Particle phase state and aerosol liquid water greatly impact secondary aerosol formation: insights into phase transition and its role in haze events

Abstract

The particle phase state is crucial for reactive gas uptake, heterogeneous, and multiphase chemical reactions, thereby impacting secondary aerosol formation. This study provides valuable insights into the significance of particle-phase transition and aerosol liquid water (ALW) in particle mass growth during winter. Our findings reveal that particles predominantly exist in a semi-solid or solid state during clean winter days with ambient relative humidity (RH) below 30 %. However, a non-liquid to liquid phase transition occurs when the ALW mass fraction exceeds 15 % (dry mass) at transition RH thresholds of 40 %–60 %. During haze episodes, the transformation rates of sulfate and nitrate aerosols rapidly increase through phase transition and increased ALW by 48 % and 11 %, respectively, resulting in noticeable increases in secondary inorganic aerosols (SIA). The presence of abundant ALW, favored by elevated RH and higher proportion of SIA, facilitates the partitioning of water-soluble compounds from the gas to the particle phase, as well as heterogeneous and aqueous processes in liquid particles. This leads to a substantial increase in the formation of secondary organic aerosols and elevated aerosol oxidation. Consequently, the overall hygroscopicity parameters exhibit a substantial enhancement, with a mean value of 23 %. These results highlight phase transition as a key factor initiating the positive feedback loops between ALW and secondary aerosol formation during haze episodes over the North China Plain. Accurate predictions of secondary aerosol formation necessitate explicit consideration of the particle phase state in chemical transport models.