An assessment of vapour pressure estimation methods.

Laboratory measurements of vapour pressures for atmospherically relevant compounds were collated and used to assess the accuracy of vapour pressure estimates generated by seven estimation methods and impacts on predicted secondary organic aerosol. Of the vapour pressure estimation methods that were applicable to all the test set compounds, the Lee-Kesler [Reid et al., The Properties of Gases and Liquids, 1987] method showed the lowest mean absolute error and the Nannoolal et al. [Nannoonal et al., Fluid Phase Equilib., 2008, 269, 117-133] method showed the lowest mean bias error (when both used normal boiling points estimated using the Nannoolal et al. [Nannoolal et al., Fluid Phase Equilib., 2004, 226, 45-63] method). The effect of varying vapour pressure estimation methods on secondary organic aerosol (SOA) mass loading and composition was investigated using an absorptive partitioning equilibrium model. The Myrdal and Yalkowsky [Myrdal and Yalkowsky, Ind. Eng. Chem. Res., 1997, 36, 2494-2499] vapour pressure estimation method using the Nannoolal et al. [Nannoolal et al., Fluid Phase Equilib., 2004, 226, 45-63] normal boiling point gave the most accurate estimation of SOA loading despite not being the most accurate for vapour pressures alone.

Surface tension of mixed inorganic and dicarboxylic acid aqueous solutions at 298.15 K and their importance for cloud activation predictions.

The following study extends previous work on modelling multicomponent surface tensions and the impact they have on aerosol and climate modelling. Mixed dicarboxylic acid and ammonium sulfate solution surface tensions have been measured experimentally and were modelled using an additive, a semi-empirical and two thermodynamic methods. A thermodynamic method with parameters fitted to binary solution data reproduced experimental results most closely with average absolute deviation from the experimental data over all measurements of 2.6%, compared with 7.7% for the additive, 8.1% for the semi-empirical and 7.3% for the other thermodynamic method. The choice of surface tension modelling method can lead to differences of up to 50% in the critical saturation ratios of aerosol particles. When applied to a trimodal aerosol distribution this leads to a difference in dry diameter for activation of 30 to 40 nm. This is greater than the difference induced by changing inorganic to organic mass ratios (>10 nm).