Abstract
Polycyclic aromatic hydrocarbons (PAHs) and their substituted derivatives (SPAHs) are persistent organic pollutants derived from incomplete combustion of fossil fuels and industrial processes. These compounds are of global concern due to their carcinogenicity and environmental persistence. This study provides the first comprehensive analysis of PAH and SPAH contamination in Suzhou's rapidly urbanizing watersheds, integrating ultra-high-performance liquid chromatography and high-resolution mass spectrometry with multidimensional risk assessment to address critical gaps in understanding pollutant dynamics in urban aquatic systems. Key findings reveal that SPAHs were significantly more abundant than parent PAHs (mean ∑19 SPAHs = 107.43 ng/L vs. ∑8 PAHs = 48.05 ng/L), with hydroxylated derivatives accounting for 67.9% of the total SPAHs, indicating active environmental transformation processes. Source apportionment identified coal combustion and industrial emissions as the dominant contributors (58.2% of PAHs), directly linking contamination patterns to localized anthropogenic activities. Notably, industrial zones exhibited unexpected toxicity hotspots, where SPAH toxicity equivalents (e.g., 3-OH-BaP) surpassed parent PAHs 2-5-fold, demonstrating substituent-driven toxicity enhancement-a critical finding for regulatory prioritization. This study advances the field by uncovering SPAHs as emerging risks in urban waterways, challenging traditional PAH-centric monitoring frameworks, and providing a novel integration of analytical chemistry and spatial risk mapping to guide targeted pollution control (e.g., prioritizing industrial discharges and non-exhaust traffic emissions). Furthermore, it highlights the urgent need for updated toxicological databases to account for substituted PAH derivatives and advocates for the regulatory inclusion of SPAHs. These insights underscore the necessity of adapting environmental policies to address complex pollutant mixtures in rapidly developing regions, emphasizing the replicability of the proposed framework for urban watershed management.