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.