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.

Fluorine mass balance analysis of selected environmental samples from Norway.

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.