• Journal of Soil and Groundwater Environment
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• v.17 no.2
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• pp.15-21
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• 2012

MTBE (Methyl tertiary-butyl ether) has been commonly used as an octane enhancer to replace tetraethyl lead in gasoline, because MTBE increases the efficiency of combustion and decreases the emission of carbon monoxide. However, MTBE has been found in groundwater from the fuel spills and leaks in the UST (Underground Storage Tank). Fenton's oxidation, an advanced oxidation catalyzed with ferrous iron, is successful in removing MTBE in groundwater. However, Fenton's oxidation requires the continuous addition of dissolved $Fe^{2+}$. Zero-valent iron is available as a source of catalytic ferrous iron of MFO (Modified Fenton's Oxidation) and has been studied for use in PRBs (Permeable Reactive Barriers) as a reactive material. Therefore, this study investigated the condition of optimization in MFO-PRBs using waste zero-valent iron (ZVI) with the waste steel scrap to treat MTBE contaminated groundwater. Batch tests were examined to find optimal molar ratio of MTBE : $H_2O_2$ on extent to degradation of MTBE in groundwater at pH 7 with 10% waste ZVI. As the results, the ratio of optimization of MTBE to hydrogen peroxide for MFO was determined to be 1:300[mM]. The column experiment was conducted to know applicability of MFO-PRBs for MTBE remediation in groundwater. As the results of column test, MTBE was removed 87% of the initial concentration during 120days of operational period. Interestingly, MTBE was degraded not only within waste ZVI column but also within sand column. It means the aquifer may affect continuously the MTBE contaminated groundwater after throughout the waste ZVI barrier. The residual products showed acetone, TBF (Tert-butyl formate) and TBA (Tert-butyl acetate) during this test. The results of the present study showed that the recycled materials can be effectively used for not only a source of catalytic ferrous iron but also a reactive material of the MFO-PRBs to remove MTBE in groundwater.

• Environmental Engineering Research
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• v.20 no.3
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• pp.205-211
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• 2015

Reduced forms of iron, such as zero-valent ion (ZVI) and ferrous ion (Fe[II]), can activate dissolved oxygen in water into reactive oxidants capable of oxidative water treatment. The corrosion of ZVI (or the oxidation of (Fe[II]) forms a hydrogen peroxide ($H_2O_2$) intermediate and the subsequent Fenton reaction generates reactive oxidants such as hydroxyl radical ($^{\bullet}OH$) and ferryl ion (Fe[IV]). However, the production of reactive oxidants is limited by multiple factors that restrict the electron transfer from iron to oxygen or that lead the reaction of $H_2O_2$ to undesired pathways. Several efforts have been made to enhance the production of reactive oxidants by iron-induced oxygen activation, such as the use of iron-chelating agents, electron-shuttles, and surface modification on ZVI. This article reviews the chemistry of oxygen activation by ZVI and Fe(II) and its application in oxidative degradation of organic contaminants. Also discussed are the issues which require further investigation to better understand the chemistry and develop practical environmental technologies.

• Journal of Soil and Groundwater Environment
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• v.19 no.1
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• pp.63-69
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• 2014

This paper presents the feasibility of using different iron oxides (microscale hematite (HT), microscale magnetite (MT), and nanoscale maghemite (NMH)) in enhancing nitrate reduction by zero-valent iron (Fe(0)) under two solution conditions (artificial acidic water and real groundwater). Addition of MT and NMH into Fe(0) system resulted in enhancement of nitrate reduction compared to Fe(0) along reaction, especially in groundwater condition, while HT had little effect on nitrate reduction in both solutions. Field emission scanning electron microscopy (FESEM) analysis showed association of MT and NMH with Fe(0) surface, presumably due to magnetic attraction. The rate enhancement effect of the minerals is presumed to arise from its role as an electron mediator that facilitated electron transport from Fe(0) to nitrate. The greater enhancement of MT and NMH in groundwater was attributed to surface charge neutralization by calcium and magnesium ions in groundwater, which in turn facilitated adsorption of nitrate on Fe(0) surface.

• Journal of Korean Society of Environmental Engineers
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• v.30 no.12
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• pp.1262-1267
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• 2008

Reductive discolorization studies were conducted. Azo-dyes usually have biological toxicity and it is known that the dyes are hardly removed by biological treatments. One of the simplest way to remove the color is to break the azo-bond and it is possible to break the bond with zero-valent metals. Three types of azo-dyes (Cibacron Briliant Yellow 3G-P (CBY3G-P), Benzopurpurin 4b (B-4B), Chicago sky blue 6b (CSB6B)) were tested. All tested azo-dyes were highly pH dependent and lower pH was preferred. The reaction mechanism was reductive cleavage and amines were expected as products. The dissolved iron ions from zero-valent iron can also remove the color through coagulation and precipitation and a set of experiments were conducted to evaluate the contribution by the dissolved iron. The results indicated that the contribution were also dependent on the type of dyes. This study showed that the reductive cleavage using zero-valent iron could be an alternative for the azo-dye waste water.

