Reactive Uptake of Ozone to Simulated Seawater: Evidence for Iodide Depletion

The reaction of ozone with iodide in the ocean is a major ozone dry deposition pathway, as well as an important source of reactive iodine to the marine troposphere. Few prior laboratory experiments have been conducted with environmentally relevant ozone mixing ratios and iodide concentrations, leading to uncertainties in the rate of the reaction under marine boundary layer conditions. As well, there remains disagreement in the literature assessment of the relative contributions of an interfacial reaction via ozone adsorbed to the ocean surface versus a bulk reaction with dissolved ozone. In this study, we measure the uptake coefficient of ozone over a buffered, pH 8 salt solution replicating the concentrations of iodide, bromide, and chloride in the ocean over an ozone mixing ratio of 60-500 ppb. Due to iodide depletion in the solution, the measured ozone uptake coefficient is dependent on the exposure time of the solution to ozone and its mixing ratio. A kinetic multilayer model confirms that iodide depletion is occurring not only within ozone's reactodiffusive depth, which is on the order of microns for environmental conditions, but also deeper into the solution as well. Best model-measurement agreement arises when some degree of nondiffusive mixing is occurring in the solution, transporting iodide from deeper in the solution to a thin, diffusively mixed upper layer. If such mixing occurs rapidly in the environment, iodide depletion is unlikely to reduce ozone dry deposition rates. Unrealistically high bulk-to-interface partitioning of iodide is required for the model to predict a substantial interfacial component to the reaction, indicating that the Langmuir-Hinshelwood mechanism is not dominant under environmental conditions.