Liquid-liquid phase separation in particles containing secondary organic material free of inorganic salts
Abstract. Particles containing secondary organic material (SOM) are ubiquitous in the atmosphere and play a role in climate and air quality. Recently, research has shown that liquid-liquid phase separation (LLPS) occurs at high relative humidities (RH) (greater than ~ 95 %) in α-pinene-derived SOM particles free of inorganic salts while LLPS does not occur in isoprene-derived SOM particles free of inorganic salts. We expand on these findings by investigating LLPS in SOM particles free of inorganic salts produced from ozonolysis of β-caryophyllene, ozonolysis of limonene, and photo-oxidation of toluene. LLPS was observed at greater than ~ 95 % RH in the biogenic SOM particles derived from β-caryophyllene and limonene while LLPS was not observed in the anthropogenic SOM particles derived from toluene at 290 ± 1 K. This work combined with the earlier work on LLPS in SOM particles free of inorganic salts suggests that the occurrence of LLPS in SOM particles free of inorganic salts is related to the average oxygen-to-carbon elemental ratio (O : C) of the organic material. When the average O : C is between 0.25 and 0.60, LLPS was observed, but when the average O : C was between 0.52 and 1.3, LLPS was not observed. These results help explain the difference between the hygroscopic parameter k of SOM particles measured above and below water saturation in the laboratory and field, and have implications for predicting the cloud condensation nucleation properties of SOM particles.