Day–night variation, size distribution, source identification, and health risk of polycyclic aromatic hydrocarbons in particulate matter in Ulsan, South Korea

Particulate matter (PM) in 11 different sizes was collected at a semi-rural site in Ulsan, a multi-industrial city in South Korea, over one year from 2019 to 2020 to investigate the temporal patterns in size distribution and potential sources of polycyclic aromatic hydrocarbons (PAHs). The mean concentration of Σ21 PAHs was higher in winter (0.29 and 0.45 ng/m3 for coarse and fine PM, respectively) than in summer (0.06 and 0.07 ng/m3). Although there was no statistically significant difference between day and night for the concentration of individual PAHs in both coarse and fine PM, the concentrations were generally higher during the day than at night. During the day, Σ21 PAHs had two distinct peaks (0.056–0.10 μm and 3.20–5.60 μm) in winter, but they tended to partition to larger particles (1.00–1.80 μm and > 18.0 μm) in summer. This result suggests that the volatilization of PAHs in smaller particles was enhanced by high-temperature conditions in summer, followed by their condensation onto larger particles. At night, Σ21 PAH peaks were mainly around the size of 0.7 μm (droplet mode), suggesting the importance of heterogeneous-aqueous reactions. The results of the conditional bivariate probability function and concentration-weighted trajectory indicate that the high concentrations of PAHs in summer and winter were more affected by local pollution and long-range atmospheric transport, respectively. The results of the health risk assessment demonstrate that PAHs in fine PM contributed significantly to cancer risk compared to those in coarse PM. In conclusion, investigating the size distribution of PAHs in particles is necessary to understand their environmental behaviors and evaluate potential health risks.