Impacts of rapidly urbanizing watershed comprehensive management on per- and polyfluoroalkyl substances pollution: Based on PFAS "diversity" assessment

The impact of watershed comprehensive management (WCM) on per- and polyfluoroalkyl substances (PFAS) pollution in rapidly urbanizing areas remains unclear. In a typical rapidly urbanizing watershed of Shenzhen, China, we investigated temporal variations in contamination level, primary source and ecological risk of 50 emerging and legacy PFAS, as well as the replacement trends of emerging PFAS before and after WCM during a six-year sampling campaign. We found that large-scale dredging was a non-negligible factor in abnormally increased PFAS concentrations (6.43 %-456.16 %) during WCM through their release from river sediments. To better characterize the diverse and complex PFAS contamination, a novel pollution assessment method, PFAS "diversity", was adopted based on a modified Shannon-Weiner diversity index and Pielou evenness index, reflecting numbers of PFAS detected and how evenly each PFAS contributed to the total PFAS concentrations at specific sampling sites. Importantly, we found that the Pielou evenness index can indicate and quantify abnormal pollution sources (especially point sources) along the river. The results revealed that WCM did not effectively reduce total PFAS concentrations and diversity in the rapidly urbanizing watershed but obviously improved point source pollution. Furthermore, 6:2 polyfluorinated phosphate diesters and hexafluoropropylene oxide dimer acid (GenX) that posed high ecological risks emerged and the number of sampling sites with high risk increased from 16 to 20 after WCM. Finally, we summarize several important issues related to PFAS contamination during WCM and propose specific countermeasures, such as adopting environmental dredging and reducing the proportion of ecological water replenished by wastewater treatment plant effluent for better control of PFAS pollution. Our study highlighted the limited effectiveness of WCM in mitigating PFAS pollution and the importance of emerging contaminant regulation in rapidly urbanizing watersheds during WCM.