Contribution of selected perfluoroalkyl and polyfluoroalkyl substances to the adsorbable organically bound fluorine in German rivers and in a highly contaminated groundwater.

Due to the lack of analytical standards the application of surrogate parameters for organofluorine detection in the aquatic environment is a complementary approach to single compound target analysis of perfluoroalkyl and polyfluoroalkyl chemicals (PFASs). The recently developed method adsorbable organically bound fluorine (AOF) is based on adsorption of organofluorine chemicals to activated carbon followed by combustion ion chromatography. This AOF method was further simplified to enable measurement of larger series of environmental samples. The limit of quantification (LOQ) was 0.77 μg/L F. The modified protocol was applied to 22 samples from German rivers, a municipal wastewater treatment plant (WWTP) effluent, and four groundwater samples from a fire-fighting training site. The WWTP effluent (AOF = 1.98 μg/L F) and only three river water samples (AOF between 0.88 μg/L F and 1.47 μg/L F) exceeded the LOQ. The AOF levels in a PFASs plume at a heavily contaminated site were in the range of 162 ± 3 μg/L F to 782 ± 43 μg/L F. In addition to AOF 17 PFASs were analyzed by high performance liquid chromatography-tandem mass spectrometry. 32-51% of AOF in the contaminated groundwater samples were explained by individual PFASs wheras in the surface waters more than 95% remained unknown. Organofluorine of two fluorinated pesticides, one pesticide metabolite and three fluorinated pharmaceuticals was recovered as AOF by >50% from all four tested water matrices. It is suggested that in the diffusely contaminated water bodies such fluorinated chemicals and not monitored PFASs contribute significantly to AOF.