Size-Dependent Liquid–Liquid Phase Separation in Atmospherically Relevant Complex Systems

Physical properties of aerosol particles, such as liquid-liquid phase separation (LLPS), have the potential to impact the climate system. Model systems have been shown to have size-dependent LLPS in the submicron regime; however, these systems are an extreme simplification of ambient aerosol, which can include myriad organic compounds. We expand the studies of LLPS in particles consisting of ammonium sulfate and more complex organic mixtures from multiple organic compounds to α-pinene secondary organic matter (SOM). All systems display a size-dependent morphology, with small particles remaining homogeneous while large particles phase-separate. Surprisingly, three-phase particles were also observed in some of the systems in addition to a new phase state that we have termed channel morphology, which can arise upon efflorescence. The existence of size-dependent LLPS in complex organic mixtures and SOM provides evidence that this is a relevant phenomenon for ambient aerosol and should be considered when modeling atmospheric aerosol.