Interlaboratory Comparison of Extractable Organofluorine Measurements in Groundwater and Eel (Anguilla rostrata): Recommendations for Methods Standardization.

Research on per- and polyfluoroalkyl substances (PFAS) frequently incorporates organofluorine measurements, particularly because they could support a class-based approach to regulation. However, standardized methods for organofluorine analysis in a broad suite of matrices are currently unavailable, including a method for extractable organofluorine (EOF) measured using combustion ion chromatography (CIC). Here, we report the results of an international interlaboratory comparison. Seven laboratories representing academia, government, and the private sector measured paired EOF and PFAS concentrations in groundwater and eel (Anguilla rostrata) from a site contaminated by aqueous film-forming foam. Among all laboratories, targeted PFAS could not explain all EOF in groundwater but accounted for most EOF in eel. EOF results from all laboratories for at least one replicate extract fell within one standard deviation of the interlaboratory mean for groundwater and five out of seven laboratories for eel. PFAS spike mixture recoveries for EOF measurements in groundwater and eel were close to the criterion (±30%) for standardized targeted PFAS methods. Instrumental operation of the CIC such as replicate sample injections was a major source of measurement uncertainty. Blank contamination and incomplete inorganic fluorine removal may introduce additional uncertainties. To elucidate the presence of unknown organofluorine using paired EOF and PFAS measurements, we recommend that analysts carefully consider confounding methodological uncertainties such as differences in precision between measurements, data processing steps such as blank subtraction and replicate analyses, and the relative recoveries of PFAS and other fluorine compounds.

Analysis and characterization of novel fluorinated compounds used in surface treatments products.

Side-chain fluorinated polymers are speculated to be potential precursors to other non-polymeric aliphatic per- and polyfluoroalkyl acids (PFAAs). Limited knowledge of environmental occurrence of this compound class is partly due to lack of structural information and authentic standards. In this study, two novel fluorinated compounds, suspected to be side-chain fluorinated copolymers used in two commercial technical mixtures (Scotchgard™ Pre-2002 formulation and Scotchgard™ Post-2002 formulation) were analyzed and characterized in order to provide information to facilitate detection and quantification. The commercial mixtures were analyzed using tandem mass spectrometry and high-resolution mass spectrometry; besides already reported C4- and C8-fluoroalkylsulfonamido (FASA) side-chains, a proposed structure was determined for the perfluorooctane (C8) sulfonamide-urethane copolymer in the Pre-2002 formulation. Structural isomers were also observed for C4- and C8-FASA-based copolymers. Total fluorine analysis revealed that the Scotchgard™ Pre-2002 Formulation contained a fluorine content of 0.5% and 1.8% for the Scotchgard™ Post-2002 Formulation. The equivalent FASA side-chain content was determined to be 0.8% for Pre-2002 and 3.1% for Post-2002. Both C4- and C8-FASA-based copolymers underwent hydrolysis and oxidation and were transformed to their respective perfluoroalkyl side chain, which suggest that transformation products can be analyzed for example after total oxidizable precursor (TOP) assay. Both compounds were shown to strongly sorb to sediment particles, which also gives indications about their environmental fate and transport pathways.

Per- and polyfluoroalkyl substances (PFAS) in sludge from wastewater treatment plants in Sweden - First findings of novel fluorinated copolymers in Europe including temporal analysis.

Thousands of per- and polyfluoroalkyl substances (PFAS) are on the global market, while only a minor proportion is monitored regularly in the environment. Wastewater treatment plants (WWTPs) have been suggested to be a point source for PFAS to the environment due to emission of effluent and sludge. In this study, 81 PFAS including two rarely studied perfluoroalkyl sulfonamide-based (FASA) copolymers were analyzed in sludge samples to understand the usage of PFAS in the society. Sludge samples (n = 28) were collected at four WWTPs in Sweden between 2004 and 2017. The total levels of 79 measured PFAS were between 50 and 1124 ng/g d.w. All sludge samples showed detectable levels of both C8- and C4-FASA-based copolymers. The concentrations of the FASA-based copolymers were proposed to be reported in fluorinated side-chain equivalents (FSC eq.), in order to compare the levels of the copolymers with the other neutral and anionic PFAS, as no authentic standards were available. The concentrations of the FASA-based copolymers in sludge were between 1.4 and 22 ng FSC eq./g d.w. A general predomination of precursor and intermediate compounds was observed. A lower contribution of perfluoroalkyl carboxylic acids was noted for the WWTPs more influenced by domestic emission when compared with more influenced by industrial emission. An overall declining trend in the total PFAS concentration was seen between the years 2004 and 2017. The present study observed a shift from the C8-based chemistry toward shorter chain lengths, included a declining trend for C8-FASA-based copolymer over the entire study period. These findings further demonstrate the occurrence of side-chain fluorinated copolymers in Sweden and that sludge is a useful matrix to reflect the usage of PFAS in society and the potential for environmental exposure.