Estuaries serve as a sink for land-based pollutants like legacy per- and polyfluoroalkyl substances (PFASs), however, the environmental behaviors of emerging PFASs (ePFASs) remain largely unknown. This study investigated the occurrence, behaviors, and sources of 18 legacy PFASs and 13 ePFASs across the Pearl River Estuary (PRE). The results indicated that the total concentrations of PFASs (ΣPFASs) in seawater, suspended particulate matter (SPM), and sediment ranged from 1.20 to 25.6 ng/L, not detected (ND) to 635 ng/g dry weight (dw), and 0.93 to 6.84 ng/g dw, respectively. Perfluorooctanoate (PFOA) was the dominant chemical (25.4 %) in seawater, while sodium p-perfluorooctanoate nonenoxybenzene sulfonate (PFNOBS) for SPM (75.0 %) and sediment (37.9 %). PFASs exhibited a nearshore-to-offshore decreasing trend in seawater, while significant enrichment was observed in SPM and sediment at the river-sea junction, primarily attributed to urban/industrial discharges and the "marginal filtration effect". Partition coefficients (log Kd, log KOC, and log Kp) exhibited strong linear correlations with carbon chain length of PFASs, indicated that long-chain PFASs were more readily adsorbed by the solid phase. SPM-mediated transport significantly enhanced long-chain PFAS distribution (log Kp =1.85-4.73), while salinity negatively influenced Kd of short-chain PFCAs (p < 0.05). Source apportionment analysis revealed the diverse sources of PFASs, including electronics, electroplating, textiles, papermaking, food packaging and emerging fluorochemical manufacturing, which aligns with PFAS releases from industrial processes and commercial products within the Pearl River Delta. Overall low ecological risk of PFASs was observed in the PRE, yet legacy PFOA and emerging substances, including 6:2 fluorotelomer sulfonic acid (6:2 FTSA), hexafluoropropylene oxide trimer acid (HFPO-TA), and PFNOBS, warrant attention due to their potential accumulation potential and associated risks. This study underscores the critical role of SPM in PFAS dynamics and provides significant insights into the partitioning behavior and sources of PFASs, particularly ePFASs, within estuarine aquatic systems.
Keywords: Ecological risk assessment; Hydrological properties; Legacy and emerging pfass; Source apportionment; Spatial variation.
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