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Nitrate (NO3−), which is mainly oxidized from NO2 by the OH radical (OH·) and O3 in the atmosphere, is a major component of inorganic aerosols. However, the contributions of the OH· and O3 pathways to NO3− in urban aerosols and the influence of air pollution to both pathways remain unclear. Oxygen isotopes of NO3− were measured for PM2.5 in Beijing in 2014. The Δ17O‐NO3− values (17.0–32.8‰) were significantly higher in winter (27.2 ± 3.6‰) than in summer (24.2 ± 1.3‰). By estimating contributions of O3 to the NOx cycle, the Δ17O values of NO3− endmembers produced via the NO2 + OH· (P1), NO3· + DMS/HC (P2), and N2O5 hydrolysis (P3) pathways were calculated for each observation. The contributions of the three pathways (P1: 32 ± 10%, P2: 34 ± 10%, and P3: 34 ± 20% annually) were calculated using the Stable Isotope Analysis in R model. We found that NO3− formation was dominated by the O3 oxidation pathways (P2 + P3; 68 ± 23% annually, 73 ± 21% in spring, 59 ± 23% in summer, 75 ± 20% in autumn, and 69 ± 22% in winter). Moreover, PM2.5, NO2, and NO3− pollution decreased the importance of the OH· pathway relative to the O3 pathways for NO3− production. However, O3 pollution increased the importance of the OH· pathway relative to the O3 pathways for NO3− production. These results provided a comprehensive analysis on the oxygen isotope records in particulate NO3− for understanding the relative importance of major oxidation pathways of NO2. Atmospheric pollution substantially influenced the pathways of NO2 oxidation to NO3− in city environments.

Large-scale and rapid improvement in wastewater treatment is common practice in developing countries, yet this influence on nutrient regimes in receiving waterbodies is rarely examined at broad spatial and temporal scales. Here, we present a study linking decadal nutrient monitoring data in lakes with the corresponding estimates of five major anthropogenic nutrient discharges in their surrounding watersheds over time. Within a continuous monitoring dataset covering the period 2008 to 2017, we find that due to different rates of change in TN and TP concentrations, 24 of 46 lakes, mostly located in China’s populated regions, showed increasing TN/TP mass ratios; only 3 lakes showed a decrease. Quantitative relationships between in-lake nutrient concentrations (and their ratios) and anthropogenic nutrient discharges in the surrounding watersheds indicate that increase of lake TN/TP ratios is associated with the rapid improvement in municipal wastewater treatment. Due to the higher removal efficiency of TP compared with TN, TN/TP mass ratios in total municipal wastewater discharge have continued to increase from a median of 10.7 (95% confidence interval, 7.6 to 15.1) in 2008 to 17.7 (95% confidence interval, 13.2 to 27.2) in 2017. Improving municipal wastewater collection and treatment worldwide is an important target within the 17 sustainable development goals set by the United Nations. Given potential ecological impacts on biodiversity and ecosystem function of altered nutrient ratios in wastewater discharge, our results suggest that long-term strategies for domestic wastewater management should not merely focus on total reductions of nutrient discharges but also consider their stoichiometric balance.

Moss N isotope (δ(15)N(bulk)) has been used to monitor N deposition, but it remains questionable whether inhibition of nitrate reductase activity (NRA) by reduced dissolved N (RDN) engenders overestimation of RDN in deposition when using moss δ(15)N(bulk). We tested this question by investigation of δ(15)N(bulk) and δ(15)NO(3)(-) in mosses under the dominance of RDN in N depositions of Guiyang, SW China. The δ(15)N(bulk) of mosses on bare rock (-7.9‰) was unable to integrate total dissolved N (TDN) (δ(15)N = -6.3‰), but it reflected δ(15)N-RDN (-7.5‰) exactly. Moreover, δ(15)N-NO(3)(-) in mosses (-1.7‰) resembled that of wet deposition (-1.9‰). These isotopic approximations, together with low isotopic enrichment with moss [NO(3)(-)] variations, suggest the inhibition of moss NRA by RDN. Moreover, isotopic mixing modeling indicated a negligible contribution from NO(3)(-) to moss δ(15)N(bulk) when the RDN/NO(3)(-) reaches 3.8, at which maximum overestimation (21%) of RDN in N deposition can be generated using moss δ(15)N(bulk) as δ(15)N-TDN. Moss δ(15)N-NO(3)(-) can indicate atmospheric NO(3)(-) under distinctly high RDN/NO(3)(-) in deposition, although moss δ(15)N(bulk) can reflect only the RDN therein. These results reveal pitfalls and new mechanisms associated with moss isotope monitoring of N deposition and underscore the importance of biotic N dynamics in biomonitoring studies.

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Studies of wintertime air quality in the North China Plain (NCP) show that particulate‐nitrate pollution persists despite rapid reduction in NOx emissions. This intriguing NOx‐nitrate relationship may originate from non‐linear nitrate‐formation chemistry, but it is unclear which feedback mechanisms dominate in NCP. In this study, we re‐interpret the wintertime observations of 17O excess of nitrate (∆17O(NO3−)) in Beijing using the GEOS‐Chem (GC) chemical transport model to estimate the importance of various nitrate‐production pathways and how their contributions change with the intensity of haze events. We also analyze the relationships between other metrics of NOy chemistry and [PM2.5] in observations and model simulations. We find that the model on average has a negative bias of −0.9‰ and −36% for ∆17O(NO3−) and [Ox,major] (≡ [O3] + [NO2] + [p‐NO3−]), respectively, while overestimating the nitrogen oxidation ratio ([NO3−]/([NO3−] + [NO2])) by +0.12 in intense haze. The discrepancies become larger in more intense haze. We attribute the model biases to an overestimate of NO2‐uptake on aerosols and an underestimate in wintertime O3 concentrations. Our findings highlight a need to address uncertainties related to heterogeneous chemistry of NO2 in air‐quality models. The combined assessment of observations and model results suggest that N2O5 uptake in aerosols and clouds is the dominant nitrate‐production pathway in wintertime Beijing, but its rate is limited by ozone under high‐NOx‐high‐PM2.5 conditions. Nitrate production rates may continue to increase as long as [O3] increases despite reduction in [NOx], creating a negative feedback that reduces the effectiveness of air pollution mitigation.