Distinct seasonal variability of source-dependent health risks from PM-bound PAHs and related derivatives in a megacity, southwest China: Implications for the significance of secondary formation.

In contrast to polycyclic aromatic hydrocarbons (PAHs) which have been regularly monitored, the source-dependent health risk of their derivatives in ambient environment has not been well understood, especially regarding seasonal variability. In this study, oxygenated and nitrated PAHs (OPAHs and NPAHs) in PM samples from different seasons in urban Chongqing were analyzed and compared with PAHs from a human health perspective. Benzo[a]pyrene equivalent concentrations (BaP) were annually averaged at 6.13 ± 8.97 ng/m (n = 118) in the present study, with highest levels in winter followed by spring, autumn, and summer. The BaP values of OPAHs were higher than PAHs in spring and summer with seasonal averaged value up to 3.7 times of that for PAHs, manifesting significant underestimation of the health impact if only PAHs were considered. Incremental lifetime cancer risk (ILCR) model results suggested that the potential cancer risks were accumulated mostly from inhalation exposure during infancy and adulthood. Furthermore, in comparison with PAHs, OPAHs, mainly 6H-Benzo[c,d]pyren-6-one, had significant contribution to cancer risks (annually averaged at 58.3 %). Source-dependent cancer risks based on positive matrix factorization model denoted secondary formed PAH derivatives as a critical contributor to cancer risk, particularly in spring and summer (attributed to about 61 % of ILCR). The enhanced secondary formation of PAH derivatives during spring and summer was partially justified by diagnostic ratios and further analysis revealed that higher temperature, higher O level, and lower relative humidity besides stronger solar intensity during these two seasons as the most likely causes of this seasonal variation. Results in this study emphasizes that more knowledge on the formation and toxicity of OPAHs is imperative, especially in the context of complex PM-ozone pollution in China.