Impact of Molecular Chlorine Production from Aerosol Iron Photochemistry on Atmospheric Oxidative Capacity in North China

Elevated levels of atmospheric molecular chlorine (Cl₂) have been observed during the daytime in recent field studies in China but could not be explained by the current chlorine chemistry mechanisms in models. Here, we propose a Cl₂ formation mechanism initiated by aerosol iron photochemistry to explain daytime Cl₂ formation. We implement this mechanism into the GEOS-Chem chemical transport model and investigate its impacts on the atmospheric composition in wintertime North China where high levels of Cl₂ as well as aerosol chloride and iron were observed. The new mechanism accounts for more than 90% of surface air Cl₂ production in North China and consequently increases the surface air Cl₂ abundances by an order of magnitude, improving the model’s agreement with observed Cl₂. The presence of high Cl₂ significantly alters the oxidative capacity of the atmosphere, with a factor of 20-40 increase in the chlorine radical concentration and a 20-40% increase in the hydroxyl radical concentration in regions with high aerosol chloride and iron loadings. This results in an increase in surface air ozone by about 10%. This new Cl₂ formation mechanism will improve the model simulation capability for reactive chlorine abundances in the regions with high emissions of chlorine and iron. © 2024 American Chemical Society.