• Journal of the Mineralogical Society of Korea
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• v.16 no.1
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• pp.107-123
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• 2003

The objective of this study was to investigate mineral precipitates, which derived from the zero valent iron (ZVI) corrosion during TCE dechlorination and to find the controlling factors in mineral precipitates. A series of column experiemnts were conducted to evaluate the location of ZVI and the effects of electrode arrangements in electro-enhanced permeable reactive barrier (E2PRB) systems. Based on mineralogical study, ZVI samples near the influent port had more lepidocrocite, ferrihydrite or Fe (oxy)hydroxide, and (phospho)siderite while backward samples had more akaganeite, magnetite/maghemite, and intermediate green rust (GR) I and GR II. A suite of mineral distribution was preferabley related to the dissolved oxygen and the increased pH. Controlling factors of mineral precipitates in an E2PRB system were found to be (1) pH, (2) dissolved oxygen, (3) the types of Fe intermediates, and (4) anionic species to form complex strongly.

• Journal of Soil and Groundwater Environment
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• v.11 no.3
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• pp.59-65
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• 2006

Reductive dechlorination of chlorophenols by nickel coated iron was investigated to understand the feasibility of using Ni/Fe for the in situ remediation of contaminated groundwater. Zero valent iron (ZVI) was amended with Ni(II) ions to form bimetal (Ni/Fe). Dechlorination of 4-chlorophenol and formation of intermediates was studied using Ni/Fe. Effects of initial contaminant concentration, bimetal loading, presence of humic acid, and solution chemistry were also evaluated. Experimental results showed that Ni/Fe bimetal was so effective that more than 95% of 4-CP degradation was achieved within 240 minutes. Pseudo first-order rate constant for the dechlorination reaction was well correlated with bimetal loading. Humic acid competed for the reactive sites on the nickel coated iron with chlorophenols, lowering the dechlorination efficiency. No significant changes in solution pH were observed in the dechlorination of chlorophenols with Ni/Fe in the absence of buffer, indicating that reactivity of bimetal (Ni/Fe) could be prolonged. Phenol was found as a dechlorination intermediate of the conversion of 4-chlorophenol compound by Ni/Fe.

• Korean Journal of Environmental Agriculture
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• v.28 no.2
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• pp.202-208
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• 2009

The dechlorination of endosulfan (6,7,8,9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepine-3-oxide) and its metabolite, endosulfan sulfate via reaction with zerovalent iron under various pH conditions was studied using aqueous solution. The reaction products, which were probably produced from endosulfan and endosulfan sulfate by ZVI were identified by GC-MS. The lower the pH of reaction solution, the higher the transformation rate of endosulfan and endosulfan sulfate. The transformation rates of endosulfan and endosulfan sulfate in pH 3.0 by ZVI were 28% and 90% but those of endosulfan and endosulfan sulfate in mixture solution of water/acetone were 65% and 92%, respectively. The pH of reaction solution after ZVI treatment was increased to pH 10. Endosulfan was hydrolyzed at pH 10 but endosulfan sulfate was not hydrolyzed. Two unknown peaks were produced from endosulfan sulfate by treatment of ZVI. As a result of GC-MS analysis, unknown peaks were guessed to be structural isomer substituted hydrogen for chlorine.

• Korean Journal of Environmental Agriculture
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• v.27 no.1
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• pp.86-91
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• 2008

Dicamba(3,6-dichloro-2-methoxybenzoic acid) is used to control for pre and post-emergence of annual and perennial broad-leaf weeds. It is very soluble in water and highly mobile, acidic herbicide. So it is easily moved and detected in groundwater. Zerovalent iron(ZVI) has been used for the reductive degradation of certain compounds through amination of nitro-substituted compounds and dechlorination of chloro-substituted compounds. In this study, we investigated the potential of ZVI for the oxidative degradation of dicamba in water. The degradation rate of dicamba by ZVI was more rapidly increased in pH 3.0 than pH 5.0 solution. The degradation percentage of dicamba was increased with increasing amount of ZVI from 0.05% to 1.0%(w/v) and reached above 90% within 3 hours of reaction. As a result of identification by GC-MS after derivatization with diazomethane, we obtained three degradation products of dicamba by ZVI. They were identified 4-hydroxy dicamba or 5-hydroxy dicamba, 4,5-dihydroxy dicamba and 3,6-dichloro-2-methoxyphenol. 4-Hydroxy dicamba or 5-hydroxy dicamba and 4,5-dihydroxy dicamba are hydroxylation products of dicamba. 3,6-dichloro-2-methoxyphenol is hydroxyl group substituted compound instead of carboxyl group in dicamba. We also confirmed the same degradation products of dicamba in the Fenton reaction which is one of oxidation processes using ferric sulfate and hydrogen peroxide. But we could not find out the dechlorinated degradation products of dicamba by ZVI.

