State Environmental Protection Key Laboratory of Environmental Risk Assessment and Control on Chemical Process, East China University of Science and Technology, Shanghai, 200237, China.
Environ Sci Pollut Res Int. 2014 Jan;21(2):1401-10. doi: 10.1007/s11356-013-2029-7. Epub 2013 Aug 1.
Most studies on the treatment of chlorinated contaminants by Fe(0) focus on aqueous system tests. However, few is known about the effectiveness of these tests for degrading chlorinated contaminants such as 1,1,1-trichloroethane (TCA) in soil. In this work, the reductive degradation performance of 1,1,1-TCA by Fe(0) was thoroughly investigated in a soil slurry system. The effects of various factors including acid-washed iron, the initial 1,1,1-TCA concentration, Fe(0) dosage, slurry pH, and common constituents in groundwater and soil such as Cl(-), HCO3 (-), SO4 (2-), and NO3 (-) anions and humic acid (HA) were evaluated. The experimental results showed that 1,1,1-TCA could be effectively degraded in 12 h for an initial Fe(0) dosage of 10 g L(-1) and a soil/water mass ratio of 1:5. The soil slurry experiments showed two-stage degradation kinetics: a slow reaction in the first stage and a fast reductive degradation of 1,1,1-TCA in the second stage. The reductive degradation of 1,1,1-TCA was expedited as the mass concentration of Fe(0) increased. In addition, high pHs adversely affected the degradation of 1,1,1-TCA over a pH range of 5.4-8.0 and the reductive degradation efficiency decreased with increasing slurry pH. The initial 1,1,1-TCA concentration and the presence of Cl(-) and SO4(2-) anions had negligible effects. HCO3(-) anions had a accelerative effect on 1,1,1-TCA removal, and both NO3(-) and HA had inhibitory effects. A Cl(-) mass balance showed that the amount of Cl(-) ions released into the soil slurry system during the 1,1,1-TCA degradation increased with increasing reaction time, suggesting that the main degradation mechanism of 1,1,1-TCA by Fe(0) in a soil slurry system was reductive dechlorination with 1,1-DCA as the main intermediate. In conclusion, this study provides a theoretical basis for the practical application of the remediation of contaminated sites containing chlorinated solvent.
大多数关于零价铁(Fe(0))处理氯化污染物的研究都集中在水相体系测试上。然而,对于这些测试在土壤中降解氯化污染物(如 1,1,1-三氯乙烷(TCA))的有效性知之甚少。在这项工作中,在土壤悬浮液体系中彻底研究了零价铁(Fe(0))对 1,1,1-TCA 的还原降解性能。评估了各种因素的影响,包括酸洗铁、初始 1,1,1-TCA 浓度、Fe(0)剂量、悬浮液 pH 值以及地下水和土壤中的常见成分,如 Cl(-)、HCO3 (-)、SO4 (2-) 和 NO3 (-)阴离子和腐殖酸(HA)。实验结果表明,在初始 Fe(0)剂量为 10 g L(-1)和土壤/水质量比为 1:5 的情况下,1,1,1-TCA 可以在 12 h 内有效降解。土壤悬浮液实验表明存在两阶段降解动力学:第一阶段反应缓慢,第二阶段 1,1,1-TCA 快速还原降解。随着 Fe(0)质量浓度的增加,1,1,1-TCA 的还原降解速度加快。此外,在 pH 值为 5.4-8.0 的范围内,高 pH 值会对 1,1,1-TCA 的降解产生不利影响,并且随着悬浮液 pH 值的升高,还原降解效率降低。初始 1,1,1-TCA 浓度以及 Cl(-)和 SO4(2-)阴离子的存在几乎没有影响。HCO3(-)阴离子对 1,1,1-TCA 的去除具有加速作用,而 NO3(-)和 HA 则具有抑制作用。Cl(-)质量平衡表明,在 1,1,1-TCA 降解过程中,释放到土壤悬浮液系统中的 Cl(-)离子量随着反应时间的增加而增加,这表明 1,1,1-TCA 被 Fe(0)在土壤悬浮液系统中的主要降解机制是还原脱氯,以 1,1-DCA 为主要中间产物。总之,本研究为含氯溶剂污染场地修复的实际应用提供了理论依据。