• 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 Impact Assessment
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• v.30 no.1
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• pp.35-48
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• 2021

In this study, the assessment of field applicability of in-situ remediation of nitrate-contaminated groundwater located in Yesan-gun was performed. Zero-valent iron/bio composite media injected PRB (Permeable Reactive Barrier) and monitoring well were installed in the contaminated groundwater site and monitored main remediation indicators during the PRB operation. Nitrate, nitrite, ammonia, Fe ion, TOC, and turbidity were analyzed and the diversity and population of microorganism in the PRB installed site were investigated for the verification of effect of injected PRB. In the study site where is an agricultural area, a river flows from west to east that forms a river boundary and the southern area has an impermeable sector. It was found that nitrate flows into the river, which is similar as groundwater flow. Simulation result for the fate of nitrate in groundwater showed steady state of nitrate arrived after 3~5 years passed. However, it is just to consider current conditions with no additional input of contaminant source, if additional input of contaminant source occurs contamination dispersion and time for steady state are expected to be increased. The monitoring results showed that Fe ion, TOC and turbidity in groundwater were not clearly changed in concentration after PRB installation, which indicates adaptability of the injected PRB for remediation of groundwater with no additional harmful effect to water quality. The concentration of nitrate maintained less than 5mg/L until 42 days after PRB installation and recovered its initial concentration after 84 days passed and showed termination of reactivity of injected zero-valent iron/bio composite media for removal nitrate. Nitrite and ammonia ions found after installation of PRB indicates reductive removal of nitrate. And the outstanding increase of microorganism diversity and population of Betaproteobacteria Class which includes denitrification microorganism explains biologically reductive removal of nitrate in injected PRB.

• Journal of the Korean GEO-environmental Society
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• v.13 no.2
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• pp.59-65
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• 2012

Solidification/Stabilization(S/S) is one of the remediation technologies that have been applied for treating inorganic hazardous wastes. This study investigated the reduction of arsenic concentration of arsenic-contaminated soil using by S/S. The binder plays a role in controlling the mobility and solubility of the contaminants in S/S process, so it is important to determine the optimum binder content. Therefore, this study evaluated the effectiveness of S/S using four different binders(cement, zero valent iron, and monosulfate and ettringite(cement-based synthesized materials) at the binder content ranged between 5%(wt.) and 20%(wt.). The leachability of arsenic in 1 N HCl was different depending on the types of binders: cement(71.41%) > monosulfate(47.45%) > ettringite(46.36%) > ZVI(33.08%) at the binder content of 20%. Additionally, three kinds of a mixture binder were prepared using cement and additives(monosulfate, ettringite, calcium sulfoaluminate(CSA)) and tested for arsenic reduction. The highest arsenic removal capacity was found at the mass ratio of cement to the additive, 4:1 in all experiments using a mixture binder, regardless of the additives types. A mixture binder(cement and additives) resulted in higher arsenic removal relative to the arsenic removal when cement was used alone.

• 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.

• Journal of Environmental Science International
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• v.23 no.5
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• pp.903-910
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• 2014

This study examined the treatment characteristics of hard-to-degrade pollutants such as TCE which are found in organic solvent and cleaning wastewater by nZVI that have excellent oxidation and reduction characteristics. In addition, this study tried to find out the degradation characteristics of TCE by Fenton-like process, in which $H_2O_2$ is dosed additionally. In this study, different ratios of nZVI and $H_2O_2$, such as 1.0 mM : 0.5 mM, 1.0 mM : 1.0 mM, and 1.0 mM : 2.0 mM were used. When 1.0 mM of nZVI was dosed with 1.0 mM of $H_2O_2$, the removal efficiency of TOC was the highest and the first order rate constant was also the highest. When 1mM of nZVI was dosed with 0.5 mM of $H_2O_2$, the first order rate constant and removal efficiency were the lowest. The size of first order rate constant and removal efficiency was in the order of nZVI 1.0 mM : $H_2O_2$ 1.0 mM > nZVI 1.0 mM : $H_2O_2$ 2.0 mM > nZVI 1.0 mM : $H_2O_2$ 0.5 mM > $H_2O_2$ 1.0 mM > nZVI 1.0 mM. It is estimated that when 1.0 mM of nZVI is dosed with 1.0 mM of $H_2O_2$, $Fe^{2+}$ ion generated by nZVI and $H_2O_2$ react in the stoichiometric molar ratio of 1:1, thus the first order rate constant and removal efficiency are the highest. And when 1.0 mM of nZVI is dosed with 2.0 mM of $H_2O_2$, excessive $H_2O_2$ work as a scavenger of OH radicals and excessive $H_2O_2$ reduce $Fe^{3+}$ into $Fe^{2+}$. As for the removal efficiency of TOC in TCE by simultaneous dose and sequential dose of nZVI and $H_2O_2$, sequential dose showed higher first order reaction rate and removal efficiency than simultaneous dose. It is estimated that when nZVI is dosed 30 minutes in advance, pre-treatment occurs and nanoscale $Fe^0$ is oxidized to $Fe^{2+}$ and TCE is pre-reduced and becomes easier to degrade. When $H_2O_2$ is dosed at this time, OH radicals are generated and degrade TCE actively.