• Journal of Korean Society of Environmental Engineers
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• v.27 no.2
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• pp.123-129
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• 2005

In situ permeable reactive barrier (PRB) technologies have been proposed to reductively remove organic contaminants from the subsurface environment. The major reactive material, zero valent iron ($Fe^0$), is oxidized to ferrous iron or ferric iron in the barriers, resulting in the decreased reactivity. Iron-reducing bacteria can reduce ferric iron to ferrous iron and iron reduced by these bacteria can be applied to dechlorinate chlorinated organic contaminants. Iron reduction by iron reducing bacteria, Shewanella algae BrY, was observed both in aqueous and solid phase and the enhancement of TCE removal by reduced iron was examined in this study. S. algae BrY preferentially reduced Fe(III) in ferric citrate medium and secondly used Fe(III) on the surface of iron oxides as an electron acceptor. Reduced iron formed reactive materials such as green rust ferrihydrite, and biochemical precipitation. These reactive materials formed by the bacteria can enhance TCE removal rate and removal capacity of the reactive barrier in the field.

• Journal of Environmental Health Sciences
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• v.26 no.2
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• pp.14-21
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• 2000

DEAE-Toyopearl 650S, Superdex pg-75, Poros HQ, Superdex H200의 각종 칼러크로마토그래피를 이용하여 C.bifermentans DPH-1균주로부터 테트라클로로에틸렌(PCE) 분해 효소를 정제했다. 이 PCE 분해효소 (PCE dehalogenase)는 PCE를 환원적 탈염소화 반응에 의해 시스디클로로에딜렌 (cis-1,2-dichloroethylene)에 전환 가능하여, 이 때의 Vmax 및 Km 치는 각각 73 nmol/h.mg protein, 12$\mu$M이었다. 본 PCE dehalogenase의 겔여과 분자량 Maker Kit를 이용한 분석결과(70kDa)는 SDS-PAGE에 나타난 분자량(35kDa)의 약 2배인 것으로 확인되었다. 따라서 본 효소는 분자량 70kDa의 이량체(Homo dimer)인 것으로 추정되었다. 본 효소의 최적온도 및 pH는 각각 35$^{\circ}C$ 및 8.0 이었다. 또한 본 효소는 PCE외의 트리클로로에틸렌, 디클로로에틸렌 이성체, 1,2-디클로로에템, 1,2-디클로로프로판, 1,1,2-트리클로로에탄에 대하여도 활성을 타나내었다. N-말단 아미노산 분석결과에서도 본 효소는 현재 알려진 PCE dehalogenase와 그 배열이 전혀 다른 것으로 나타나 각종 유기염소 화합물의 분해능을 보유한 신종의 PCE 분해효소인 것이 확인되었다.

• Journal of Soil and Groundwater Environment
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• v.12 no.6
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• pp.38-45
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• 2007

Trichloroethylene (TCE) is a representative dense non-aqueous phase liquid (DNAPL) and has contaminated substance environments including soil and groundwater due to leakage and careless. DNPAL, has been treated by surfactant-enhanced aquifer remediation (SEAR). After application of SEAR, groundwater contains still surfactant as well as little amount of residual TCE. Permeable reactive barrier using zero-valent iron (ZW) is a very effective technology to treat the residual TCE in groundwater. In this study, the effect of the residual surfactant on the reductive dechlorination of residual TCE was investigated using ZVI. Mixed surfactant composed of nonioinic surfactant and cationic surfactant was used as a residual surfactant because of toxicity and enhancement of dechlorination rate. Structure of surfactant affected significantly the decrhlorination rate of TCE. Mixed surfactant system with relatively short polyethylene oxide (PEO) chain in nonionic surfactant, cationic surfactant did not affect TCE dechlorination rate. However, mixed surfactant system with relatively long PEO chain in nonionic surfactant shows that TCE dechlorination rate was significantly dependent on fraction of cationic surfactant and HLB of nonionic surfactant. Cationic surfactant with trimethyl ammonium group enhanced reductive dechlorination rate compared to that surfactant with pyridinium group.

