Until now, there has been a lack of knowledge regarding the vertical profiles of nitrate formation in the urban boundary layer (BL) based on triple oxygen isotopes. Here, we conducted vertical measurements of the oxygen anomaly of nitrate (Δ 17 O-NO 3 − ) on a 325 m meteorological tower in urban Beijing during the winter and summer. The simultaneous vertical measurements suggested different formation mechanisms of nitrate aerosols at ground level and 120 and 260 m in the winter due to the less efficient vertical mixing under stable atmospheric conditions. Particularly, different chemical processes of nitrate aerosols at the three heights were found between clean days and polluted days in the winter. On clean days, nocturnal chemistry (NO 3 + HC and N 2 O 5 uptake) contributed to nitrate production equally with OH/H 2 O + NO 2 at ground level, while it dominated aloft (contributing 80% of nitrate production at 260 m), due to the higher aerosol liquid water content and O 3 concentration there. On polluted days, nocturnal reactions dominated the formation of nitrate at the three heights. Particularly, the contribution of the OH/H 2 O + NO 2 pathway to nitrate production increased from the ground level to 120 m might be attributed to the hydrolysis of NO 2 to HONO and then further photolysis to OH radicals in the day. In contrast, the proportion of N 2 O 5 + H 2 O decreased at 260 m, likely due to the low relative humidity aloft that inhibited the N 2 O 5 hydrolysis reactions in the residual layer. Our results highlighted that the differences between meteorology and gaseous precursors could largely affect particulate nitrate formation at different heights within the polluted urban BL.

Inorganic nitrate production is critical in atmospheric chemistry that reflects the oxidation capacity and the acidity of the atmosphere. Here we use the oxygen anomaly of nitrate (Δ17O($$\rm{NO}_{3}^{-}$$ NO 3 − )) in high-time-resolved (3 h) aerosols to explore the chemical mechanisms of nitrate evolution in fine particles during the winter in Nanjing, a megacity of China. The continuous Δ17O($$\rm{NO}_{3}^{-}$$ NO 3 − ) observation suggested the dominance of nocturnal chemistry (NO3 + HC/H2O and N2O5 + H2O/Cl−) in nitrate formation in the wintertime. Significant diurnal variations of nitrate formation pathways were found. The contribution of nocturnal chemistry increased at night and peaked (72%) at midnight. Particularly, nocturnal pathways became more important for the formation of nitrate in the process of air pollution aggravation. In contrast, the contribution of daytime chemistry (NO2 + OH/H2O) increased with the sunrise and showed a highest fraction (48%) around noon. The hydrolysis of N2O5 on particle surfaces played an important role in the daytime nitrate production on haze days. In addition, the reaction of NO2 with OH radicals was found to dominate the nitrate production after nitrate chemistry was reset by the precipitation events. These results suggest the importance of high-time-resolved observations of Δ17O($$\rm{NO}_{3}^{-}$$ NO 3 − ) for exploring dynamic variations in reactive nitrogen chemistry.

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