Anthropogenic Sources of Chlorine and Ozone Formation in Urban Atmospheres

Abstract

In this paper, we present ambient monitoring data from Houston, TX along with results from environmental chamber studies to suggest that molecular chlorine (Cl2), a photolytic source of chlorine atoms (Cl•), may contribute significantly to ozone (O3) formation in some urban environments. The ambient data were collected during an ozone episode in August 1993 that involved an alkane-rich hydrocarbon plume passing over anthropogenic sources of Cl2. Two unusual observations were made about the plume a few hours after it had passed over the Cl2 sources: (1) a rapid loss of alkanes and (2) a large increase in ozone concentration. Neither of these observations could be explained with models employing hydroxyl radical (OH•) chemistry (OH• are generally accepted to control oxidative chemistry in the daytime troposphere). Environmental chamber experiments were performed to determine whether the addition of Cl2 to a mixture of air, hydrocarbons, and nitrogen oxides (NOx) representative of conditions in the Houston ...