Modeling the effect of non-ideality, dynamic mass transfer and viscosity on SOA formation in a 3-D air quality model

摘要

In this study, assumptions (ideality and thermodynamic equilibrium) commonly made in three-dimensional (3-D) air quality models were reconsidered to evaluate their impacts on secondary organic aerosol (SOA) formation over Europe. To investigate the effects of non-ideality, dynamic mass transfer and aerosol viscosity on the SOA formation, the Secondary Organic Aerosol Processor (SOAP) model was implemented in the 3-D air quality model Polyphemus. This study presents the first 3-D modeling simulation which describes the impact of aerosol viscosity on the SOA formation. The model uses either the equilibrium approach or the dynamic approach with a method specially designed for 3-D air quality models to efficiently solve particle-phase diffusion when particles are viscous. Sensitivity simulations using two organic aerosol models implemented in Polyphemus to represent mass transfer between gas and particle phases show that the computation of the absorbing aerosol mass strongly influences the SOA formation. In particular, taking into account the concentrations of inorganic aerosols and hydrophilic organic aerosols in the absorbing mass of the aqueous phase increases the average SOA concentration by 5?% and 6?%, respectively. However, inorganic aerosols influence the SOA formation not only because they constitute an absorbing mass for hydrophilic SOA, but also because they interact with organic compounds. Non-ideality (short-, medium- and long-range interactions) was found to influence SOA concentrations by about 30?%. Concerning the dynamic mass transfer for the SOA formation, if the viscosity of SOA is not taken into account and if ideality of aerosols is assumed, the dynamic approach is found to give generally similar results to the equilibrium approach (indicating that equilibrium is an efficient hypothesis for inviscid and ideal aerosols). However, when a non-ideal aerosol is assumed, taking into account the dynamic mass transfer leads to a decrease of concentrations of the hydrophilic compounds (compared to equilibrium). This decrease is due to differences in the values of activity coefficients, which are different between values computed for bulk aerosols and those for each size section. This result indicates the importance of non-ideality on the dynamic evolution of SOA. For viscous aerosols, assuming a highly viscous organic phase leads to an increase in SOA concentrations during daytime (by preventing the evaporation of the most volatile organic compounds). The partitioning of nonvolatile compounds is not affected by viscosity, but the aging of more volatile compounds (that leads to the formation of the less volatile compounds) slows down as the evaporation of those compounds is stopped due to the viscosity of the particle. These results imply that aerosol concentrations may deviate significantly from equilibrium as the gas–particle partitioning could be higher than predicted by equilibrium. Furthermore, although a compound evaporates in the simulation using the equilibrium approach, the same compound can condense in the simulation using the dynamic approach if the particles are viscous. The results of this study emphasize the need for 3-D air quality models to take into account the effect of non-ideality on SOA formation and the effect of aerosol viscosity for the more volatile fraction of semi-volatile organic compounds.