Phase transitions of aqueous atmospheric particles: Crystallization of ammonium salts promoted by oxide mineral constituents

Knowledge of the hygroscopic response of aerosols is a fundamental factor necessary for the accurate quantitative modeling of visibility degradation, global warming, PM-10 health issues, cloud microphysics, and the oxidizing capacity of the troposphere. At the present time, however, our current understanding of phase transitions is insufficient to develop accurate quantitative models. The discrepancy between current atmospheric models and field measurements originates mainly from a lack of understanding of the efflorescence of real atmospheric particles. While there have been many studies on the homogeneous nucleation of the soluble organic, inorganic, or multi-component materials, many recent in situ field measurements with single-particle mass spectrometry reveal that the individual particles in the troposphere are primarily composed of more than one component. One of the common mixed component particle types contains both water-soluble and insoluble components. Through atmospheric processes, the soluble component can be expected to form a coating around the insoluble constituents. This type of atmospheric particles is very important because the insoluble constituent can play a role as a template for the crystallization of the soluble components by heterogeneous nucleation. In the atmosphere, the most prevalent insoluble constituents are mineral dusts, which have their origin from Saharan and Gobbi deserts. The existence of these coated particles has been supported by several field measurements as well as model studies. Therefore, it becomes imperative to simulate more realistic atmospheric particles for more exact (or realistic) understanding the phase transition of the ambient aerosol particles in the real world.; In this context, a series of studies has been completed to solve the aforementioned problems in the phase transition study and to better understand the heterogeneous nucleation of these internally mixed particles. An in-line tube furnace has been developed and characterized to generate the internally mixed particles consisting of the soluble and insoluble components. Spray pyrolysis was employed in order to have the control of the size and crystalline phase of the insoluble constituents and combined with the in-line tube furnace to manipulate the coated particles (i.e., internally mixed particles). Employing the stable and well-characterized generation source for the coated particles, the roles of the insoluble constituents (i.e., metal oxides) in heterogeneous nucleation were investigated extensively in terms of their size (i.e., surface area) and crystalline structure as nucleation templates. Ammonium sulfate and ammonium nitrate were selected as the soluble components because they are the most common atmospheric aerosol particles from anthropogenic activities. As for insoluble components, corundum (α-Al₂O₃), hematite (α-Al₂O₃), mullite (Al₆Si ₂O₁₃), silica (am-SiO₂), rutile (TiO₂), ZrO₂, and δ-Al₂O₃ were selected with the reasoning that some of them represent the abundant crustal components in the atmosphere and that others have interesting chemical compositions and/or crystalline structures.