Examining the impact of nitryl chloride chemistry on summertime air quality

Abstract

Results of recent field campaigns suggest that heterogeneous reactions can form nitryl chloride (ClNO2) at night. ClNO2 photodissociates into nitrogen dioxide and chlorine radicals during the day. Subsequent photolysis of nitrogen dioxide and reactions of chlorine radicals with volatile organic compounds increase ozone production. Thus, the presence of ClNO2 in the atmosphere can enhance ozone. In this study, the impact of the heterogeneous production of ClNO2 on summertime air quality in the United States is examined by using the Community Multiscale Air Quality (CMAQ) model. Laboratory chamber experimental studies have parameterized the yield of ClNO2 and the heterogeneous uptake of dinitrogen pentoxide on aerosols. We implement these parameterizations into the CMAQ model. In addition to the typical emissions, the model also includes emissions of sea-salt, anthropogenic particulate chloride, anthropogenic hydrochloric acid and molecular chlorine from the National Emissions Inventory. Model simulations are conducted without and with the heterogeneous ClNO2 formation reaction for September 1-10, 2006. The results of the study suggest that the heterogeneous reaction produces ClNO2 in many coastal areas as well as inland locations in the United States. The ClNO2 increase in coastal areas is caused by chloride emissions from sea-salt and in inland-areas by chloride emissions from fire and anthropogenic sources. Predicted ClNO2 levels reach nighttime peaks of up to 4.0 ppb in the Los Angeles area and up to 1.2 ppb near Houston, similar to the measured values reported in the literature. The ClNO2 chemistry decreases nitric acid as well as particulate nitrate by a large margin; consequently it changes composition of NOz. It increases hourly and daily maximum 8-hr ozone by up to 9 ppbv and 6 ppbv, respectively. It increases aerosol sulfate while decreasing aerosol nitrate and ammonium. The accompanying presentation identifies predicted spatial patterns of ClNO2 concentrations across the United States and describes the detailed impact of the ClNO2 chemistry on ozone, nitric acid, sulfate, particulate nitrate, ammonium, and particulate chloride. To evaluate the impact of the ClNO2 chemistry on an ozone control strategy, two additional model simulations were conducted with reduced NOx emissions. Relative response factors were determined without and with the ClNO2 chemistry; the accompanying presentation discusses the impact on ozone control strategy.