Treatment of non-ideality in the multiphase model SPACCIM – Part 1: Model development

Abstract

Abstract. Ambient tropospheric deliquesced particles generally comprise a complex mixture of electrolytes, organic compounds, and water. Dynamic modeling of physical and chemical processes in this complex matrix is challenging. Thus, up-to-date multiphase chemistry models do generally not consider non-ideal solution effects. Therefore, the present study was aimed at the further development of the SPACCIM model to treat both complex multiphase chemistry and phase transfer processes considering newly non-ideality properties of concentrated aerosol solutions. The present paper describes firstly, the performed model development including (i) the kinetic implementation of the non-ideality in the SPACCIM framework, (ii) the advancements in the coupling scheme of microphysics and multiphase chemistry and (iii) the required adjustments of the numerical schemes, especially in the sparse linear solver and the calculation of the Jacobian. Secondly, results of performed sensitivity investigations are outlined aiming at the evaluation of different activity coefficient modules and the examination of the contributions of different intermolecular forces to the overall activity coefficients. Finally, first results obtained with the new model framework are presented. The main product of the performed model development is the new kinetic model approach SPACCIM-SpactMod, which utilizes activities in reaction terms instead of aqueous concentrations. Based on an intercomparison of different activity coefficient models and the comparison with experimental data, AIOMFAC was selected as base model and extended by additional interaction parameters from literature for mixed organic–inorganic systems. Moreover, the performance and the capability of the applied activity coefficient module were evaluated by means of water activity measurements, literature data and results of other thermodynamic equilibrium models. Comprehensive comparison studies showed that the SpactMod (SPACCIM activity coefficient module) is valuable to predict the thermodynamic behavior of complex mixtures of multicomponent atmospheric aerosol particles. First simulations with a detailed chemical mechanism have demonstrated the applicability of SPACCIM-SpactMod. The simulations have implied that the treatment of non-ideality should be mandatory for modeling multiphase chemistry processes in deliquesced particles. The modeled activity coefficients implicate that turnovers of chemical processes in deliquesced particles can be both decreased and increased depending on the particular species involved in the reactions. For key ions, activity coefficients on the order of 0.1–0.8 and a strong dependency on the charge state as well as the RH conditions are modeled implicating a lowered chemical ion processing in concentrated solutions. In contrast, modeled activity coefficients of organic compounds are partly > 1 and suggest the possibility of an increased organic processing. Moreover, the model runs have shown noticeable differences in the pH values calculated with and without consideration of non-ideality. On average, the predicted pH values of the simulations considering non-ideality are −0.27 and −0.44 pH units lower under 90 and 70% RH conditions, respectively. More comprehensive results of detailed SPACCIM-SpactMod studies on the multiphase processing in organic–inorganic mixtures of deliquesced particles are described in a companion paper.