Assessment of VOCs emission inventory in Seoul through spatiotemporal observations using passive and online PAMS measurements

We have conducted a quantitative analysis of volatile organic compounds (VOCs) in Seoul from September 2022 to June 2023, employing passive air samplers (PAS) at 25 sites and continuous monitoring at five photochemical assessment monitoring stations (PAMS). Comparing VOCs concentrations and compositions from PAS and PAMS during the same time periods, we found that most VOCs showed no significant difference (p-value >0.05) between the methods, except for olefins, which were overestimated by 24 % in passive sampling, confirming PAS as an effective tool for assessing the spatial distribution of VOCs species over large areas. Throughout Seoul, median values of total volatile organic compounds (TVOCs) concentrations collected with passive samplers remained stable with a standard deviation of 1.22 ppbv, typically ranging from 11 to 13 ppbv, except for an increase during winter in the southwestern regions of the city, where intense industrial and vehicular emissions are reported in the current Clean Air Policy Support System (CAPSS) emissions inventory. Positive matrix factorization (PMF) analysis using the passive data revealed general consistency in the spatial distribution of area and road emissions when compared with CAPSS emission inventory, although localized discrepancies were observed. In quantitative assessments of TVOCs comparing PAS observations with emission-based models, modeled values were within 1.5 times the interquartile range of observed PAS concentrations over Seoul. However, the lack of detection of emission hotspots in southeastern Seoul in the PAS data, coupled with the omission of photochemical loss in our dispersion-only models, indicates that the current CAPSS emission inventory may significantly underestimate actual ambient VOCs levels, especially in summer. • Passive air sampling effectively mapped the spatial distribution of VOCs across Seoul. • PMF factors reasonably matched the spatial distributions of area and road emissions. • Notable winter increases in VOCs were observed in the industrial and commercial areas. • Current emission inventory overestimates aromatic composition including benzene. • The study identified an underestimation of VOCs emissions, particularly during summer.