Passive air sampling of halogenated polycyclic aromatic hydrocarbons in the largest industrial city in Korea: Spatial distributions and source identification

Some halogenated polycyclic aromatic hydrocarbons (Halo-PAHs) are known to be more toxic than their corresponding parent PAHs, but studies on Halo-PAHs have been somewhat limited. In this study, passive air samplers were used to monitor Halo-PAH and PAH contamination at 20 sampling sites in Ulsan, one of the largest industrial cities in South Korea. The mean concentrations of Sigma(24) ClPAHs, BrPAHs, and Sigma(13) PAHs were 207 pg/m(3), 84 pg/m(3), and 26 ng/m(3), respectively. Industrial areas displayed higher concentrations of both Halo-PAHs and PAHs than urban and rural areas. Strong correlations between energetically unfavorable Halo-PAHs and their corresponding parent PAHs suggest that the main formation mechanism of Halo-PAHs is not direct halogenation of PAHs. Low molecular weight Halo-PAHs with one halogen atom and their parent PAHs were dominant. The profiles of ClPAHs and BrPAHs in petrochemical, automobile, shipbuilding, and non-ferrous industrial complexes were distinguished. The toxicity equivalency quantities (TEQs) of ClPAHs, BrPAHs, and PAHs at the industrial sites also showed the highest values of 4.2, 0.5, and 18.3 pg-TEQ/m(3), respectively, reflecting the high toxicity of Halo-PAHs. To the best of our knowledge, this is the first study reporting atmospheric levels of both ClPAHs and BrPAHs using passive air samplers.