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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.

Aerosol phase state is critical for quantifying aerosol effects on climate and air quality. However, significant challenges remain in our ability to predict and quantify phase state during its evolution in the atmosphere. Herein, we demonstrate that aerosol phase (liquid, semisolid, solid) exhibits a diel cycle in a mixed forest environment, oscillating between a viscous, semisolid phase state at night and liquid phase state with phase separation during the day. The viscous nighttime particles existed despite higher relative humidity and were independently confirmed by bounce factor measurements and atomic force microscopy. High-resolution mass spectrometry shows the more viscous phase state at night is impacted by the formation of terpene-derived and higher molecular weight secondary organic aerosol (SOA) and smaller inorganic sulfate mass fractions. Larger daytime particulate sulfate mass fractions, as well as a predominance of lower molecular weight isoprene-derived SOA, lead to the liquid state of the daytime particles and phase separation after greater uptake of liquid water, despite the lower daytime relative humidity. The observed diel cycle of aerosol phase should provoke rethinking of the SOA atmospheric lifecycle, as it suggests diurnal variability in gas-particle partitioning and mixing time scales, which influence aerosol multiphase chemistry, lifetime, and climate impacts.