Atmos. Chem. Phys. Discuss., 7, 849-910, 2007
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Reformulating atmospheric aerosol thermodynamics and hygroscopic growth into haze and clouds
S. Metzger and J. Lelieveld
Max Planck Institute for Chemistry, Mainz, Germany

Abstract. Modeling atmospheric aerosol and cloud microphysics is rather complex, even if chemical and thermodynamical equilibrium is assumed. We show, however, that the thermodynamics can be considerably simplified by reformulating equilibrium to include water, and transform laboratory-based concepts to atmospheric conditions. We generalize the thermodynamic principles that explain hydration and osmosis – merely based on solute solubilities. In chemical and thermodynamical equilibrium the relative humidity (RH) determines the saturation molality, including solute and solvent activities (and activity coefficients), since the water content is fixed by RH for a given aerosol concentration and type. As a consequence, gas/liquid/solid aerosol equilibrium partitioning can be solved analytically and non-iteratively. Our new concept enables an efficient and accurate calculation of the aerosol water mass and to directly link the aerosol hygroscopic growth to haze and cloud formation.

We apply our new concept in the 3rd Equilibrium Simplified Aerosol Model (EQSAM3). Its input is limited to the species' solubilities from which a newly introduced stoichiometric coefficient for water is derived. Analogously, we introduce effective stochiometric coefficients for the solutes to account for complete or incomplete dissociation. We show that these coefficients can be assumed constant over the entire activity range and calculated for various inorganic, organic and non-electrolyte compounds, including alcohols, sugars and dissolved gases. EQSAM3 calculates the aerosol composition and gas/liquid/solid partitioning of mixed inorganic/organic multicomponent solutions and the associated water uptake for almost 100 major compounds. It explicitly accounts for particle hygroscopic growth by computing aerosol properties such as single solute molalities, molal based activities, including activity coefficients for volatile compounds, and deliquescence relative humidities of mixed solutes. Various applications and a model inter-comparison indicate that a) the application is not limited to dilute binary solutions, b) sensitive aerosol properties such as the pH of binary and mixed inorganic/organic salt solutions up to saturation can be computed accurately, and c) aerosol associated water is important for atmospheric chemistry, visibility, weather and climate.

Citation: Metzger, S. and Lelieveld, J.: Reformulating atmospheric aerosol thermodynamics and hygroscopic growth into haze and clouds, Atmos. Chem. Phys. Discuss., 7, 849-910, doi:10.5194/acpd-7-849-2007, 2007.
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