Relative humidity-dependent viscosity of secondary organic material from toluene photo-oxidation and possible implications for organic particulate matter over megacities

To improve predictions of air quality, visibility, and climate change, knowledge of the viscosities and diffusion rates within organic particulate matter consisting of secondary organic material (SOM) is required. Most qualitative and quantitative measurements of viscosity and diffusion rates within organic particulate matter have focused on SOM particles generated from biogenic volatile organic compounds (VOCs) such as alpha-pinene and isoprene. In this study, we quantify the relative humidity (RH)-dependent viscosities at 295 +/- 1K of SOM produced by photo-oxidation of toluene, an anthropogenic VOC. The viscosities of toluene-derived SOM were 2 x 10(-1) to similar to 6 x 10(6) Pa s from 30 to 90% RH, and greater than similar to 2 x 10(8) Pa s (similar to or greater than the viscosity of tar pitch) for RH <= 17 %. These viscosities correspond to Stokes-Einstein-equivalent diffusion coefficients for large organic molecules of similar to 2 x 10(-15) cm(2) s(-1) for 30% RH, and lower than similar to 3 x 10(-17) cm(2) s(-1) for RH <= 17 %. Based on these estimated diffusion coefficients, the mixing time of large organic molecules within 200 nm toluene-derived SOM particles is 0.1-5 h for 30% RH, and higher than similar to 100 h for RH <= 17 %. As a starting point for understanding the mixing times of large organic molecules in organic particulate matter over cities, we applied the mixing times determined for toluene-derived SOM particles to the world's top 15 most populous megacities. If the organic particulate matter in these megacities is similar to the toluene-derived SOM in this study, in Istanbul, Tokyo, Shanghai, and Sao Paulo, mixing times in organic particulate matter during certain periods of the year may be very short, and the particles may be wellmixed. On the other hand, the mixing times of large organic molecules in organic particulate matter in Beijing, Mexico City, Cairo, and Karachi may be long and the particles may not be well-mixed in the afternoon (15:00-17:00 LT) during certain times of the year.