Comprehensive multiphase chlorine chemistry in the box model CAABA/MECCA: implications for atmospheric oxidative capacity

Abstract

Tropospheric chlorine chemistry can strongly impact the atmospheric oxidation capacity and composition, especially in urban environments. To account for these reactions, the gas- and aqueous-phase Cl chemistry of the community atmospheric chemistry box model Chemistry As A Boxmodel Application/Module Efficiently Calculating the Chemistry of the Atmosphere (CAABA/MECCA) has been extended. In particular, an explicit mechanism for ClNO2 formation following N2O5 uptake to aerosols has been developed. The updated model has been applied to two urban environments with different concentrations of NOx (NO + NO2): New Delhi (India) and Leicester (United Kingdom). The model shows a sharp build-up of Cl at sunrise through Cl2 photolysis in both the urban environments. Besides Cl2 photolysis, ClO+NO reaction and photolysis of ClNO2 and ClONO are also prominent sources of Cl in Leicester. High-NOx conditions in Delhi tend to suppress the nighttime build-up of N2O5 due to titration of O3 and thus lead to lower ClNO2, in contrast to Leicester. Major loss of ClNO2 is through its uptake on chloride, producing Cl2, which consequently leads to the formation of Cl through photolysis. The reactivities of Cl and OH are much higher in Delhi; however, the Cl/OH reactivity ratio is up to ≈ 9 times greater in Leicester. The contribution of Cl to the atmospheric oxidation capacity is significant and even exceeds (by ≈ 2.9 times) that of OH during the morning hours in Leicester. Sensitivity simulations suggest that the additional consumption of volatile organic compounds (VOCs) due to active gas- and aqueous-phase chlorine chemistry enhances OH, HO2, and RO2 near sunrise. The simulation results of the updated model have important implications for future studies on atmospheric chemistry and urban air quality.