Man-Technology-Environment (MTM) Research Centre, School of Science and Technology, Örebro University, SE-701 82, Sweden.
Man-Technology-Environment (MTM) Research Centre, School of Science and Technology, Örebro University, SE-701 82, Sweden.
Chemosphere. 2022 Sep;302:134720. doi: 10.1016/j.chemosphere.2022.134720. Epub 2022 Apr 26.
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.
侧链氟化聚合物被推测为其他非聚合脂肪族全氟和多氟烷基酸 (PFAAs) 的潜在前体。这种化合物类别的环境出现的知识有限，部分原因是缺乏结构信息和真实的标准。在这项研究中，分析和表征了两种新型氟化化合物，它们被怀疑是两种商业技术混合物（Scotchgard™ Pre-2002 配方和 Scotchgard™ Post-2002 配方）中使用的侧链氟化共聚物，以便提供有助于检测和定量的信息。使用串联质谱和高分辨率质谱分析了商业混合物；除了已经报道的 C4-和 C8-氟烷基亚磺酰胺 (FASA) 侧链外，还确定了 Pre-2002 配方中全氟辛烷 (C8) 磺酰胺-氨基甲酸酯共聚物的建议结构。还观察到了基于 C4-和 C8-FASA 的共聚物的结构异构体。总氟分析表明，Scotchgard™ Pre-2002 配方的氟含量为 0.5%，Scotchgard™ Post-2002 配方的氟含量为 1.8%。确定 Pre-2002 的等效 FASA 侧链含量为 0.8%，Post-2002 的等效 FASA 侧链含量为 3.1%。基于 C4-和 C8-FASA 的共聚物都经历了水解和氧化，转化为各自的全氟烷基侧链，这表明可以分析转化产物，例如在总可氧化前体 (TOP) 测定之后。这两种化合物都强烈地吸附到沉积物颗粒上，这也表明了它们的环境命运和迁移途径。
