Evolution of Atmospheric Total Organic Carbon from Petrochemical Mixtures.

Reactive organic compounds play a central role in the formation of ozone and secondary organic aerosols. The ability to accurately predict their fate, in part, relies upon quantitative knowledge of the chemical and physical parameters associated with the total organic carbon (TOC), which includes both precursors and oxidation products that evolve in the atmosphere over short to long time scales. However, such knowledge, obtained via limited carbon closure experiments, has not been attained for complex anthropogenic emissions. Here we present the first comprehensive characterization of TOC in the atmospheric oxidation of organic vapors from light and heavy oil mixtures associated with oil sand operations. Despite the complexity of the investigated oil mixtures, we are able to achieve carbon closure (83-116%) within the uncertainties (±20%), with the degree of the closure being dependent upon the vapor composition and NOx levels. In contrast to biogenic precursors (e.g., α-pinene), the photochemical time scale required for a largely complete oxidation and evolution of chemical parameters is very long for the petrochemical vapors (i.e., ∼7-10 days vs ∼1 day), likely due to the lower initial precursor reactivity. This suggests that petrochemical emissions and their impacts are likely to extend further spatially than biogenic emissions, and retain more of their complex composition and reactivity for many days. The results of this work provide key parameters to regional models for further improving the representation of the chemical evolution of petrochemical emissions.