Chemical Implications of Rapid Reactive Absorption of I₂O₄ at the Air-Water Interface

Marine aerosol formation involving iodine-bearing species significantly affects the global climate and radiation balance. Although recent studies outline the critical role of iodine oxide in nucleation, much less is known about its contribution to aerosol growth. This paper presents molecular-level evidence that the air–water interfacial reaction of I₂O₄ mediated by potent atmospheric chemicals, such as sulfuric acid (H₂SO₄) and amines [e.g., dimethylamine (DMA) and trimethylamine (TMA)], can occur rapidly on a picosecond time scale by Born–Oppenheimer molecular dynamics simulations. The interfacial water bridges the reactants while facilitating the DMA-mediated proton transfer and stabilizing the ionic products of H₂SO₄-involved reactions. The identified heterogeneous mechanisms exhibit the dual contribution to aerosol growth: (i) the ionic products (e.g., IO₃^–, DMAH⁺, TMAH⁺, and HSO₄^–) formed by reactive adsorption possess less volatility than the reactants and (ii) these ions, such as alkylammonium salts (e.g., DMAH⁺), are also highly hydrophilic, further facilitating hygroscopic growth. This investigation enhances not only our understanding of heterogeneous iodine chemistry but also the impact of iodine oxide on aerosol growth. Also, these findings can bridge the gap between the abundance of I₂O₄ in the laboratory and its absence in field-collected aerosols and provide an explanation for the missing source of IO₃^–, HSO₄^–, and DMAH⁺ in marine aerosols.