Kim Hong-Seok, Kang Wan-Hyup, Kim Meejeong, Park Joo-Yang, Hwang Inseong
School of Civil and Environmental Engineering, Pusan National University, 30 Jangjeon-Dong, Geumjeong-Gu, Busan 609-735, Republic of Korea.
Chemosphere. 2008 Oct;73(5):813-9. doi: 10.1016/j.chemosphere.2008.04.092. Epub 2008 Jul 1.
Reactive reductants of cement/Fe(II) systems in dechlorinating chlorinated hydrocarbons are unknown. This study initially evaluated reactivities of potential reactive agents of cement/Fe(II) systems such as hematite (alpha-Fe(2)O(3)), goethite (alpha-FeOOH), lepidocrocite (gamma-FeOOH), akaganeite (beta-FeOOH), ettringite (Ca(6)Al(2)(SO(4))(3)(OH)(12)), Friedel's salt (Ca(4)Al(2)Cl(2)(OH)(12)), and hydrocalumite (Ca(2)Al(OH)(6)(OH).3H(2)O) in reductively dechlorinating trichloroethylene (TCE) in the presence of Fe(II). It was found that a hematite/Fe(II) system shows TCE degradation characteristics similar to those of cement/Fe(II) systems in terms of degradation kinetics, Fe(II) dose dependence, and final products distribution. It was therefore suspected that Fe(III)-containing phases of cement hydrates in cement/Fe(II) systems behaved similarly to the hematite. CaO, which was initially introduced as a pH buffer, was observed to participate in or catalyze the formation of reactive reductants in the hematite/Fe(II) system, because its addition enhanced the reactivities of hematite/Fe(II) systems. From the SEM (scanning electron microscope) and XRD (X-ray diffraction) analyses that were carried out on the solids from hematite/Fe(II) suspensions, it was discovered that a sulfate green rust with a hexagonal-plate structure was probably a reactive reductant for TCE. However, SEM analyses conducted on a cement/Fe(II) system showed that hexagonal-plate crystals, which were presumed to be sulfate green rusts, were much less abundant in the cement/Fe(II) than in the hematite/Fe(II) systems. It was not possible to identify any crystalline minerals in the cement/Fe(II) system by using XRD analysis, probably because of the complexity of the cement hydrates. These observations suggest that major reactive reductants of cement/Fe(II) systems may differ from those of hematite/Fe(II) systems.
水泥/Fe(II)体系中用于脱除氯代烃的活性还原剂尚不明确。本研究首先评估了水泥/Fe(II)体系中潜在的活性试剂的反应活性,这些试剂包括赤铁矿(α-Fe₂O₃)、针铁矿(α-FeOOH)、纤铁矿(γ-FeOOH)、四方纤铁矿(β-FeOOH)、钙矾石(Ca₆Al₂(SO₄)₃(OH)₁₂)、弗里德尔盐(Ca₄Al₂Cl₂(OH)₁₂)以及水铝钙石(Ca₂Al(OH)₆(OH)·3H₂O),它们在Fe(II)存在的情况下对三氯乙烯(TCE)进行还原性脱氯。研究发现,在降解动力学、Fe(II)剂量依赖性和最终产物分布方面,赤铁矿/Fe(II)体系表现出与水泥/Fe(II)体系相似的TCE降解特性。因此,人们怀疑水泥/Fe(II)体系中水泥水化物的含Fe(III)相的行为与赤铁矿相似。最初作为pH缓冲剂引入的CaO被观察到参与或催化了赤铁矿/Fe(II)体系中活性还原剂的形成,因为它的添加增强了赤铁矿/Fe(II)体系的反应活性。通过对赤铁矿/Fe(II)悬浮液中的固体进行扫描电子显微镜(SEM)和X射线衍射(XRD)分析发现,具有六方板结构的硫酸绿锈可能是TCE的活性还原剂。然而,对水泥/Fe(II)体系进行的SEM分析表明,假定为硫酸绿锈的六方板状晶体在水泥/Fe(II)体系中的含量远低于赤铁矿/Fe(II)体系。由于水泥水化物的复杂性,使用XRD分析无法在水泥/Fe(II)体系中鉴定出任何晶体矿物。这些观察结果表明,水泥/Fe(II)体系的主要活性还原剂可能与赤铁矿/Fe(II)体系的不同。