Efficient N₂O₅ uptake and NO₃ oxidation in the outflow of urban Beijing

Abstract

Nocturnal reactive nitrogen compounds play an important role in regional air pollution. Here we present the measurements of dinitrogen pentoxide (N2O5) associated with nitryl chloride (ClNO2) and particulate nitrate (pNO3−) at a suburban site of Beijing in the summer of 2016. High levels of N2O5 and ClNO2 were observed in the outflow of the urban Beijing air masses, with 1 min average maxima of 937 and 2900 pptv, respectively. The N2O5 uptake coefficients, γ, and ClNO2 yield, f, were experimentally determined from the observed parameters. The N2O5 uptake coefficient ranged from 0.012 to 0.055, with an average of 0.034 ± 0.018, which is in the upper range of previous field studies reported in North America and Europe but is a moderate value in the North China Plain (NCP), which reflects efficient N2O5 heterogeneous processes in Beijing. The ClNO2 yield exhibited high variability, with a range of 0.50 to unity and an average of 0.73 ± 0.25. The concentration of the nitrate radical (NO3) was calculated assuming that the thermal equilibrium between NO3 and N2O5 was maintained. In NOx-rich air masses, the oxidation of nocturnal biogenic volatile organic compounds (BVOCs) was dominated by NO3 rather than O3. The production rate of organic nitrate (ON) via NO3 + BVOCs was significant, with an average of 0.10 ± 0.07 ppbv h−1. We highlight the importance of NO3 oxidation of VOCs in the formation of ON and subsequent secondary organic aerosols in summer in Beijing.