Rayleigh based concept to track NOx emission sources in urban areas of China.

Despite the implementation of some effective measures to control emissions of nitrogen oxides (NOx = NO + NO2) in recent years, the ambient NOx concentration in urban cities of China remains high. Therefore, a quantitative understanding of NOx emission sources is critical to developing effective mediation policies. In the present study, the dual isotopic compositions of nitrate (p-NO3-) in fine-particle aerosol (PM2.5) collected daily at a regional scale (Beijing-Tianjin-Shijiazhuang) were measured to better constrain the NOx emission sources. The specific focus was on a typical haze episode that occurred simultaneously in the three urban cities (October 22-29, 2017). It was found that the nitrogen isotopic values of nitrate in PM2.5 (hereafter as δ15N-NO3-) ranged widely from -3.1‰ to + 11.4‰, with a mean value of 3.5 ± 3.7‰. Furthermore, a negative relationship between the δ15N-NO3- values and the corresponded p-NO3- concentrations during the haze period was observed. This implied the preferential formation of 15N-enriched NO3- into a fine-particle aerosol. Taking a different approach to previous publications, the Rayleigh fractionation model was used to characterize the initial isotopic signatures of ambient NOx. After accounting for the δ15N difference between p-NO3- and the source NOx, the estimated initial δ15N-NOx ranged from -20‰ to 0‰, which indicated a cosniderable contribution of non-fossil fuel emissions. The individual contributions of potential sources were further quantified using the Bayesian mixing model, revealing that NOx from coal or natural gas combustion, vehicle exhausts, biomass burning, and the microbial activity contributed 17.9 ± 11.4%, 29.4 ± 19.6%, 29.1 ± 18.9% and 23.5 ± 12.7% to NO3- in PM2.5, respectively. These results highlighted that tightening controls of gaseous NOx emissions from non-fossil sources may represent an opportunity to mitigate PM2.5 pollution in urban cities of China.