• Clean Technology
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• v.29 no.2
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• pp.118-125
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• 2023

Once a site is contaminated with polychlorinated biphenyls (PCBs), serious environmental and human health risks are inevitable. Therefore, innovative but economical in situ remediation technologies must be immediately applied to the contaminated site. Recently, nanoscale zero-valent iron (nano-ZVI) particles have successfully been applied for the dechlorination of various chlorinated organic compounds like TCE, PCE and DDT, and they are considered to be environmentally safe due to the high abundance of iron in the earth's crust. Nano-ZVIs are much more reactive than granular ones, but tend to agglomerate due to their high surface energy and magnetic properties. In order to prevent them from being agglomerated toward larger particles, TiO₂ was used as a support to immobilize the nano-ZVI particles as much as possible. 10wt% ZVI/TiO₂ was prepared by adding NaBH₄ slowly into an FeSO₄/TiO₂ aqueous slurry. In spite of their non-uniformity in size, the nano-ZVI particles were quite successfully dispersed onto the exterior surface of a non-porous TiO₂ powder. The ZVI/TiO₂ was then employed to degrade Aroclor 1242, a kind of PCBs standard, in spiked soil, and its reactivity towards the degradation of Aroclor 1242 was investigated. The fabricated ZVI/TiO₂ degraded Aroclor 1242 in soil quite effectively, but the creation of remaining dechlorinated compounds, possibly high molecular weight hydrocarbons, in the soil was unavoidable.

• Journal of Korean Society of Environmental Engineers
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• v.33 no.6
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• pp.413-419
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• 2011

Nanoscale zero-valent iron (NZVI) particles were tested as remediation media for groundwater contaminated by organic pollutants (e.g., TCE, trichloroethylene). The contaminated groundwater contained anions ($NO_3^-$, $Cl^-$, $SO_4^{2-}$, and $HCO_3^-$) and natural organic matter (NOM). Treatability of commercial NZVI particles (NANOFER 25, Nanoiron, Czech) was tested by using a synthetic groundwater and the field groundwater samples. More than 95% of 1.8 mM TCE was removed within 20 hours with a NZVI dosage of 25 g/L ($k=0.15hr^{-1}$). Repetitive degradation experiments revealed that the removal capacity of NANOFER 25 was 0.19 mmole TCE/g NZVI. TCE degradation reactions were not substantially affected by the presence of each anion with concentrations as high as 100 times the average field concentrations. However, when the four anions ($NO_3^-$, $Cl^-$, $SO_4^{2-}$, $HCO_3^-$) were present simultaneously. the degradation reactivity and removal capacity were decreased by 60% ($k=0.069hr^{-1}$) and 10%, respectively. The k value of TCE degradation in the presence of NZVI (25 g/L) with dissovled organic carbon of 2.5 mg/L was also decreased by 84% ($k=0.025hr^{-1}$). In the experiments with the field groundwater, more than 90% of $1.8{\mu}M$ TCE, which is the concentration of TCE at the source zone, was removed within 10 hours with a NANOFER 25 dosage of 25 g/L. The results imply that the contaminated groundwater can effectively be treated by NANOFER 25 with more information on the hydrogeology of the site.

• Journal of Soil and Groundwater Environment
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• v.13 no.6
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• pp.93-102
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• 2008

Experimental studies were conducted to characterize the synthesized nanoscale zero-valent iron (NZVI) which is resistant to oxidation in the atmospheric environment. XRD, XPS, and TEM analyses revealed that the oxidation-resistant NZVI particles formed under various controlled air contact conditions (4, 8 and 12 mL/min) have shells with ${\sim}$5 nm thickness. The shells consist of magnetite (${Fe_3}{O_4}$) and maghemite (${\gamma}-{Fe_2}{O_3}$), predominantly. No substantial differences were found in the shell components and thickness among NZVI particles formed under the various air flow rates. On the other hand, shell was not detected in the TEM image of rapidly oxidized NZVI particles. NZVI particles synthesized under the various air flow rates showed similar TCE degradation performances ($k_{obs}$= 0.111, 0.102, and 0.086 $hr^{-1}$), which are equivalent to approximately 80% of those obtained by the fresh NZVI particles. TCE degradation efficiencies of the NZVI particles(fresh, controlled air contact and rapidly oxidized) were improved after equilibrating with water for one day, indicating that depassivation of the shells occurred. The performances of NZVI particles decreased to 90% and 50% of those of the fresh NZVI particles, when they were equilibrated with the atmosphere for a week and two months, respectively. The NZVI particles synthesized under the controlled air contact would have advantages over traditional NZVI particles in terms of practical application into the site, because of their inertness toward atmospheric oxygen.