Characteristics and health risks of parent, alkylated, and oxygenated PAHs and their contributions to reactive oxygen species from PM2.5 vehicular emissions in the longest tunnel in downtown Xi?an, China

A vehicular emission study was conducted in the longest inner-city tunnel in Xi'an, northwestern China in four time periods (I: 07:30-10:30, II: 11:00-14:00, III: 16:30-19:30, and IV: 20:00-23:00 LST). A sum of 40 PAHs, including parent (p-PAHs), alkylated (a-PAHs), and oxygenated (o-PAHs) in fine particulate matter (PM2.5) were quantified. The relationships between the PAHs and the formation of reactive oxygen species (ROS) were also studied. The average total quantified PAHs concentration was 236.3 +/- 48.3 ng m- 3. The p-PAHs were found to be the most dominated group, accounting for an average of 88.1% of the total quantified PAHs, followed by aPAHs (6.1%) and o-PAHs (5.8%). On the base of the number of aromatic rings, the groups of <= 5 rings (92.5 +/- 1.2%) had higher fractions than the high ones (>= 6 rings, 7.5 +/- 1.2%) for pPAHs. Diurnal variations of PAHs subgroups exhibited the highest levels in Period III, consistent with the largest traffic counts in evening rush hours. However, less reduction of few PAHs in the night period demonstrates that the emissions of compressed natural gas (CNG) and methanol-fueled vehicles cannot be ignored while their contribution increased. High ROS activity levels were observed in the traffic-dominated samples, implying the potential oxidative damages to humans. Additionally, diurnal variation of the ROS activity was consistent with the total quantified PAHs and toxic equivalency of benzo[a]pyrene. Good correlations (R > 0.6, p < 0.05) were seen between individual groups of PAHs (especially for 3-5 rings p-PAHs, 4 rings a-PAHs, and 2-3 rings o-PAHs) and ROS activity, supporting that the vehicular emitted PAHs possibly initiate oxidative stress. The multiple linear regression analysis further illustrated that chrysene contributed the highest (25.0%) to ROS activity. In addition to highlighting the potential hazards to the PAHs from the vehicular emission, their roles to mitigate the health effects by formations of ROS were firstly reported in northwestern China.