Abstract
Abstract. Recent work has demonstrated that organic and mixed organic–inorganic particles can exhibit multiple phase states depending on their chemical composition and on ambient conditions such as relative humidity (RH). To explore the extent to which water uptake varies with particle-phase behavior, hygroscopic growth factors (HGFs) of nine laboratory-generated, organic and organic–inorganic aerosol systems with physical states ranging from well-mixed liquids to phase-separated particles to viscous liquids or semi-solids were measured with the Differential Aerosol Sizing and Hygroscopicity Spectrometer Probe at RH values ranging from 40 to 90%. Water-uptake measurements were accompanied by HGF and RH-dependent thermodynamic equilibrium calculations using the Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) model. In addition, AIOMFAC-predicted growth curves are compared to several simplified HGF modeling approaches: (1) representing particles as ideal, well-mixed liquids; (2) forcing a single phase but accounting for non-ideal interactions through activity coefficient calculations; and (3) a Zdanovskii–Stokes–Robinson-like calculation in which complete separation of the inorganic and organic components is assumed at all RH values, with water uptake treated separately in each of the individual phases. We observed variability in the characteristics of measured hygroscopic growth curves across aerosol systems with differing phase behaviors, with growth curves approaching smoother, more continuous water uptake with decreasing prevalence of liquid–liquid phase separation and increasing oxygen : carbon ratios of the organic aerosol components. We also observed indirect evidence for the dehydration-induced formation of highly viscous semi-solid phases and for kinetic limitations to the crystallization of ammonium sulfate at low RH for sucrose-containing particles. AIOMFAC-predicted growth curves are generally in good agreement with the HGF measurements. The performances of the simplified modeling approaches, however, differ for particles with differing phase states. This suggests that no single simplified modeling approach can be used to capture the water-uptake behavior for the diversity of particle-phase behavior expected in the atmosphere. Errors in HGFs calculated with the simplified models are of sufficient magnitude to produce substantial errors in estimates of particle optical and radiative properties, particularly for the assumption that water uptake is driven by absorptive equilibrium partitioning with ideal particle-phase mixing.
Highlights
Atmospheric aerosols alter the Earth’s radiation budget, reduce visibility, and are associated with adverse health effects (Finlayson-Pitts and Pitts, 2000; Pöschl, 2005; Seinfeld and Pandis, 2006)
As a result, such measurements may not accurately reflect equilibrium water-uptake behavior. This is an important consideration when applying similar instruments to measure the hygroscopic behavior of ambient aerosols, for the highly oxygenated secondary organic aerosol (SOA) for which sucrose serves as a surrogate in our experiments
Our results add support to the growing body of literature suggesting that accounting for the influence of viscous liquid or semi-solid phases to water uptake and release can be important for accurately modeling the hygroscopic behavior of atmospheric aerosols
Summary
Atmospheric aerosols alter the Earth’s radiation budget, reduce visibility, and are associated with adverse health effects (Finlayson-Pitts and Pitts, 2000; Pöschl, 2005; Seinfeld and Pandis, 2006). The magnitude of these impacts is influenced by aerosol water content, as this is a major determinant of aerosol particle size. N. Hodas et al.: Influence of particle-phase state on the hygroscopic behavior is key to representing aerosol properties and behavior in atmospheric models and to improving our understanding of their impacts on climate and air quality
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