Relative humidity-dependent viscosities of isoprene-derived secondary organic material and atmospheric implications for isoprene-dominant forests

Abstract

Oxidation of isoprene is an important source of secondary organic material (SOM) in atmospheric particles, especially in areas such as the Amazon Basin. Information on the viscosities, diffusion rates, and mixing times within isoprene-derived SOM is needed for accurate predictions of air quality, visibility, and climate. Currently, however, this information is not available. Using a bead-mobility technique and a poke-flow technique combined with fluid simulations, the relative humidity (RH)-dependent viscosities of SOM produced from isoprene photo-oxidation were quantified for 20-60 μm particles at 295 ± 1 K. From 84.5 to 0% RH, the viscosities for isoprene-derived SOM varied from ∼ 2 × 10 -1 to ∼ 3 × 10 5 Pa s, implying that isoprene-derived SOM ranges from a liquid to a semisolid over this RH range. These viscosities correspond to diffusion coefficients of ∼ 2 × 10 -8 to ∼ 2 × 10 -14 cm 2 s -1 for large organic molecules that follow the Stokes-Einstein relation. Based on the diffusion coefficients, the mixing time of large organic molecules within 200 nm isoprene-derived SOM particles ranges from approximately 0.1 h to less than 1 s. To illustrate the atmospheric implications of this study's results, the Amazon Basin is used as a case study for an isoprene-dominant forest. Considering the RH and temperature range observed in the Amazon Basin and with some assumptions about the dominant chemical compositions of SOM particles in the region, it is likely that SOM particles in this area are liquid and reach equilibrium with large gas-phase organic molecules on short time scales, less than or equal to approximately 0.1 h.