To Örebro University

Recent publications have highlighted the ubiquitous presence of unidentified organofluorine compounds, whose environmental occurrence is poorly understood. In this study, wastewater treatment plant (WWTP) effluent and sludge samples from seven countries were analyzed for extractable organofluorine (EOF) and target PFAS, to evaluate which compounds are released back into the environment. Fluorine mass balance analysis of effluent samples (n = 14) revealed that on average 90% of the EOF could not be explained by the 73 PFAS monitored in this investigation. The levels of EOF in effluent (324–1460 ng of F/L) and sludge (39–210 ng of F/g of dry weight) indicate that a substantial amount of organofluorine compounds is released back into nature. A commonly overlooked PFAS class, ultra-short-chain PFCAs, accounted for 4% of EOF on average, while the remaining 71 compounds explained only a further 6% of EOF on average. The highest number of PFAS was detected in the effluent dissolved phase (37), compared to 29 and 23 PFAS in sludge and effluent particulate phase, respectively. The increased concentrations of EOF in both WWTP effluent and sludge are of concern, as the chemical species contained therein remain largely unknown, and thus, their potential health and environmental risks cannot be assessed.

The presence of unidentified organofluorine compounds (UOF) has been investigated in recent publication, but their environmental occurrence is still poorly understood. Fluorine mass balance analysis was performed on environmental samples from lake Mjøsa and river Alna (surface water (n = 9), sediment (n = 5) and fish liver (n = 4)) and sewage samples from Oslo (n = 5), to reveal to the fraction of UOF. In samples that had extractable organofluorine (EOF) concentrations above the limit of detection (LoD), more than 70% of their EOF could not be accounted for by the 37 PFAS monitored in this study. The surface water samples from lake Mjøsa had EOF concentrations several times higher than what has been reported elsewhere in Nordic nations. The flux of EOF in river Alna and selected sewage pipes revealed that it was 1-2 orders of magnitude higher than the flux of the measured PFAS. The elevated concentrations of EOF in all samples pose a potential health and environmental hazard, as their composition remains mostly unknown.

This review summarizes and discusses eight analytical methods for organofluorine (OF) analysis, which offer detection limits suitable for consumer products and environmental samples. Direct sample analysis of OF only applies to some techniques on consumer products, whereas others require sample pretreatment or concentration before measurements. Comparison between methods for OF analysis were found to be difficult because of different selectivity (between OF and fluoride), sensitivity and type of samples (bulk, extract, surface) analysed. Neither inter-laboratory comparison on OF analysis nor suitable certified reference materials have been used for method validation, which makes data comparability between studies challenging. A top down approach for the comprehensive assessment of OF is proposed, where OF/extractable OF is first measured, followed by target analysis to obtain unquantifiable OF concentrations using the mass balance approach. For further identification of unquantifiable OF, approaches such as total oxidizable precursor assay, suspect and non-target screening are briefly discussed.