Predictions of diffusion rates of large organic molecules in secondary organic aerosols using the Stokes-Einstein and fractional Stokes-Einstein relations

Information on the rate of diffusion of organic molecules within secondary organic aerosol (SOA) is needed to accurately predict the effects of SOA on climate and air quality. Diffusion can be important for predicting the growth, evaporation, and reaction rates of SOA under certain atmospheric conditions. Often, researchers have predicted diffusion rates of organic molecules within SOA using measurements of viscosity and the Stokes–Einstein relation (D∝1/η, where D is the diffusion coefficient and η is viscosity). However, the accuracy of this relation for predicting diffusion in SOA remains uncertain. Using rectangular area fluorescence recovery after photobleaching (rFRAP), we determined diffusion coefficients of fluorescent organic molecules over 8 orders in magnitude in proxies of SOA including citric acid, sorbitol, and a sucrose–citric acid mixture. These results were combined with literature data to evaluate the Stokes–Einstein relation for predicting the diffusion of organic molecules in SOA. Although almost all the data agree with the Stokes–Einstein relation within a factor of 10, a fractional Stokes–Einstein relation (D∝1/η^ξ) with ξ=0.93 is a better model for predicting the diffusion of organic molecules in the SOA proxies studied. In addition, based on the output from a chemical transport model, the Stokes–Einstein relation can overpredict mixing times of organic molecules within SOA by as much as 1 order of magnitude at an altitude of ∼3 km compared to the fractional Stokes–Einstein relation with ξ=0.93. These results also have implications for other areas such as in food sciences and the preservation of biomolecules.