Distribution and ecological risk of substituted and parent polycyclic aromatic hydrocarbons in surface waters of the Bai, Chao, and Chaobai rivers in northern China

Like their parent polycyclic aromatic hydrocarbons (PAHs), substituted polycyclic aromatic hydrocarbons (SPAHs), including methyl PAHs (MPAHs), oxygenated PAHs (OPAHs), and chlorinated PAHs (ClPAHs), exist ubiquitously in urban and agricultural rivers. Although laboratory studies have found the biological toxicities of certain SPAHs to be higher than that of their parent PAHs, the ecological risk of SPAHs in rivers has been largely ignored. Here, we studied the distribution, source and transport of PAHs and SPAHs as well as ecological risks in the Chaobai River System, which experiences a high level of anthropogenic activity. The results show that the concentration of ΣOPAHs (321 ± 651 ng/L) was higher than that of ΣPAHs (158 ± 105 ng/L), ΣMPAHs (28 ± 22 ng/L), and ΣClPAHs (30 ± 12 ng/L). We also found that (S)PAHs in Chaobai River mainly originated from Beiyun River (53%–65%), which receives considerable municipal wastewater treatment plant effluent from Beijing. The major transport pathway of (S)PAHs from Chaobai River was likely for irrigation (83%–86%) and transportation into Yongdingxin River (13%–16%), which finally merged into the Bohai Sea. The mixed chronic risk of (S)PAHs (risk quotient = 45 ± 53) was higher than the mixed acute risk (risk quotient = 1.9 ± 1.4), with all sites facing chronic risk and 90% of sites experiencing acute risk. Although the chronic and acute risks of (S)PAHs to plants, invertebrates, and vertebrates were mainly from PAHs (97.5% to chronic risk and 96.5% to acute), SPAHs still posed a chronic risk to invertebrates and vertebrates (risk quotient > 1). Accordingly, the ecological risk of (S)PAHs in Chaobai River should be taken into consideration for ecosystem protection. The transmission of PAHs and SPAHs from Chaobai River may also pose potential risks to farmland through irrigation, as well as to the Bohai Sea via river water discharge.