A predictive group-contribution model for the viscosity of aqueous organic aerosol

Abstract

The viscosity of primary and secondary organic aerosol (SOA) has important implications for the processing of aqueous organic aerosol phases in the atmosphere, their involvement in climate forcing, and transboundary pollution. Here we introduce a new thermodynamics-based groupcontribution model, which is capable of accurately predicting the dynamic viscosity of a mixture over several orders of magnitude ( ∼ 10-3 to < 1012 Pa s) as a function of temperature and mixture composition, accounting for the effect of relative humidity on aerosol water content. The mixture viscosity modelling framework builds on the thermodynamic activity coefficient model AIOMFAC (Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients) for predictions of liquid mixture non-ideality, including liquid-liquid phase separation, and the calorimetric glass transition temperature model by DeRieux et al. (2018) for pure-component viscosity values of organic components. Comparing this new model with simplified modelling approaches reveals that the group-contribution method is the most accurate in predicting mixture viscosity, although accurate pure-component viscosity predictions (and associated experimental data) are key and one of the main sources of uncertainties in current models, including the model presented here. Nonetheless, we find excellent agreement between the viscosity predictions and measurements for systems in which mixture constituents have a molar mass below 350gmol-1. As such, we demonstrate the validity of the model in quantifying mixture viscosity for aqueous binary mixtures (glycerol, citric acid, sucrose, and trehalose), aqueous multicomponent mixtures (citric acid plus sucrose and a mixture of nine dicarboxylic acids), and aqueous SOA surrogate mixtures derived from the oxidation of pinene, toluene, or isoprene. We also use the model to assess the expected change in SOA particle viscosity during idealized adiabatic air parcel transport from the surface to higher altitudes within the troposphere. This work demonstrates the capability and flexibility of our model in predicting the viscosity for organic mixtures of varying degrees of complexity and its applicability for modelling SOA viscosity over a wide range of temperaturesand relative humidities.