Abstract. Tropospheric deliquesced particles are characterised by concentrated non-ideal solutions (“aerosol liquid water” or ALW) that can affect the occurring multiphase chemistry. However, such non-ideal solution effects have generally not yet been considered in and investigated by current complex multiphase chemistry models in an adequate way. Therefore, the present study aims at accessing the impact of non-ideality on multiphase chemical processing in concentrated aqueous aerosols. Simulations with the multiphase chemistry model (SPACCIM-SpactMod) are performed under different environmental and microphysical conditions with and without a treatment of non-ideal solutions in order to assess its impact on aqueous-phase chemical processing. The present study shows that activity coefficients of inorganic ions are often below unity under 90 % RH-deliquesced aerosol conditions and that most uncharged organic compounds exhibit activity coefficient values of around or even above unity. Due to this behaviour, model studies have revealed that the inclusion of non-ideality considerably affects the multiphase chemical processing of transition metal ions (TMIs), oxidants, and related chemical subsystems such as organic chemistry. In detail, both the chemical formation and oxidation rates of Fe(II) are substantially lowered by a factor of 2.8 in the non-ideal base case compared to the ideal case. The reduced Fe(II) processing in the non-ideal base case, including lowered chemical rates of the Fenton reaction (−70 %), leads to a reduced processing of HOx∕HOy under deliquesced aerosol conditions. Consequently, higher multiphase H2O2 concentrations (larger by a factor of 3.1) and lower aqueous-phase OH concentrations (lower by a factor of ≈4) are modelled during non-cloud periods. For H2O2, a comparison of the chemical reaction rates reveals that the most important sink, the reaction with HSO3-, contributes with a 40 % higher rate in the non-ideal base case than in the ideal case, leading to more efficient sulfate formation. On the other hand, the chemical formation rates of the OH radical are about 50 % lower in the non-ideal base case than in the ideal case, leading to lower degradation rates of organic aerosol components. Thus, considering non-ideality influences the chemical processing and the concentrations of organic compounds under deliquesced particle conditions in a compound-specific manner. For example, the reduced oxidation budget under deliquesced particle conditions leads to both increased and decreased concentration levels, e.g. of important C2∕C3 carboxylic acids. For oxalic acid, the present study demonstrates that the non-ideality treatment enables more realistic predictions of high oxalate concentrations than observed under ambient highly polluted conditions. Furthermore, the simulations imply that lower humidity conditions, i.e. more concentrated solutions, might promote higher oxalic acid concentration levels in aqueous aerosols due to differently affected formation and degradation processes.
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