Suppressed atmospheric chemical aging of cooking organic aerosol particles in wintertime conditions

Abstract

Cooking organic aerosol (COA) is one of the major constituents of particulate matter in urban areas. COA is oxidized by atmospheric oxidants such as ozone, changing its physical, chemical and toxicological properties. However, atmospheric chemical lifetimes of COA and its tracers such as oleic acid are typically longer than those that have been estimated by laboratory studies. We tackled the issue by considering temperature. Namely, we hypothesize that increased viscosity of COA at ambient temperature accounts for its prolonged atmospheric chemical lifetimes in wintertime. Laboratory-generated COA particles from cooking oil were exposed to ozone in an aerosol flow tube reactor for the temperature range of -20 to 35 °C. The pseudo-second-order chemical reaction rate constants (k2) were estimated from the experimental data by assuming a constant ozone concentration in the flow tube. The estimated values of k2 decreased by orders of magnitude for lower temperatures. The temperature dependence in k2 was fit well by considering the diffusion-limited chemical reaction mechanism. The result suggested that increased viscosity was likely the key factor to account for the decrease in chemical reactivity at the reduced temperature range, though the idea will still need to be verified by temperature-dependent viscosity data in the future. In combination with the observed global surface temperature, the atmospheric chemical lifetimes of COA were estimated to be much longer in wintertime (> 1 h) than in summertime (a few minutes) for temperate and boreal regions. Our present study demonstrates that the oxidation lifetimes of COA particles will need to be parameterized as a function of temperature in the future for estimating environmental impacts and fates of this category of particulate matter.