Exploring the long-term variations and high concentration episodes of peroxyacetyl nitrate in Megacity Seoul

Over the past few years, peroxyacetyl nitrate (PAN) has drawn significant attention as a key indicator of photochemical pollution owing to its intimate relationship with ozone and associated health effects. This study presents measurements conducted at the Korea University campus in Seoul during the high-ozone seasons from 2018 to 2021. PAN concentration was measured using fast gas chromatography with luminol chemiluminescence detection (GC-LCD), alongside measurements of O 3 , volatile organic compounds (VOCs), NO, NO 2 , and meteorological variables, including boundary layer height (BLH). The mean concentrations of PAN and O 3 over the years were 0.56 ppbv and 35 ppbv in 2018, 1.29 ppbv and 58 ppbv in 2019, 0.21 ppbv and 50 ppbv 2020, and 0.53 ppbv and 46 ppbv in 2021, respectively. The annual variation observed in Seoul is consistent with trends seen in major cities worldwide during the COVID19 pandemic, reflecting a substantial reduction in urban emissions. Notably, the mean concentration of NOx and VOCs decreased significantly by more than 50 % and 25%, respectively, from 2019 to 2021. At temperatures above 30 °C, PAN decomposition was accelerated, decoupling a consistent positive relationship between PAN and O 3 in 2020 and 2021. The results of a 0-D photochemical model (F0AM) calculation demonstrated that PAN formation primarily stems from anthropogenic VOCs, particularly > C2 alkenes. Elevated PAN concentrations during nighttime were attributed to boundary layer expansion and upper-air entrainment. Instances where PAN concentrations surged to at least 3 ppbv or higher in 2019 were attributed to biomass burning impacted air, as evidenced by concurrent elevations in K + and OC in PM 2.5 , and O 3 . This study underscores the complex interplay of factors influencing PAN and ozone enhancements under decreased precursor levels, with an emphasis on dynamic change in the boundary layer, and long-distance transport of non-fossil sources during agricultural burning seasons. • PAN variations correlate mainly with precursor changes, with very high PAN levels occurring under specific conditions. • Evening PAN and O 3 surges linked to a sudden rise in boundary layer, suggesting PAN-rich air entrainment from upper layers. • PAN rises with PM2.5 in continental outflow, making PAN a strong photochemical indicator of secondary pollutants.