PNNL

Abstract

The fate of many atmospheric trace species, including pollutants such as nitrogen oxides and some volatile organic compounds, is controlled by oxidation reactions. In the daytime troposphere, these reactions are dominated by photochemically produced OH radicals; at night and in polluted environments, NO3 radicals are an important oxidant. Ozone can contribute to the oxidation of atmospheric species during both day and night. In recent years, laboratory investigations, modelling studies, measured Cl deficits in marine aerosols and species-nonspecific observations of gaseous inorganic chlorine compounds other than HCl have suggested that reactive halogen species may contribute significantly to—or even locally dominate—the oxidative capacity of the lower marine troposphere. Here we report nighttime observations of molecular chlorine concentrations at a North American coastal site during onshore wind flow conditions that cannot be explained using known chlorine chemistry. The measured Cl2 mixing ratios range from