Stable oxygen isotope constraints on nitrate formation in Beijing in springtime

Rapid accumulation of aerosol nitrate (NO₃^-) contributes to haze pollution; however, studies quantifying NO₃^- formation mechanisms remain scarce. To explore aerosol nitrate formation pathways, total suspended particulate (TSP) samples were collected in Beijing during the spring of 2013, and the concentration of NO₃^- and δ¹⁸O- NO₃^- value were analyzed. The NO₃^- concentrations on polluted days (PD) were higher than those on non-polluted days (NPD). Furthermore, higher δ¹⁸O- NO₃^- values were observed on PD (86.8 ± 8.1‰) as compared with NPD (73.7 ± 11.0‰) suggest that more nitrate was produced by pathways with relative high δ¹⁸O-HNO₃ values during PD. Based on the calculated δ¹⁸O-HNO₃ values from different formation pathways and the observed δ¹⁸O- NO₃^- values, the possible fractional contributions of HNO₃ formed via various pathways to TSP NO₃^- were estimated using the Bayesian isotope mixing model. The δ¹⁸O- NO₃^- constrained calculations suggest that the pathways of N₂O₅ + H₂O/Cl^-, NO₃ + VOCs, and ClNO₃ + H₂O possibly contributed 53%-89% to nitrate production during PD. During NPD, the NO₂ + OH pathway produced 37%-69% of the NO₃^-. Using the δ¹⁸O- NO₃^- value combined with the isotope mixing model is a promising approach for exploring NO₃^- formation pathways.