Nitrate dynamics and source identification of rainwater in Beijing during rainy season: Insight from dual isotopes and Bayesian model

Anthropogenic reactive nitrogen emissions have a significant impact on atmospheric chemical composition and earth surface ecosystem. As one of the most important sinks of atmospheric nitrogen, the wet deposition of nitrate (rainwater NO3-) has been widely concerned. Yet, the sources and transformation processes of wet deposited NO3- were not well revealed in megacity during rainy season in the context of global climate change. Here, we investigated the concentrations of nitrogen components and dual isotopes of rainwater nitrate collected in Beijing during July to August 2021 (rainy season). The main findings showed that the concentrations of NH4+-N, NO3--N, and NO2--N ranged 0.5- 6.7 mg L-1, 0.3- 4.5 mg L-1, and 0.05- 0.18 mg L-1, respectively, with the average relative percentages of 69 %, 29 %, and 2 %. The stoichiometry analysis of characteristic ion ratios indicated that the contribution of municipal wastes and agricultural sources to rainwater NH4+-N is relatively significant, while traffics were the major contributor of NO3--N instead of the fixed emission. Rainwater delta 15N-NO3- and delta 18O-NO3- presented slightly 15N-depleted characteristic compared to previous studies with the average values of -3.9 +/- 3.1 parts per thousand and 58.7 +/- 12.6 parts per thousand. These isotope compositions suggesting an origin of rainwater NO3- from the mixing of multi-sources and was mainly generated via the pathway of OH radical oxidization. Further source apportionment of rainwater NO3- by Bayesian mixing model evaluated that traffic (30.3 %) and soil (30.3 %) emissions contributed mostly to NO3-, while the contribution of biomass burning (18.8 %) and coal combustion (20.6 %) were relatively lower. This study highlighted the important role of dual isotopes in rainwater nitrate source identification and formation processes in megacity.