• Journal of Environmental Science International
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• v.31 no.1
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• pp.77-85
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• 2022

Environmental contamination by organic compounds are not only restricted to water, but extends to soil and groundwater as well. However, highly oxidized compounds, such as halogenated organics and nitro-compounds, can be detoxified employing reducing methods. Permeable reactive barrier is one of the representative technologies where zero-valent metals (ZVMs) are employed for groundwater remediation. However, organics contaminates often contaminate the unsaturated zone above the groundwater. Despite the availability of technologies like soil vapor extraction and bioremediation, removing organic compounds from this zone represents several challenges. In this study, the reduction of nitrobenzene to aniline was achieved using zero-valent iron (ZVI) under unsaturated conditions. Results indicated that the water content was an important variable in this reaction. Under dry conditions (water content = 0.2%), the reduction reaction was inhibited; however, when the water content was between 10% and 25% (saturated condition), ZVI can reduce nitrobenzene. Palladized iron (Pd/Fe) can be used to reduce nitrobenzene when the water content is between 2.5% and 10%. The reaction was evaluated over a wide range of temperatures (10 - 40 ℃), and the results indicated that increasing the temperature resulted in increased reaction rates under unsaturated conditions.

• Environmental Engineering Research
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• v.24 no.3
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• pp.463-473
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• 2019

Nanoscale zero-valent iron (nZVI) has proved to be an effective tool in applied environmental nanotechnology, where the decreased particle diameter provides a drastic change in the properties and efficiency of nanomaterials used in water purification. However, the agglomeration and colloidal instability represent a problematic and a remarkable reduction in nZVI reactivity. In view of that, this study reports a simple and cost-effective new strategy for ultra-small (< 7.5%) distributed functionalized nZVI-EG (1-9 nm), with high colloidal stability and reduction capacity. These were obtained without inert conditions, using a simple, economical synthesis methodology employing two stabilization mechanisms based on the use of non-aqueous solvent (methanol) and ethylene glycol (EG) as a stabilizer. The information from UV-Vis absorption spectroscopy and Fourier transform infrared spectroscopy suggests iron ion coordination by interaction with methanol molecules. Subsequently, after nZVI formation, particle-surface modification occurs by the addition of the EG. Size distribution analysis shows an average diameter of 4.23 nm and the predominance (> 90%) of particles with sizes < 6.10 nm. Evaluation of the stability of functionalized nZVI by sedimentation test and a dynamic light-scattering technique, demonstrated very high colloidal stability. The ultra-small particles displayed a rapid and high nitrate removal capacity from water.

• Journal of the Mineralogical Society of Korea
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• v.28 no.2
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• pp.95-108
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• 2015

Nano-sized iron colloids are formed as acid mine drainage is exposed to surface environments and is introduced into surrounding water bodies. These iron nanomaterials invoke aesthetic contamination as well as adverse effects on aqueous ecosystems. In order to control them, the characteristics of their behaviour should be understood first, but the cumulative research outputs up to now are much less than the expected. Using zero-valent iron (ZVI) and magnetite, this study aims to investigate the behaviour of iron nanomaterials according to the change in the composition and pH of background electrolyte and the concentration of natural organic matter (NOM). The size and surface zeta potential of iron nanomaterials were measured using dynamic light scattering. Characteristic behaviour, such as aggregation and dispersion was compared each other based on the DLVO (Derjaguin, Landau, Verwey, and Overbeek) theory. Whereas iron nanomaterials showed a strong tendency of aggregation at the pH near point of zero charge (PZC) due to electrostatic attraction between particles, their dispersions became dominant at the pH which was higher or lower than PZC. In addition, the behaviour of iron nanomaterials was likely to be more significantly influenced by cations than anions in the electrolyte solutions. Particularly, it was observed that divalent cation influenced more effectively than monovalent cation in electrostatic attraction and repulsion between particles. It was also confirmed that the NOM enhanced the dispersion nanomaterials with increasing the negative charge of nanomaterials by coating on their surface. Under identical conditions, ZVI aggregated more easily than magnetite, and which would be attributed to the lower stability and larger reactivity of ZVI.

• 한국방재학회:학술대회논문집
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• 2009.02b
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• pp.155.2-155.2
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• 2009

• Proceedings of the KSEEG Conference
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• 1999.04a
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• pp.4-4
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• 1999

• Proceedings of the KSEEG Conference
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• 1999.04a
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• pp.335-335
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• 1999