Primary Radical Effectiveness: Do the Different Chemical Reactivities of Hydroxyl and Chlorine Radicals Matter for Tropospheric Oxidation?

The atmospheric oxidation of organics occurs primarily via reaction cycles involving gas phase radical species, catalysed by nitric oxide (NO), which result in the production of secondary pollutants such as ozone. For these oxidation cycles to occur, they must be initialized by a primary radical, i.e., a radical formed from non-radical precursors. Once formed, these primary radicals can result in the oxidation of organic compounds to produce peroxy radicals that, providing sufficient NO is present, can re-generate "secondary" radicals which can go on to oxidize further organics. Thus, one primary radical can result in the catalytic oxidation of multiple organics. Although the photolysis of ozone in the presence of water vapor to form two hydroxyl (OH) radicals is accepted as the dominant tropospheric primary radical source, multiple other primary radical sources exist and can dominate in certain environments. The chemical reactivity of different radicals to organic and inorganic compounds can be very different, however, and how these differences in radical chemistry impact atmospheric organic oxidation under different atmospheric conditions has not been previously demonstrated. In this work, we use a series of model simulations to investigate the impact of the chemical reactivity of the primary radical on the effectiveness in initializing organic oxidation and thus the production of the secondary pollutant ozone. We compare the chemistries of the OH and atomic chlorine (Cl) radicals and their effectiveness at initializing organic oxidation under different nitrogen oxide and organic concentrations. The OH radical is the dominant tropospheric radical, with both primary and secondary sources. In contrast, Cl has primary sources that show significant spatial heterogeneity throughout the troposphere but is not typically regenerated in catalytic cycles. Both primary OH and Cl can initiate organic oxidation, but this work shows that the relative effectiveness with which they oxidize organics and produce ozone depends on their balance of propagation vs termination reactions which is in turn determined by the chemical environment in which they are produced. In particular, our work shows that in high NOx radical-limited environments, like those found in many urban areas, Cl will be more efficient at oxidizing organics than OH.

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