State Key Lab of Biogeology and Environmental Geology, China University of Geosciences, 388 Lumo Road, Wuhan 430074, PR China.
Environ Sci Technol. 2012 Mar 20;46(6):3398-405. doi: 10.1021/es204546u. Epub 2012 Mar 1.
Degradation of trichloroethylene (TCE) in simulated groundwater by Pd and electro-generated H(2) and O(2) is investigated in the absence and presence of Fe(II). In the absence of Fe(II), hydrodechlorination dominates TCE degradation, with accumulation of H(2)O(2) up to 17 mg/L. Under weak acidity, low concentrations of oxidizing •OH radicals are detected due to decomposition of H(2)O(2), slightly contributing to TCE degradation via oxidation. In the presence of Fe(II), the degradation efficiency of TCE at 396 μM improves to 94.9% within 80 min. The product distribution proves that the degradation pathway shifts from 79% hydrodechlorination in the absence of Fe(II) to 84% •OH oxidation in the presence of Fe(II). TCE degradation follows zeroth-order kinetics with rate constants increasing from 2.0 to 4.6 μM/min with increasing initial Fe(II) concentration from 0 to 27.3 mg/L at pH 4. A good correlation between TCE degradation rate constants and •OH generation rate constants confirms that •OH is the predominant reactive species for TCE oxidation. Presence of 10 mM Na(2)SO(4), NaCl, NaNO(3), NaHCO(3), K(2)SO(4), CaSO(4), and MgSO(4) does not significantly influence degradation, but sulfite and sulfide greatly enhance and slightly suppress degradation, respectively. A novel Pd-based electrochemical process is proposed for groundwater remediation.
在不存在和存在 Fe(II) 的情况下,研究了 Pd 和电生成的 H(2) 和 O(2) 在模拟地下水中对三氯乙烯 (TCE) 的降解作用。在不存在 Fe(II) 的情况下,氢脱氯作用占主导地位,导致 H(2)O(2) 积累至 17mg/L。在弱酸性条件下,由于 H(2)O(2) 的分解,检测到低浓度的氧化性 •OH 自由基,它们通过氧化作用略微促进 TCE 的降解。在存在 Fe(II) 的情况下,396μM 的 TCE 在 80 分钟内的降解效率提高到 94.9%。产物分布证明,在不存在 Fe(II) 的情况下,降解途径从 79%的氢脱氯作用转变为存在 Fe(II) 时的 84%的 •OH 氧化作用。TCE 降解遵循零级动力学,随着初始 Fe(II) 浓度从 0 增加到 27.3mg/L(pH4),速率常数从 2.0 增加到 4.6μM/min。TCE 降解速率常数与 •OH 生成速率常数之间存在良好的相关性,证实了 •OH 是 TCE 氧化的主要反应性物质。存在 10mM 的 Na(2)SO(4)、NaCl、NaNO(3)、NaHCO(3)、K(2)SO(4)、CaSO(4) 和 MgSO(4) 不会显著影响降解,但亚硫酸盐和硫化物分别大大增强和略微抑制降解。提出了一种基于 Pd 的新型电化学过程用于地下水修复。