Representation of Multiphase OH Oxidation of Amorphous Organic Aerosol for Tropospheric Conditions.

Abstract

Organic aerosol (OA) is ubiquitous in the atmosphere and, during transport, can experience chemical transformation with consequences for air quality and climate. Prediction of the chemical evolution of OA depends on its reactivity with atmospheric oxidants such as the OH radical. OA particles undergo amorphous phase transitions from liquid to solid (glassy) states in response to temperature changes, which, in turn, will impact its reactivity toward OH oxidation. To improve the predictability of OA reactivity toward OH oxidation, the reactive uptake coefficients (γ) of OH radicals reacting with triacontane and squalane serving as amorphous OA surrogates were measured at temperatures from 213-293 K. γ increases strongest with temperature when the organic species is in the liquid phase, compared to when being in the semisolid or solid phase. The resistor model is applied, accounting for the amorphous phase state changes using the organic species' glass transition temperature and fragility, to evaluate the physicochemical parameters of the temperature dependent OH uptake process. This allows for the derivation of a semiempirical formula, applicable to models, to predict the degree of oxidation and chemical lifetime of the condensed-phase organic species for typical tropospheric temperature and humidity when OA particle viscosity is known.