Persistence after prohibition: Revealing the drivers of traditional and novel organochlorine pesticide residues in river sediments

Legacy organochlorine pesticides (OCPs) persist as global environmental threats despite international bans, while novel OCPs have been widely adopted as alternatives; however, the spatiotemporal dynamics and regulatory drivers of both legacy and novel OCPs in river systems remain poorly quantified. This study revealed the spatiotemporal distribution, source contributions, drivers, and historical trends of traditional and novel OCPs in 131 river sediment samples. Total OCP concentrations (42.5 ± 25.4 ng/g dry weight [dw]) exhibited significant spatiotemporal heterogeneity, peaking during the wet season in industrial sections (industrial > suburban > urban sections). Traditional OCPs, especially dichlorodiphenyltrichloroethane and their metabolites (DDXs) dominated the contaminant profile (95.4 % of total OCPs). Isomeric ratios and Positive Matrix Factorization (PMF) model revealed 89.3 % of OCPs originated from historical residues, contrasting with 10.7 % from recent inputs. Notably, industrial sections retained technical OCPs, while degradation products (DDDs and DDEs) and pesticide-derived sources prevailed in other sections. Machine learning-driven random forest modeling identified sedimentary organic matter (SOM) compositions and anthropogenic activities as key drivers of OCP accumulation. Historical trends (2003-2019) further demonstrated the interaction of anthropogenic emissions and regulations in shaping OCP accumulation. These findings underscore the enduring legacy of historical OCPs in urbanized watersheds and expose prolonging ecological threats amplified by SOM-mediated retention. By integrating multi-source tracer (n-alkanes, PMF, and machine learning), this study advances predictive frameworks for source apportionment and provides science-based guidance for targeted sediment remediation to mitigate "forever chemical" impacts in SOM-rich and vulnerable ecosystems.