Legacy and Emerging Per- and Polyfluoroalkyl Substances Behave Distinctly in Spatial Distribution and Multimedia Partitioning: A Case Study in the Pearl River, China

Per- and polyfluoroalkyl substances (PFASs) have attracted worldwide attention due to their ubiquitous occurrence, bioaccumulation, and toxicological effects, yet the fate of PFASs in a lotic ecosystem is largely unknown. To elucidate spatial distribution and multimedia partitioning of legacy and emerging PFASs in a lotic river flowing into an estuary, PFASs were synchronously analyzed in water, suspended particulate matter (SPM), sediment, and biota samples collected along Guangzhou reach of the Pearl River, South China. Geographically, the concentrations of PFASs in the water phase showed a decreasing trend from the upper and middle sections (urban area) to the down section (suburban area close to estuary) of the river. While perfluorooctanoic acid predominated in water and SPM, more diverse compositions were observed in sediment and biota with the increase in contributions of long-chain PFASs. Field-derived sediment–water partitioning coefficients ( K d ) and bioaccumulation factors (BAFs) of PFASs increased with the increase in perfluorinated carbons. Besides hydrophobicity, water pH and salinity significantly affected the multimedia partitioning of PFASs in a lotic ecosystem. In addition, 87 homologues (63 classes) were identified as emerging PFASs in four media using suspect analysis. Interestingly, K d and BAF of the emerging PFASs were often higher than legacy PFASs containing the same perfluorinated carbons, raising a special concern on the environmental risk of emerging PFASs.