CAPRAM reduction towards an operational multiphase halogen and DMS chemistry treatment in the chemistry transport model COSMO-MUSCAT(5.04e)

Abstract

Abstract. A condensed multiphase halogen and dimethyl sulfide (DMS) chemistry mechanism for application in chemical transport models is developed by reducing the CAPRAM DMS module 1.0 (CAPRAM-DM1.0) and the CAPRAM halogen module 3.0 (CAPRAM-HM3.0). The reduction is achieved by determining the main oxidation pathways from analysing the mass fluxes of complex multiphase chemistry simulations with the air parcel model SPACCIM. These simulations are designed to cover both pristine and polluted marine boundary layer conditions. Overall, the reduced DM1.0 contains 32 gas-phase reactions, 5 phase transfers, and 12 aqueous-phase reactions, of which two processes are described as equilibrium reactions. The reduced CAPRAM-HM3.0 contains 199 gas-phase reactions, 23 phase transfers, and 87 aqueous-phase reactions. For the aqueous-phase chemistry, 39 processes are described as chemical equilibrium reactions. A comparison of simulations using the complete DM1.0 and CAPRAM-HM3.0 mechanisms against the reduced ones indicates that the percentage deviations are below 5 % for important inorganic and organic air pollutants and key reactive species under pristine ocean and polluted conditions. The reduced mechanism has been implemented into the chemical transport model COSMO-MUSCAT and tested by performing 2D-simulations under prescribed meteorological conditions that investigate the effect of stable (stratiform cloud) and more unstable weather conditions (convective clouds) on marine multiphase chemistry. The simulated maximum concentrations of HCl are in the range of 109 molecules cm−3 and those of BrO are at around 1 · 107 molecules cm −3 reproducing the range of ambient measurements. Afterwards, the oxidation pathway of DMS in a cloudy marine atmosphere has been investigated in detail. The simulations demonstrate that clouds have both a direct and an indirect photochemical effect on the multiphase processing of DMS and its oxidation products. The direct photochemical effect is related to in-cloud chemistry that leads to high DMSO oxidation rates and a subsequently enhanced formation of methane sulfonic acid compared to aerosol chemistry. The indirect photochemical effect is characterised by cloud shading, which occurs particularly in the case of stratiform clouds. The lower photolysis rate affects the activation of Br atoms and consequently lowers the formation of BrO radicals. The corresponding DMS oxidation flux is lowered by up to 30 % under thick optical clouds. Moreover, high updraft velocities lead to a strong vertical mixing of DMS into the free troposphere predominately under cloudy conditions. Furthermore, HOX photolysis is reduced as well, resulting in higher HOX-driven sulfite oxidation in aerosol particles below stratiform clouds. Altogether, the present model simulations have demonstrated the ability of the reduced mechanism to be applied in studying marine aerosol cloud processing effects in regional models such as COSMO-MUSCAT and can be applied for more adequate interpretations of complex marine field measurement data, also by other regional models.