Predicting Liquid–Liquid Phase Separation of Submicrometer Proxies for Atmospheric Secondary Aerosol

Abstract

Liquid–liquid phase separation (LLPS) of atmospheric aerosols can significantly impact climate, air quality, and human health. However, their complex composition, small size, and history-dependent properties result in great uncertainty in the modeling of aerosol phase state and atmospheric processes. Herein, using cryogenic transmission electron microscopy (cryo-TEM), we examined model submicron aerosols composed of organic compounds and ammonium sulfate and established a parametrization for the separation relative humidity (SRH) that accounts for chemical composition, particle size, and equilibration time. We evaluated different variables that describe chemical composition: O/C ratio, partition coefficient, solubility, molar mass, and polarizability. The O/C ratio fits the SRH of micrometer droplets best, and by using a scaling factor to translate the micrometer SRH parametrization to submicron aerosols, we incorporate the effects of size and equilibration time. The measured scaling factor for the submicron mean SRH (30 nm–1 μm, 20 min equilibration times) is 0.80, and the factor becomes 1 with equilibration time over 1 h and is equal to 0, meaning that SRH is absent, when the aerosol dry diameter is smaller than 30 nm. Our parametrization will aid in universal SRH modeling, potentially leading to more accurate predictions of aerosol mass, optical properties, hygroscopicity, and heterogeneous chemistry.