Accelerated Sulfur Oxidation by Ozone on Surfaces of Single Optically Trapped Aerosol Particles

Abstract

The sulfur oxidation in mixed sodium thiosulfate/sucrose/aqueous microdroplets by gaseous ozone is studied in this work via aerosol optical tweezers coupled with Raman spectroscopy, which can simultaneously determine various physicochemical properties and the heterogeneous reaction kinetics of single optically trapped microdroplets, allowing for elucidating their complicated interplay. According to the kinetics measurement results at different relative humidities, ozone concentrations, and stoichiometries of inorganic and organic solutes, this work finds that a high aerosol ionic strength can accelerate the ozone oxidation of thiosulfate at air–water interfaces, while a high aerosol viscosity prolongs the reaction time scales due to diffusion-limited kinetics. The kinetic multilayer model of aerosol surface and bulk chemistry (KM-SUB) is utilized to investigate the observed heterogeneous kinetics results and to retrieve the surface reaction rate coefficients. The KM-SUB model fit results indicate that the observed kinetics of sulfur oxidation in binary sodium thiosulfate aqueous microdroplets with high ionic strengths is dominated by interfacial reactions, and the fitted surface reaction rate coefficients increase 1 order of magnitude when the droplet ionic strength increases around 40 M. This work further utilizes the kinetics measurements of ozone dependence to discuss the coupling among properties of ozone gas-interface-bulk partitioning and surface reaction rate in the kinetics model. Finally, this work also exploits the surface reaction of thiosulfate with ozone to retrieve the aerosol viscosity of microdroplets containing ternary aqueous sodium thiosulfate and sucrose mixtures, demonstrating the feasibility of pinning down aerosol viscosities via reaction kinetics.