Viscosity of aqueous ammonium nitrate–organic particles: equilibrium partitioning may be a reasonable assumption for most tropospheric conditions

Abstract

The viscosity of aerosol particles determines the critical mixing time of gas–particle partitioning of volatile compounds in the atmosphere. The partitioning of the semi-volatile ammonium nitrate (NH4NO3) might alter the viscosity of highly viscous secondary organic aerosol particles during their lifetimes. In contrast to the viscosity of organic particles, data on the viscosity of internally mixed inorganic–organic aerosol particles are scarce. We determined the viscosity of an aqueous ternary inorganic–organic system consisting of NH4NO3 and a proxy compound for a highly viscous organic, sucrose. Three techniques were applied to cover the atmospherically relevant humidity range: viscometry, fluorescence recovery after photobleaching, and the poke-flow technique. We show that the viscosity of NH4NO3–sucrose–H2O with an organic to inorganic dry mass ratio of 4:1 is 4 orders of magnitude lower than the viscosity of the aqueous sucrose under low-humidity conditions (30 % relative humidity (RH), 293 K). By comparing viscosity predictions of mixing rules with those of the Aerosol Inorganic–Organic Mixtures Functional groups Activity Coefficients Viscosity (AIOMFAC-VISC) model, we found that a mixing rule based on mole fractions performs similarly when data from corresponding binary aqueous subsystems are available. Applying this mixing rule, we estimated the characteristic internal mixing time of aerosol particles, indicating significantly faster mixing for inorganic–organic mixtures compared to electrolyte-free particles, especially at lower RH. Hence, the assumption in global atmospheric chemistry models of quasi-instantaneous equilibrium gas–particle partitioning is reasonable for internally mixed single-phase particles containing dissolved electrolytes (but not necessarily for phase-separated particles), for most conditions in the planetary boundary layer. Further data are needed to see whether this assumption holds for the entire troposphere at midlatitudes and at RH > 35 %.