Influence of Particle Phase Morphology on the Hygroscopic Behavior of Atmospheric Aerosols

While current models generally treat organic and mixed organic-inorganic aerosol particles as well-mixed liquids, these particles can exist in multiple phase states depending on their chemical composition and on ambient conditions such as relative humidity (RH). For example, multi-component particles can undergo phase separations in which an inorganic-electrolyte-rich phase and an organic-rich phase coexist within one particle. Organic aerosols have been shown to exist in an amorphous, highly viscous semi-solid state under atmospherically relevant conditions. Hygroscopic growth factors (GFs) of ten laboratory-generated, organic-inorganic aerosol systems with phase morphologies ranging from well-mixed liquids, to phase-separated particles, to viscous semi-solids were measured with the Differential Aerosol Sizing and Hygroscopicity Spectrometer Probe at RH values ranging from 30 - 90%. Measured GFs were compared to water-uptake calculations in which it was assumed that particles could be represented as thermodynamically ideal, well-mixed liquids, as well as those predicted by the Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) model. Both ideal and AIOMFAC-predicted GFs were in good agreement with experimental GFs for aerosol systems that exist as well-mixed liquids across the range of RHs tested; however, substantial disagreement between experimental and ideal GFs was observed for phase-separated particles. This disagreement was greatest at low to moderate RHs, whereas experimental GFs approached the ideal curve at high RH as phase-separated particles merged to a single phase with increased water content. AIOMFAC, which offers the ability to predict liquid-liquid and liquid-solid phase separations within a thermodynamic equilibrium computation, was within 10% of experimental GFs at all RHs for all aerosol systems. The assumption that water uptake is driven by ideal, equilibrium partitioning leads to errors in calculated particle size and refractive index and has implications for predicted aerosol scattering efficiencies and radiative properties.