Determining Aerosol Volatility Parameters Using a “Dual Thermodenuder” System: Application to Laboratory-Generated Organic Aerosols

<div><p>Thermodenuders (TD) are a tool widely used for measuring aerosol volatility in the laboratory and field. Extracting the parameters that dictate organic aerosol volatility from TD data is challenging because gas-particle partitioning rarely reaches equilibrium inside a TD operating under atmospheric conditions, thus a wide variety of parameter sets can explain observed evaporation. Component volatilities (as represented by saturation vapor pressure, <i>C</i><sub><i>sat</i></sub>), cannot be directly extracted due to uncertainties in potential limitations to mass transfer (represented by mass accommodation coefficient, α) and components’ enthalpies of evaporation (Δ<i>H</i><sub><i>vap</i></sub>). To address these limitations, we have developed a “dual TD” experimental approach in which one line uses a temperature-stepping TD (TS-TD) with a relatively long residence time (RT) and the other operates isothermally at variable residence time (VRT-TD). Data from this approach are used in tandem with an optimizing evaporation kinetics model to extract the values of parameters dictating volatility (C<sub><i>sat</i></sub>, and associated values of ΔH<sub><i>vap</i></sub> and α). The system was evaluated using laboratory generated dicarboxylic acid aerosols (adipic acid and succinic acid). Excellent agreement with previously published evaporation data collected with other TD systems was observed. Parameter values reported in the literature for the tested acids vary widely, but our results are generally consistent with those from studies that allow for nonunity values of α. For example, our results suggest that α for these aerosols are of order 0.1, in agreement with results determined by Saleh et al. (2009, 2012). Modeling results suggest that the addition of VRT-TD data provides tighter constraint on feasible Δ<i>H</i><sub><i>vap</i></sub> and α values. The dual TD approach presented here does not rely on equilibration in the TD and thus can be directly applied to extract volatility parameters for more complex laboratory and ambient organic aerosol systems.</p><p>Copyright 2015 American Association for Aerosol Research</p></div>