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 odor nuisance of urban surface water after rainfall events has aroused public concerns and threaten the aquatic organisms. Herein, the first study to investigate 150 odorants in storm sewer discharge was performed in humid regions of China. During rainfall events, the total concentrations of odorants at storm sewer outlet increased by 1.3–2.1 fold from 1.7–9.4 μg/L to 2.1–20.0 μg/L with 37 odorants having detection frequencies above 50 % on rainy days, and the concentrations of total odorants in air also significantly increased resulting in worse odor nuisance. The accumulation of odorants in sewer sediment and the remobilization of sewer sediment were factors resulting in more intensified emission of odorants from storm sewer on rainy days. More than half of odorants discharged during rainfall were contributed by sewer sediment. Thioethers, indoles, 2-isopropyl-3‑methoxy pyrazine, acetophenone and coumarin exhibited high sediment-accumulation. Quantitative structure-property relationship models revealed that enhanced sediment-accumulation of chained aliphatic and aromatic odorants can be explained by the electrostatic attraction and topological characteristic, respectively. The multicriteria analysis was further introduced for relative odorants ranking by considering the variations in hazard criteria of environmental occurrence, ecotoxicity, persistence, odor nuisance and sediment accumulation. Among priority odorants, thioethers and indoles were attributed by their distinct sediment-accumulation and odor nuisance potential, while chlorinated anisole and pinenes prioritized due to their higher ecotoxicity. These findings provide novel insights into the odorants from storm sewer discharges and explore the environmental behaviors of odorants in sewer sediment.

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.

The illicit connection of sewage pipes to stormwater pipes commonly occurs in urban stormwater systems. This brings problems that sewage might be directly discharges into natural water and even drinking water sources without treatment, posing risks to ecological safety. Sewage contains various unknown dissolved organic matter (DOM), which could react with disinfectants and lead to the formation of carcinogenic disinfection byproducts (DBPs). Thus, understanding the impacts of illicit connections on downstream water quality is of significance. This study firstly investigated the characteristics of DOM using fluorescence spectroscopy and the formation of DBPs after chlorination in an urban stormwater drainage system in the case of illicit connections. The results found that the concentrations of dissolved organic carbon and dissolved organic nitrogen ranged from 2.6 to 14.9 mg/L and from 1.8 to 12.6 mg/L, respectively, with the highest levels occurring at the illicit connection points. Concerning DBP precursors, pipe illicit connections introduced considerable precursors of highly toxic haloacetaldehydes and haloacetonitriles into the stormwater pipes. Furthermore, illicit connections introduced more contents of tyrosine-like and tryptophan-like aromatic proteins, which may be related to foods, nutrients, personal care products, etc. in the untreated sewage. This indicated that the urban stormwater drainage system was a significant input source of DOM and DBP precursors to natural water. The results of this study are of great significance for protecting the security of water sources and promoting the sustainability of urban water environment.