Multicomponent diffusion in atmospheric aerosol particles

Abstract

Condensed phase mass transport in single aerosol particles is investigated using a linear quadrupole electrodynamic balance (LQ-EDB) and the Maxwell-Stefan (MS) framework. In the LQ-EDB experiments, water loss from model aqueous inorganic-organic aerosol particles composed of water, ammonium sulfate (AS) and citric acid (CA) is measured by tracking morphology-dependent resonances that appear in light scattering spectra. Characteristic equilibration times are found to not follow simple mixing rules and can be much longer than those of either aqueous CA or aqueous AS. To understand these observations, we develop a multicomponent (more than two components) model based on the MS diffusion model. Activities in the mixture are calculated using the aerosol inorganic-organic mixtures functional groups activity coefficients (AIOMFAC) thermodynamic model. Fluxes from the MS equation are incorporated into an adaptive finite-volume scheme that we use to numerically solve the mass transport problem in a spherical particle with a moving boundary. The resulting model is applied to the aqueous AS/CA system and is able to provide an accurate quantitative description of measured equilibration times. The longer equilibration times in aqueous AS/CA can be understood to result from thermodynamic nonideality rather than, for instance, a phase change.