Volatility and aging of atmospheric organic aerosol. 2014

Neil M Donahue, and Allen L Robinson, and Erica R Trump, and Ilona Riipinen, and Jesse H Kroll
Carnegie Mellon University Center for Atmospheric Particle Studies, Pittsburgh, PA, USA, nmd@andrew.cmu.edu.

Organic-aerosol phase partitioning (volatility) and oxidative aging are inextricably linked in the atmosphere because partitioning largely controls the rates and mechanisms of aging reactions as well as the actual amount of organic aerosol. Here we discuss those linkages, describing the basic theory of partitioning thermodynamics as well as the dynamics that may limit the approach to equilibrium under some conditions. We then discuss oxidative aging in three forms: homogeneous gas-phase oxidation, heterogeneous oxidation via uptake of gas-phase oxidants, and aqueous-phase oxidation. We present general scaling arguments to constrain the relative importance of these processes in the atmosphere, compared to each other and compared to the characteristic residence time of particles in the atmosphere.

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