Direct observation for relative-humidity-dependent mixing states of submicron particles containing organic surfactants and inorganic salts

Abstract

Abstract. Aerosol mixing state plays an important role in heterogeneous reactions and cloud condensation nuclei (CCN) activity. Organic surfactants could affect aerosol mixing state through bulk–surface partitioning. However, the mixing state of surfactant-containing particles remains unclear due to the lack of direct measurements. Here, direct characterizations of the mixing state for 20 kinds of submicron particles containing inorganic salts (NaCl and (NH4)2SO4) and atmospheric organic surfactants (organosulfates, organosulfonates, and dicarboxylic acids) were conducted upon relative humidity (RH) cycling by environmental scanning electron microscopy (ESEM). As the RH increased, the surfactant shells inhibited water diffusion being exposed to the inorganic core, leading to notably increased inorganic deliquescence RH (88.3 %–99.5 %) when compared with pure inorganic aerosol. Meanwhile, we directly observed an obvious Ostwald ripening process (that is, the growth of larger crystals at the expense of smaller ones) in 6 out of 10 NaCl–organic surfactant systems. As a result of water inhibition by the organic surfactant shell, Ostwald ripening in all systems occurred at RH above 90 %, which were higher than the reported RH range for pure NaCl measured at 27 ∘C (75 %–77 %). As RH decreased, eight systems underwent liquid–liquid-phase separation (LLPS) before efflorescence, showing a strong dependence on the organic molecular oxygen-to-carbon ratio (O:C). Quantitatively, LLPS was always observed when O:C≤0.43 and was never observed when O:C>∼0.57. Separation RH (SRH) of inorganic salt–organic surfactant mixtures generally followed the trend of (NH4)2SO4 < NaCl, which is consistent with their salting-out efficiencies reported in previous studies. Solid-phase separations were observed after efflorescence for systems without LLPS. Our results provide a unique insight into the consecutive mixing processes of the inorganic salt–organic surfactant particles, which would help improve our fundamental knowledge of model development on radiative effect.

Unlocking the Mystery of Aerosol Phase Transitions Governed by Relative Humidity History Through an Advanced Outdoor Nephelometer System

“…Their findings reveal that atmospheric aerosols can undergo sudden or gradual deliquescence or exhibit crystalline behavior, especially when aerosols are predominantly composed of ammoniated sulfate or sea salt. The characteristics of ambient aerosols exhibiting deliquescent behavior, along with the corresponding deliquescence relative humidity (DRH) and efflorescence RH (ERH), are influenced by aerosol chemical composition, including the proportions of nitrate (Sun et al., 2018) and secondary organic aerosols (SOA) (Saukko et al., 2015; Wang et al., 2021), as well as other factors such as mixing state (Li et al., 2021; Xiong et al., 2023). Over the past decade, in China, aerosol phase state has become a focal point in atmospheric aerosol research (Kuang et al., 2016; Y. Liu et al., 2017; Qiu et al., 2023; Sun et al., 2018).…”