The Reactive-Diffusive Length of OH and Ozone in Model Organic Aerosols.

Abstract

A key step in the heterogeneous oxidation of atmospheric aerosols is the reaction of ozone (O3) and hydroxyl radicals (OH) at the gas-particle interface. The formation of reaction products and free radical intermediates and their spatial distribution inside the particle is a sensitive function of the length over which these oxidants diffuse prior to reaction. The reactive-diffusive length of OH and ozone at organic aerosol interfaces is determined by observing the change in the effective uptake coefficient for size-selected model aerosols comprising a reactive core and a thin nanometer-sized (0-12 nm) organic shell. The core and shell materials are selected so that they are immiscible and adopt an assumed core-shell configuration. The results indicate a reactive-diffusive length of 1.4 nm for hydroxyl (OH) radicals in squalane and 1.0 nm for ozone in squalene. Measurements for a purely diffusive system allow for an estimate for diffusion constant (1.6 × 10(-6) cm(2)/s) of ozone in squalane to be determined. The reactive-diffusive length offers a simple first order estimate of how shielding of aerosols by immiscible layers can alter estimates of oxidative lifetimes of aerosols in the atmosphere.