| Summary: | We measured a wide range of hazardous air pollutants (HAPs) simultaneously at five sites over four seasons in 2009–2010 in Ulsan, the largest industrial city in Korea. Target analytes included volatile organic compounds (VOCs), carbonyls, polycyclic aromatic hydrocarbons (PAHs), phthalates, and heavy metals (HMs). The objectives of this study were to evaluate the occurrence and spatiotemporal distributions of HAPs, and to identify important HAPs based on health risk assessment. Industrial emissions affected ambient levels of VOCs and HMs, as demonstrated by spatial distribution analysis. However, concentrations of PAHs and phthalates were relatively uniform at all sites. VOCs and HMs exhibited little seasonal variation, while formaldehyde increased in the summer due to its secondary formation. PAHs exhibited notable seasonal variation; higher in cold seasons and lower in warm seasons. Cumulative cancer risks imposed by 35 HAPs were 4.7 × 10<sup>−4</sup> and 1.7 × 10<sup>−4</sup> in industrial and residential areas, respectively. The top five major cancer risk drivers appeared to be formaldehyde, benzene, benzo[a]pyrene, As, and Co. The sums of hazard quotients (HQ) derived by 47 HAPs were 10.0 (industrial) and 2.4 (residential). As the individual species, only two HAPs exceeded the HQ of 1, which are As (3.1) and Pb (2.1) in the industrial area. This study demonstrated the importance of a comprehensive monitoring and health risk assessment to prioritize potentially toxic pollutants in the ambient air of a large industrial city.
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