Effects of Molecular-Level Compositional Variability in Organic Aerosol on Phase State and Thermodynamic Mixing Behavior.

The molecular-level composition and structure of organic aerosol (OA) affect its chemical/physical properties, transformations, and impacts. Here, we use the molecular-level chemical composition of functionalized OA from three diverse field sites to evaluate the effect of molecular-level compositional variability on OA phase state and thermodynamic mixing favorability. For these ambient sites, modeled aerosol phase state ranges from liquid to semisolid. The observed variability in OA composition has some effect on resulting phase state, but other factors like the presence of inorganic ions, aerosol liquid water, and internal versus external mixing with water are determining factors in whether these particles exist as liquids, semisolids, or solids. Organic molecular composition plays a more important role in determining phase state for phase-separated (verus well-mixed) systems. Similarly, despite the observed OA compositional differences, the thermodynamic mixing favorability for OA samples with aerosol liquid water, isoprene oxidation products, or monoterpene oxidation products remains fairly consistent within each campaign. Mixing of filter-sampled OA and isoprene or monoterpene oxidation products is often favorable in both seasons, while mixing with water is generally unfavorable.