Influence of acidity on liquid-liquid phase transitions of mixed secondary organic aerosol (SOA) proxy-inorganic aerosol droplets

The phase state and morphology of aerosol particles play a critical role in determining their effect on climate. While aerosol acidity has been identified as a key factor affecting multiphase chemistry and phase transitions, the impact of acidity on the phase transition of multicomponent aerosol particles has not been extensively studied in situ. In this work, we employed aerosol optical tweezers (AOT) to probe the impact of acidity on the phase transition behavior of levitated aerosol particles. Our results revealed that higher acidity decreases the separation relative humidity (SRH) of aerosol droplets mixed with ammonium sulfate (AS) and secondary organic aerosol (SOA) proxy, such as 3-methylglutaric acid (3-MGA), 1,2,6-hexanetriol (HEXT) and 2,5-hexanediol (HEXD) across aerosol pH in atmospheric conditions. Phase separation of organic acids was more sensitive to acidity compared to organic alcohols. We found the mixing relative humidity (MRH) was consistently higher than the SRH in several systems. Phase-separating systems, including 3-MGA / AS, HEXT / AS and HEXD / AS, exhibited oxygen-to-carbon ratios (O:C) of 0.67, 0.50 and 0.33, respectively. In contrast, liquid-liquid phase separation (LLPS) did not occur in the high-O:C system of glycerol / AS, which had an O:C ratio of 1.00. Additionally, the morphology of 42 out of the 46 aerosol particles that underwent LLPS was observed to be a core-shell structure. Our findings provide a comprehensive understanding of the pH-dependent LLPS in individual suspended aerosol droplets and pave the way for future research on phase separation of atmospheric aerosol particles.