Storm-driven runoff scours accumulated sediments within stormwater drainage systems, transporting multi-source pollutants (including pathogens) into surface water through stormwater overflows, thereby elevating contamination risks in the recipient. Chlorine-based disinfection of overflowed stormwater applied in related storage tanks mitigates these risks before release. This study reveals that chlorophenylacetonitriles (CPANs), which are formed during the disinfection process, exhibit toxicity levels higher than conventional trihalomethanes and haloacetonitriles. Laboratory analyses conducted in this work demonstrated that sewer sediments — not runoff or stormwater — are the dominant precursor source for CPAN formation during overflow disinfection. Source apportionment further identified a robust linear correlation (R² = 0.95) between sediment indole concentrations (0.093–0.91 μg/g) and CPAN formation, experimentally confirming for the first time that indole is a critical precursor. Laboratory experiments also uncovered the presence of monochloroindoles in indole chlorination, a novel class of aromatic nitrogenous disinfection byproducts (DBPs). In addition, density functional theory calculations demonstrated that monochloroindole formation has lower activation energy barriers compared to CPAN pathways, resulting in new molecular-level insights into their preferential transformation. Given that indole serves as a shared precursor for both highly toxic CPANs and even more ecotoxic monochloroindoles, this study emphasizes the urgent need for sewer sediment management to mitigate the ecological and human health risks associated with these highly toxic nitrogenous DBPs.

The illicit connections between sewage and stormwater pipes result in the discharge of untreated sewage into receiving rivers, posing significant odor and health hazards. While thioethers are recognized as key odorants in sewage systems, their distribution in stormwater systems remain poorly characterized. This study analyzed 12 types of thioethers in stormwater pipes sampled at 21 sites in China. Advanced analytical techniques, including Mantel analysis and Structural Equation Modeling, were employed to examine the relationships between overlying water properties, sediment microbial characteristics, and thioether concentrations. Results showed that sediment thioether loads (36.77 ± 50.14 μg S/m; range: 7.24–99.96 μg S/m) were substantially higher than those in the overlying water (12.02 ± 42.52 μg S/m; range: 0.03–92.76 μg S/m), highlighting sediment as a critical pollution reservoir. Dissolved oxygen, NH₃-N, and terrestrial-derived dissolved organic nitrogen were identified as key factors shaping sediment microbiome composition, particularly fermentative, sulfate-reducing, and denitrifying bacteria, which in turn drives thioether formation. Specifically, dominant compounds like dimethyl disulfide and dimethyl trisulfide were found to be produced through the anaerobic fermentation of methionine and redox conversion of methanethiol, as well as the anaerobic fermentation of cysteine and methylation of polysulfides. Humic substances could facilitate methanethiol redox conversion and polysulfide methylation by serving as methyl donors and enhancing electron transfer efficiency. Additionally, NH₃-N may promote microbial metabolism by providing amino groups essential for the synthesis of metabolic precursors. Therefore, effective mitigation of odorous thioethers in stormwater systems necessitates integrated strategies targeting both sulfur-containing organic precursors and nitrogen-rich pollutants.