Changes in NO3 Radical and Its Nocturnal Chemistry in Shanghai From 2014 to 2021 Revealed by Long‐Term Observation and a Stacking Model: Impact of China's Clean Air Action Plan

Nitrate radical (NO3), an important nocturnal tropospheric oxidant, was observed continuously in the eastern Chinese megalopolis of Shanghai from July 2018 to August 2021using differential optical absorption spectroscopy equipped with LED lamp. To assess changes in NO3 radical during the implementation of China's Clean Air Action Plan, a stacking model was developed to predict historical NO3 radical from 2014 to 2018 with good performance. Combining the observed and predicted data sets, the highest concentration of NO3 exceeded 300 pptv in 2021, while the highest monthly mean of 36.2 ± 30.9 pptv occurred in summer 2017. The impact of meteorology, precursors, and emissions on the evolution of nocturnal NO3 was quantified using the Kolmogorov‐Zurbenko filter. The rapid increase in annual NO3 from 2014 to 2017 was caused by a combination of persistently high precursor O3 concentrations, insufficient SO2‐represented primary pollutant reductions, and meteorological conditions favorable to NO3. As China's clean air actions advanced further, significant CO‐represented and SO2‐represented emission reductions overcame the impact of meteorological conditions and significantly lowered the NO3 levels between 2018 and 2021. These efforts drastically affected nocturnal NO3 chemistry, reducing NO3 loss rates by approximately 30% in both spring and summer in 2021 compared to 2014, although the NO3 levels were comparable between the 2 years. In addition, substantial reductions in CO‐represented and SO2‐represented primary pollutants, as well as effective management of NO2 and PM2.5, resulted in varying decreases in the rates of direct (removal by reactions with VOCs, etc.) and indirect (removal by heterogeneous consumption of N2O5) losses, thereby moderating secondary aerosol formation.