Fast heterogeneous N2O5 uptake and ClNO2 production in power plant and industrial plumes observed in the nocturnal residual layer over the North China Plain

Abstract

Dinitrogen pentoxide (N2O5) and nitryl chloride (ClNO2) are key species in nocturnal tropospheric chemistry and have significant effects on particulate nitrate formation and the following day's photochemistry through chlorine radical production and NOx recycling upon photolysis of ClNO2. To better understand the roles of N2O5 and ClNO2 in the high-aerosol-loading environment of northern China, an intensive field study was carried out at a high-altitude site (Mt. Tai, 1465ma.s.l.) in the North China Plain (NCP) during the summer of 2014. Elevated ClNO2 plumes were frequently observed in the nocturnal residual layer with a maximum mixing ratio of 2.1 ppbv (1 min), whilst N2O5 was typically present at very low levels (< 30 pptv), indicating fast heterogeneous N2O5 hydrolysis. Combined analyses of chemical characteristics and backward trajectories indicated that the ClNO2-laden air was caused by the transport of NOx rich plumes from the coal-fired industry and power plants in the NCP. The heterogeneous N2O5 uptake coefficient (gamma) and ClNO2 yield (phi) were estimated from steady-state analysis and observed growth rate of ClNO2. The derived gamma and phi exhibited high variability, with means of 0.061 +/- 0.025 and 0.28 +/- 0.24, respectively. These values are higher than those derived from previous laboratory and field studies in other regions and cannot be well characterized by model parameterizations. Fast heterogeneous N2O5 reactions dominated the nocturnal NOx loss in the residual layer over this region and contributed to substantial nitrate formation of up to 17 mu gm(-3). The estimated nocturnal nitrate formation rates ranged from 0.2 to 4.8 mu g m(-3) h(-1) in various plumes, with a mean of 2.2 +/- 1.4 mu gm(-3) h(-1). The results demonstrate the significance of heterogeneous N2O5 reactivity and chlorine activation in the NCP, and their unique and universal roles in fine aerosol formation and NOx transformation, and thus their potential impacts on regional haze pollution in northern China.