Department of Chemistry, University of Toronto , 80 St. George Street, Toronto, Ontario Canada , M5S 3H6.
Environ Sci Technol. 2014 Nov 4;48(21):12783-90. doi: 10.1021/es502986w. Epub 2014 Oct 22.
Fluorotelomer-based acrylate polymers (FTACPs) are a class of side-chain fluorinated polymers used for a variety of commercial applications. The degradation of FTACPs through ester hydrolysis, cleavage of the polymer backbone, or both could serve as a significant source of perfluoroalkyl carboxylates (PFCAs). The biodegradation of FTACPs was evaluated in a soil-plant microcosm over 5.5 months in the absence/presence of wastewater treatment plant (WWTP) biosolids using a unique FTACP determined to be a homopolymer of 8:2 fluorotelomer acrylate (8:2 FTAC). Although structurally different from commercial FTACPs, the unique FTACP possesses 8:2 fluorotelomer side chain appendages bound to the polymer backbone via ester moieties. Liberation and subsequent biodegradation of the 8:2 fluorotelomer appendages was indirectly determined by monitoring for PFCAs of varying chain lengths (C6-C9) and known fluorotelomer intermediates by liquid chromatography tandem mass spectrometry (LC-MS/MS). A FTACP biodegradation half-life range of 8-111 years was inferred from the 8:2 fluorotelomer alcohol (8:2 FTOH) equivalent of the unique FTACP and the increase of degradation products. The progress of FTACP biodegradation was also directly monitored qualitatively using matrix-assisted laser desorption/ionization (MALDI-TOF) time-of-flight mass spectrometry. The combination of indirect and direct analysis indicated that the model FTACP biodegraded predominantly to perfluorooctanoate (PFOA) in soils and at a significantly higher rate in the presence of a plant and WWTP biosolids.
含氟端基丙烯酸酯聚合物（FTACPs）是一类侧链氟化聚合物，用于各种商业应用。FTACPs 通过酯水解、聚合物主链断裂或两者同时发生的降解可能成为全氟羧酸酯（PFCAs）的重要来源。在缺乏/存在污水处理厂（WWTP）生物固体的情况下，通过使用一种独特的 FTACP 在土壤-植物微宇宙中评估了 FTACPs 的生物降解，该 FTACP 被确定为 8:2 氟端基丙烯酸酯（8:2 FTAC）的均聚物。尽管在结构上与商业 FTACPs 不同，但独特的 FTACP 具有通过酯基结合到聚合物主链上的 8:2 氟端基侧链。通过监测不同链长（C6-C9）和已知氟端基中间体的 PFCAs，间接确定了 8:2 氟端基侧链的释放和随后的生物降解，这是通过液相色谱串联质谱（LC-MS/MS）进行的。从独特的 FTACP 的 8:2 氟端基醇（8:2 FTOH）当量和降解产物的增加推断出 FTACP 生物降解半衰期范围为 8-111 年。还使用基质辅助激光解吸/电离（MALDI-TOF）飞行时间质谱直接定性监测 FTACP 生物降解的进展。间接和直接分析的结合表明，模型 FTACP 主要在土壤中生物降解为全氟辛酸（PFOA），并且在存在植物和 WWTP 生物固体的情况下生物降解速度显著提高。
