We developed a quantitative method for classifying land uses for PFAS-related investigations in freshwater environments and determined PFAS ambient concentrations associated with specific land-use classes. Furthermore, our study presents a comprehensive assessment of the ambient occurrence and risks of PFAS mixtures beyond the usually studied PFOS-PFOA mixtures. Eighty-five inland (freshwater only) sites were sampled for water, sediment, and riparian soil in Victoria, south-east Australia, and analysed for 33 PFAS. PFAS were detected in 91% of water samples, 34% of sediment samples, and 28% of riparian soil samples. Four land-use classes were defined: remote, agricultural, mixed, and urban. In the remote land-use class, only PFOS was detected at a low ambient concentration (0.0002 μg/L) in one water sample. Short-chain PFCA were frequently detected in the agricultural and mixed water samples. PFBA had the highest median ambient concentration in both land uses (ca. 0.01 μg/L), contributing to both ΣPFAS (40%) and ΣPFCA (50%) concentrations. In the urban land-use class, several congeners (PFBA, PFPeA, PFHxA, PFOA, PFHxS, and PFOS) had median ambient concentrations at or close to 0.01 μg/L and contributed similarly to ΣPFAS (10-20%). Elevated risk to the aquatic environment was found only for PFOS in two mixed and eight urban sites. This pattern was consistent with the finding for PFAS mixtures, where the elevated risk was driven by PFOS at those same sites. Our study provides critical information about environmentally relevant ambient concentrations and PFAS mixtures. This information, together with the land-use classification approach presented herein, can be used as reference levels for several critical purposes, including identifying PFAS-contaminated sites, informing land use planning and development decisions, setting standards and guidelines, and tracking changes over time.
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