Distribution and primary source analysis of per- and poly-fluoroalkyl substances with different chain lengths in surface and groundwater in two cities, North China

• Poly- and per-fluoroalkyl substances (PFASs) were detected widely in studied waters.
• Short-chain PFASs was found to increase in Tianjin due to manufacturing switch.
• Rainfall and surface runoff acted as non-point sources for PFASs in surface waters.
• The analogue distributions in different phases can be used for PFAS source analysis.

Per- and poly-fluoroalkyl substances (PFASs) have been widely detected in the hydrosphere. The knowledge on the distribution and composition patterns of PFAS analogues with different chain length significantly contribute to their source analysis. In the present study, a regional scale investigation of PFASs in surface river waters and adjacent ground waters was carried out in two cities of China with potential contamination, Tianjin and Weifang. A total of 31 water samples were collected, and 20 PFASs therein were measured by a high-performance liquid chromatograph–tandem mass spectrometer (HPLC–MS/MS). The possible sources of PFASs in the aquatic environment were assessed primarily by concentration patterns as well as hierarchical cluster analysis. In all 4 rivers investigated in the two cities, perfluoroalkyl carboxylic acids (PFCAs) were the dominant compounds contributing over 70% of the PFASs detected. Perfluorooctanoic acid (PFOA) was the dominant PFCA with a concentration range of 8.58–20.3 ng/L in Tianjin and 6.37–25.9 ng/L in Weifang, respectively. On the average, the highest concentration was observed in samples from Dagu Drainage Canal (Dagu) in Tianjin and those short-chain PFASs (C4–C6) was detected with a comparable level of the longer-chain PFASs (>C6). Specifically, perfluorobutanoic acid (PFBA) was dominant in the short-chain analogues. This indicates that a remarkably increasing input of short-chain PFASs might be related to wastewater treatment plant effluent or industrial discharges, which could be possibly due to the switch of manufacturing to short-chain products. In Weifang, precipitation and subsequent surface runoff as non-point sources could be significant inputs of PFASs into surface water while groundwater was possibly subjected to severe point sources with ∑PFASs concentration up to ~100 ng/L. The inconsistent distribution patterns in groundwater suggest complicated pathways of contamination.