Stable Sulfur Isotopes Revealed a Major Role of Transition-Metal Ion-Catalyzed SO₂ Oxidation in Haze Episodes

Secondary sulfate aerosols played an important role in aerosol formation and aging processes, especially during haze episodes in China. Secondary sulfate was formed via atmospheric oxidation of SO₂ by OH, O₃, H₂O₂, and transition-metal-catalyzed (TMI) O₂. However, the relative importance of these oxidants in haze episodes was strongly debated. Here, we use stable sulfur isotopes (δ³⁴S) of sulfate aerosols and a Rayleigh distillation model to quantify the contributions of each oxidant during a haze episode in Nanjing, a megacity in China. The observed δ³⁴S values of sulfate aerosols showed a negative correlation with sulfur oxidation ratios, which was attributed to the sulfur isotopic fractionations during the sulfate formation processes. Using the average fractionation factor calculated from our observations and zero-dimensional (0-D) atmospheric chemistry modeling estimations, we suggest that OH oxidation was trivial during the haze episode, while the TMI pathway contributed 49 ± 10% of the total sulfate production and O₃/H₂O₂ oxidations accounted for the rest. Our results displayed good agreement with several atmospheric chemistry models that carry aqueous and heterogeneous TMI oxidation pathways, suggesting the role of the TMI pathway was significant during haze episodes.