The aim of the present study was to assess the presence of perfluoroalkyl acids (PFAAs), namely perfluoroalkane sulfonates and perfluoroalkyl carboxylic acids, in Spanish river basins in order to: identify potential spatiotemporal variations; evaluate the effectiveness of the measures implemented for the reduction/elimination of these pollutants; verify the fulfillment of the Environmental Quality Standards (EQSs) in the European Union. PFOS and PFOA were determined in 116 water samples from four sites in the Duero basin, the largest in the Iberian Peninsula, collected seasonally from 2013 to 2020. In addition, 30 fish sample composites from the sample banks of Duero, Tagus, Ebro, Eastern Cantabrian and Catalonian basins were analyzed for 15 PFAAs. Median PFOS and PFOA concentrations were 0.72 and 0.42 ng/L, ranging from values below the limit of quantification (LOQ) to 81 and 22 ng/L, respectively. During the studied period, 51% of water samples were above the EQS of 0.65 ng/L for PFOS. In the case of fish, the PFOS range was <LOQ-59 with 33% of the samples above the EQS of 9.1 ng/g wet weight. Moreover, fish from the Tagus and Catalonian basins showed median concentrations above the EQS. Particularly, fish collected around highly populated areas such as Madrid and Barcelona showed the greatest PFAA concentrations. Overall, PFAA concentrations in water and fish increased significantly with population density suggesting urban areas as their main source. Although our results suggested decreasing tendencies for PFOS and PFOA in water, significant trends only could be confirmed at two sampling sites.
Keywords: Environmental quality standards; Freshwater pollution; PFOA; PFOS; POPs; River.
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