Insight into the Mechanism and Kinetics of the Heterogeneous Reaction between SO2 and NO2 on Diesel Black Carbon under Light Irradiation

The heterogeneous oxidation of SO2 by NO2 has been extensively proposed as an important pathway of sulfate production during haze events in China. However, the kinetics and mechanism of oxidation of SO2 by NO2 on the surface of complex particles remain poorly understood. Here, we systematically explore the mechanism and kinetics of the reaction between SO2 and NO2 on diesel black carbon (DBC) under light irradiation. The experimental results prove that DBC photochemistry can not only significantly promote the heterogeneous reduction of NO2 to produce HONO via transferring photoinduced electrons but also indirectly promote OH radical formation. These reduction products of NO2 as well as NO2 itself greatly promote the heterogeneous oxidation of SO2 on DBC. NO2 oxidation, HONO oxidation, and the surface photo-oxidation process are proven to be three major surface oxidation pathways of SO2. The kinetics results indicate that the surface photooxidation pathway accounts for the majority of the total SO2 uptake (similar to 63%), followed by the HONO oxidation pathway (similar to 27%) and direct oxidation by NO2 (similar to 10%). This work highlights the significant synergistic roles of DBC, NO2, and light irradiation in enhancing the atmospheric oxidation capacity and promoting the heterogeneous formation of sulfate.