Explicit modelling of SOA formation from ??-pinene photooxidation: Sensitivity to vapour pressure estimation
The sensitivity of the formation of secondary organic aerosol (SOA) to the estimated vapour pressures of the condensable oxidation products is explored. A highly detailed reaction scheme was generated for alpha-pinene photooxidation using the Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A). Vapour pressures (P-vap) were estimated with three commonly used structure activity relationships. The values of P-vap were compared for the set of secondary species generated by GECKO-A to describe alpha-pinene oxidation. Discrepancies in the predicted vapour pressures were found to increase with the number of functional groups borne by the species. For semi-volatile organic compounds (i.e. organic species of interest for SOA formation), differences in the predicted Pvap range between a factor of 5 to 200 on average. The simulated SOA concentrations were compared to SOA observations in the Caltech chamber during three experiments performed under a range of NOx conditions. While the model captures the qualitative features of SOA formation for the chamber experiments, SOA concentrations are systematically overestimated. For the conditions simulated, the modelled SOA speciation appears to be rather insensitive to the P-vap estimation method.