Nocturnal downward transport of NO3 radical from the residual layer to a surface site by the mountain breeze in Seoul, South Korea

Abstract

Using the long-path differential optical absorption spectroscopy (LP-DOAS) technique, the nocturnal mixing ratios of NO3 radicals were measured at an urban site in Seoul, South Korea, from May 13 to June 12, 2022. The primary objectives of the study were to estimate the NO3 radical concentration in the nighttime boundary layer and to examine the variations in their generation and loss over time, including an evaluation of their sources and sinks. The observed mean NO3 mixing ratios and lifetimes were 16 pptv and 73 s, respectively. NO3 concentrations and lifetimes were closely associated with their production, involving O3 and NO2, as well as the loss processes regulated by NO, VOCs, and aerosol surface area. Applying the steady-state assumption for NO3 and N2O5, the mean N2O5 uptake coefficient on the aerosol surface for the entire period was 0.031. When foggy nights were excluded from the analysis, the uptake coefficient decreased to 0.025. These values are within the higher range of the results reported in other studies. High relative humidity, which averaged 75% at night throughout the collection period, favored high N2O5 uptake coefficients. NO3 concentrations generally peaked shortly after sunset and gradually declined until sunrise. However, we frequently observed distinct increases in NO3 throughout the early morning hours, especially during clear nights, when local circulation with the westerly mountain breeze prevailed at the research site. The mountain breeze transported residual air downward, resulting in 110% and 38% higher NO3 and O3 levels at the sampling locations, respectively, compared to normal conditions. This additional source of nocturnal radicals and O3 has consequences for increased secondary aerosols and O3 production, particularly at urban surface levels where they are readily depleted in the early morning hours. To this end, a more thorough examination is required to measure N2O5 and a larger spectrum of VOCs species, as these parameters are crucial for nighttime radical budgets, secondary aerosols, and O3 generation in cities like Seoul.