Enhanced Chlorine and Bromine Atom Activation by Hydrolysis of Halogen Nitrates from Marine Aerosols at Polluted Coastal Areas.

Detailed multiphase chemistry box model studies are carried out, investigating halogen radical activation at polluted coastal areas. Simulations are performed for a nonpermanent cloud and a cloud-free scenario and reveal that ClNO2 photolysis and ICl photolysis are crucial for gas-phase Cl atom activation. In the cloud scenario, the integrated ClNO2 and ICl photolysis rates are 3.7 × 107 and 3.1 × 107 molecules cm-3 s-1. In the cloud-free scenario, the integrated ClNO2 and ICl photolysis rates are 8.1 × 107 and 3.6 × 107 molecules cm-3 s-1. The simulations show larger contributions of ClNO2 photolysis in the morning and higher ones of ICl photolysis during afternoon. Throughout the simulation, average contributions to Cl atom activation in the cloud and cloud-free scenarios by ClNO2 photolysis are 42% and 62% and by ICl photolysis 35% and 28%, respectively. ICl is formed through an aqueous-phase reaction of HOI with chloride. Two thirds of the formed ICl is released into the gas phase. The residual third reacts with bromide, creating IBr. Overall, the simulations emphasize the crucial role of INO3 hydrolysis for Cl and Br atom activation in polluted coastal areas. Therefore, it needs to be considered in chemical transport models to improve air quality predictions.