Amorphous and crystalline aerosol particles interacting with water vapor – Part 1: Microstructure, phase transitions, hygroscopic growth and kinetic limitations

Abstract

Interactions with water are crucial for the properties, transformation and climate effects of atmospheric aerosols. Here we outline characteristic features and differences in the interaction of amorphous and crystalline aerosol particles with water vapor. Using a hy-groscopicity tandem differential mobility analyzer (H-TDMA), we performed hydration, 5 dehydration and cyclic hydration&dehydration experiments with aerosol particles composed of levoglucosan, oxalic acid and ammonium sulfate (diameters ∼100-200 nm, relative uncertainties <0.4%, relative humidities <5% to 95% at 298 K). The measurements and accompanying K ¨ ohler model calculations provide new insights into particle microstructure, surface adsorption, bulk absorption, phase transitions and hygroscopic 10 growth. The results of these and related investigations lead to the following main conclusions: 1. Many organic substances (including carboxylic acids, carbohydrates and proteins) tend to form amorphous rather than crystalline phases upon drying of aqueous solution droplets. Depending on viscosity and microstructure, the amorphous 15 phases can be classified as glasses, rubbers, gels or viscous liquids. 2. Amorphous organic substances tend to absorb water vapor and undergo gradual deliquescence and hygroscopic growth at much lower relative humidity than their crystalline counterparts. 3. In the course of hydration and dehydration, certain organic substances can form 20 rubber-or gel-like structures (supra-molecular networks) and undergo stepwise transitions between swollen and collapsed network structures. 4. Organic gels or (semi-)solid amorphous shells (glassy, rubbery, ultra-viscous) with low molecular diffusivity can kinetically limit the uptake and release of water by submicron aerosol particles on (multi-)second time scales, which may influence 25 the hygroscopic growth and activation of aerosol particles as cloud condensation nuclei (CCN) and ice nuclei (IN). 7334 5. The shape and porosity of amorphous and crystalline particles formed upon dehydration of aqueous solution droplets depend on chemical composition and drying conditions. The apparent volume void fractions of particles with highly porous structures can range up to ∼50% or more (xerogels, aerogels). Void fractions as well as residual water in dried aerosol particles that are not water-free (due 5 to kinetic limitations of drying or stable hydrate formation) should be taken into account in K ¨ ohler model calculations of hygroscopic growth and CCN activation. 6. For efficient description of water uptake and phase transitions of amorphous and crystalline organic and inorganic aerosol particles and particle components, we propose not to limit the terms deliquescence and efflorescence to equilibrium 10 phase transitions of crystalline substances interacting with water vapor. Instead we propose the following generalized definitions: Deliquescence is the transformation of a (semi-)solid substance into a liquid aqueous solution, whereby water is absorbed from the gas phase ("liquefaction upon humidification/hydration"). Ef-florescence is the transformation of a substance from a liquid aqueous solution 15 into a (semi-)solid phase, whereby water is evaporated ("solidification upon dry-ing/dehydration"). According to these definitions, individual components as well as entire aerosol particles can undergo gradual or prompt, partial or full deliques-cence or efflorescence.