Lawrence Berkeley National Laboratory

Chemical transformations in aerosols impact the lifetime of particle phase species, the fate of atmospheric pollutants, and both climate- and health-relevant aerosol properties. Timescales for multiphase reactions of ozone in atmospheric aqueous phases are governed by coupled kinetic processes between the gas phase, the particle interface, and its bulk, which respond dynamically to reactive consumption of O₃. However, models of atmospheric aerosol reactivity often do not account for the coupled nature of multiphase processes. To examine these dynamics, we use new and prior experimental observations of aqueous droplet reaction kinetics, including three systems with a range of surface affinities and ozonolysis rate coefficients (trans-aconitic acid (C₆H₆O₆), maleic acid (C₄H₄O₄), and sodium nitrite (NaNO₂)). Using literature rate coefficients and thermodynamic properties, we constrain a simple two-compartment stochastic kinetic model which resolves the interface from the particle bulk and represents O₃ partitioning, diffusion, and reaction as a coupled kinetic system. Our kinetic model accurately predicts decay kinetics across all three systems, demonstrating that both the thermodynamic properties of O₃ and the coupled kinetic and diffusion processes are key to making accurate predictions. An enhanced concentration of adsorbed O₃, compared to gas and bulk phases is rapidly maintained and remains constant even as O₃ is consumed by reaction. Multiphase systems dynamically seek to achieve equilibrium in response to reactive O₃ loss, but this is hampered at solute concentrations relevant to aqueous aerosol by the rate of O₃ arrival in the bulk by diffusion. As a result, bulk-phase O₃ becomes depleted from its Henry's law solubility. This bulk-phase O₃ depletion limits reaction timescales for relatively slow-reacting organic solutes with low interfacial affinity (i.e., trans-aconitic and maleic acids, with k_rxn ≈ 10³-10⁴ M^-1 s^-1), which is in contrast to fast-reacting solutes with higher surface affinity (i.e., nitrite, with k_rxn ≈ 10⁵ M^-1 s^-1) where surface reactions strongly impact the observed decay kinetics.