High Chlorine Concentrations in an Unconventional Oil and Gas Development Region and Impacts on Atmospheric Chemistry.

Growth in unconventional oil and gas development (UOGD) in the United States has increased airborne emissions, raising environmental and human health concerns. To assess the potential impacts on air quality, we deployed instrumentation in Karnes City, Texas, a rural area in the middle of the Eagle Ford Shale. We measured several episodes of elevated Cl2 levels, reaching maximum hourly averages of 800 ppt, the highest inland Cl2 concentration reported to date. Concentrations peak during the day, suggesting a strong local source (given the short photolysis lifetime of Cl2) and/or a photoinitiated production mechanism. Well preproduction activity near the measurement site is a plausible source of these high Cl2 levels via direct emission and photoactive chemistry. ClNO2 is also observed, but it peaks overnight, consistent with well-known nocturnal formation processes. Observations of organochlorines in the gas and particle phases reflect the contribution of chlorine chemistry to the formation of secondary pollutants in the area. Box modeling results suggest that the formation of ozone at this location is influenced by chlorine chemistry. These results suggest that UOGD can be an important source of reactive chlorine in the atmosphere, impacting radical budgets and the formation of secondary pollutants in these regions.

Isoprene-Chlorine Oxidation in the Presence of NOx and Implications for Urban Atmospheric Chemistry.

Fine particulate matter (PM2.5) is a key indicator of urban air quality. Secondary organic aerosol (SOA) contributes substantially to the PM2.5 concentration. Discrepancies between modeling and field measurements of SOA indicate missing sources and formation mechanisms. Recent studies report elevated concentrations of reactive chlorine species in inland and urban regions, which increase the oxidative capacity of the atmosphere and serve as sources for SOA and particulate chlorides. Chlorine-initiated oxidation of isoprene, the most abundant nonmethane hydrocarbon, is known to produce SOA under pristine conditions, but the effects of anthropogenic influences in the form of nitrogen oxides (NOx) remain unexplored. Here, we investigate chlorine-isoprene reactions under low- and high-NOx conditions inside an environmental chamber. Organic chlorides including C5H11ClO3, C5H9ClO3, and C5H9ClO4 are observed as major gas- and particle-phase products. Modeling and experimental results show that the secondary OH-isoprene chemistry is significantly enhanced under high-NOx conditions, accounting for up to 40% of all isoprene oxidized and leading to the suppression of organic chloride formation. Chlorine-initiated oxidation of isoprene could serve as a source for multifunctional (chlorinated) organic oxidation products and SOA in both pristine and anthropogenically influenced environments.