species. Day/night and seasonal differences in halogen chemistry are shown.