Department of Agronomy, Purdue University, West Lafayette, IN 47907-2054, USA.
Department of Agronomy, Purdue University, West Lafayette, IN 47907-2054, USA.
Chemosphere. 2016 Feb;144:2482-8. doi: 10.1016/j.chemosphere.2015.11.021. Epub 2015 Dec 6.
Aerobic soil biodegradation of toluene-2,4-di(8:2 fluorotelomer urethane) (FTU) and hexamethylene-1,6-di(8:2 fluorotelomer urethane) (HMU) in a forest soil and FTU in an agricultural silty clay loam soil was monitored for up to 6 months. Fluorotelomer alcohols were measured in headspace and parent monomers and all metabolites in soil extracts. Negligible degradation of FTU biodegradation occurred in the agricultural soil with 94 ± 15% recovered at day 180. However, in the forest soil, both FTU and HMU degradation was evident with significant losses of 24% (117 d) and 27% (180 day), respectively, and concomitant increases in the terminal metabolite, perfluorooctanoic acid (PFOA) concentrations were well above what could result from residual 8:2 FTOH. Kinetic modeling estimated half-lives for FTU (aromatic backbone) and HMU (aliphatic backbone) in the forest soil to be 3-5 months and 15.9-22.2 months, respectively. The addition of a structurally similar non-fluorinated FTU analog, toluene-2,4-dicarbamic acid diethyl ester (TDAEE) enhanced production of terminal end products from 8:2 FTOH degradation. However, there was no clear evidence that TDAEE enhanced cleavage of the urethane bond, thus TDAEE appeared to just serve as an additional carbon source. TDAEE's half-life was ∼ one week. A second addition of TDAEE appeared to retard subsequent degradation of FTU exemplifying the microbial dynamics and diversity impacting degradation of polyfluoroalkyl substances. Enhanced degradation of HMU was observed upon re-aeration indicating oxygen may have been limiting during some periods although degradation of intermediate metabolites to terminal metabolites was still occurring, albeit at slower rates.
在森林土壤中监测了甲苯-2,4-双(8:2 氟代四氢呋喃基)脲(FTU)和六亚甲基-1,6-双(8:2 氟代四氢呋喃基)脲(HMU)的有氧土壤生物降解,以及在农业粉质粘壤土中 FTU 的生物降解,最长可达 6 个月。在顶空和母体单体中测量了氟代四氢呋喃醇,并在土壤提取物中测量了所有代谢物。在农业土壤中,FTU 生物降解几乎没有发生,在 180 天回收了 94±15%。然而,在森林土壤中,FTU 和 HMU 的降解都很明显,分别损失了 24%(117 天)和 27%(180 天),并且末端代谢物全氟辛酸(PFOA)的浓度显著增加,远高于残留 8:2 FTOH 所致的浓度。动力学模型估计 FTU(芳环骨架)和 HMU(脂肪族骨架)在森林土壤中的半衰期分别为 3-5 个月和 15.9-22.2 个月。添加结构相似的非氟代 FTU 类似物,甲苯-2,4-二氨基甲酸二乙酯(TDAEE),增强了 8:2 FTOH 降解产生末端产物的能力。然而,没有明显证据表明 TDAEE 增强了氨基甲酸酯键的断裂,因此 TDAEE 似乎只是作为额外的碳源。TDAEE 的半衰期约为一周。第二次添加 TDAEE 似乎会延缓 FTU 的后续降解,这说明了微生物动力学和多样性对全氟烷基物质降解的影响。重新通气后观察到 HMU 的降解增强,表明在某些时期可能缺氧,尽管中间代谢物向末端代谢物的降解仍在继续,但速度较慢。