A survey of per- and polyfluoroalkyl substances (PFAS) was conducted in Melbourne, Australia to determine background concentrations in residential, industrial, municipal wastewater treatment plants, and rural land uses. Surface water and sediment samples collected from 65 sites with different catchment land uses were analysed for thirty-three PFAS. Twenty-two out of thirty-three targeted PFAS were detected, with at least one PFAS species was detected in 98% water samples and 8% sediment samples. One site was determined to have point-source pollution from an airport (surface water Σ33PFAS = 4261 ng/L) and was excluded from statistical analyses. The median Σ33PFAS concentration in surface water was 63.5 ng/L and the average was 78.6 ng/L (range < DL-526 ng/L). PFAS species with the highest median concentrations were PFBA (11.3 ng/L), PFHxA (9.2 ng/L), PFOA (8.3 ng/L), PFOS (8.0 ng/L), PFPeA (7.5 ng/L), PFHpA (3.2 ng/L), and PFHxS (2.9 ng/L).The average Σ4PFAS in sediments was 0.35 ng/g d.w. (range = <DL-6.7 ng/g) and the congeners detected were PFOS, N-MeFOSAA, N-EtFOSAA, and N-EtFOSE. Significantly higher concentrations of all PFAS were found in urban areas than rural, except for PFBA which was evenly dispersed throughout all areas. Short-chain perfluoroalkyl carboxylic acids (PFCAs), PFBA, PFPeA, PFHxA, PFHpA, and the PFSA, PFBS were evenly dispersed throughout urban and industrial areas. PFOA, PFNA, and PFDA were higher, but not significantly, in residential catchments than industrial catchments. Industrial areas had significantly higher concentrations of perfluoroalkyl sulfonic acids (PFSAs), PFPeS, PFHxS, and PFOS, and 6:2 FTS than other urbanised areas. The distribution of PFAS throughout catchment types in this study displayed similar trends to other studies including findings of PFBA in background areas. Ongoing monitoring of defined catchments is recommended to improve understanding of PFAS sources and changes in environmental profiles, and to assess the implications of its occurrence throughout the environment.
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