Ozone in the remote marine boundary layer: A possible role for halogens

On the spring 1995 cruise of the National Oceanic and Atmospheric Administration research vessel Malcolm Baldrige, we measured very large diurnal variations in ozone concentrations in the marine boundary layer. Average diurnal variations of about 32% of the mean were observed over the tropical Indian Ocean. We simulated these observations with the Model of Chemistry in Clouds and Aerosols, a photochemical box model with detailed aerosol chemistry. The model was constrained with photolysis rates, humidity, aerosol concentrations, NO, CO, and O-3 specified by shipboard observations and ozonesondes. Conventional homogeneous chemistry, where ozone photolysis to O(D-1) and HOx chemistry dominate ozone destruction, can account for a diurnal variation of only about 12%. On wet sea-salt aerosols (at humidities above the deliquescence point), absorption of HOBr leads to release of BrCl and Br-2, which photolyze to produce Br atoms that may provide an additional photochemical ozone sink. After 8 days of simulation, these Br atoms reach a peak concentration of 1.2 x 10(7) cm(-3) at noon and destroy ozone through a catalytic cycle involving BrO and HOBr. Reactive Br lost to HBr can be absorbed into the aerosol phase and reactivated. The model predicts a diurnal variation in O-3 of 22% with aerosol-derived Br reaction explaining much, but not all, of the observed photochemical loss. The lifetime of ozone under these conditions is short, about 2 days. These results indicate that halogens play an important role in oxidation processes and the ozone budget in parts of the remote marine boundary layer.