• Journal of Soil and Groundwater Environment
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• v.6 no.3
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• pp.13-20
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• 2001

In this Study, application of ${H_2}{O_2}$/$Fe^0 oxidation System (Fenton-like oxidation) for the oxidative treatment of high-level soil contamination with hydrocarbon was suggested. The characteristics of Fenton-like oxidation of diesel-contaminated fine soil was experimentally probed in a batch system varying initial pH, zero valent iron and hydrogen peroxide levels, and initial diesel concentration. Contaminant degradation was identified by total petroleum hydrocarbon(TPH) concentration with gas chromatography. The batch experiments showed that the optimal ${H_2}{O_2}$and $Fe^0 dosage, 10% ${H_2}{O_2}$+ 20% $Fe^0 removed 65% of initial TPH concentration (10,000mg/kg) at a retention time of 24h. And the TPH removal in the ${H_2}{O_2}$/$Fe^0 system effectively proceeded only within a limited pH range of 3-4. The zero valent iron-catalyzed Fenton-like oxidation of diesel-contaminated soil was more competitive to the $FeSO_4-catalyzed system (Fenton oxidation) in removal efficiency and cost especially for the treatment of high level contamination.

• Journal of Soil and Groundwater Environment
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• v.25 no.1
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• pp.62-73
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• 2020

PAHs commonly found in industrial sites such as manufactured gas plants (MGP) are potentially toxic, mutagenic and carcinogenic, and thus require immediate remediation. In-situ chemical oxidation (ISCO) is known as a highly efficient technology for soil and groundwater remediation. Among the several types of oxidants utilized in ISCO, persulfate has gained significant attention in recent years. Peroxydisulfate ion (S₂O₈^2-) is a strong oxidant with very high redox potential (E⁰ = 2.01 V). When mixed with Fe²⁺, it is capable of forming the sulfate radical (SO₄^-·) that has an even higher redox potential (E⁰ = 2.6 V). In this study, the influence of various iron activators on the persulfate oxidation of PAHs in contaminated soils was investigated. Several iron sources such as ferrous sulfate (FeSO₄), ferrous sulfide (FeS) and zero-valent iron (Fe(0)) were tested as a persulfate activator. Acenaphthene (ANE), dibenzofuran (DBF) and fluorene (FLE) were selected as model compounds because they were the dominant PAHs found in the field-contaminated soil collected from a MGP site. Oxidation kinetics of these PAHs in an artificially contaminated soil and the PAH-contaminated field soil were investigated. For all soils, Fe(0) was the most effective iron activator. The maximum PAHs removal rate in Fe(0)-mediated reactions was 92.7% for ANE, 83.0% for FLE, and 59.3% for DBF in the artificially contaminated soil, while the removal rate of total PAHs was 72.7% in the field-contaminated soil. To promote the iron activator effect, the effects of hydroxylamine as a reducing agent on reduction of Fe³⁺ to Fe²⁺, and EDTA and pyrophosphate as chelating agents on iron stabilization in persulfate oxidation were also investigated. As hydroxylamine and chelating agents (EDTA, pyrophosphate) dosage increased, the individual PAH removal rate in the artificially contaminated soil and the total PAHs removal rate in the field-contaminated soil increased.

• Economic and Environmental Geology
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• v.53 no.3
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• pp.297-306
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• 2020

The red mud generated from bauxite during the Bayer alumina production process has been regarded as an industrial waste due to the high alkaline property and high content of Na. Despite of its environmental problem, various studies for recovery of the valuable resources from red mud has been also carried out because of high content (25.7 wt.% as Fe₂O₃ in this study) of iron in red mud. In order to recover the iron resource in the red mud, microwave heating experiments were performed with adding of activated carbon and elemental sulfur to the red mud. Through the microwave heating the powdered red mud mixtures converted to porous and vitrified solid aggregates. The vitrified aggregates produced by microwave heating are composed of goethite, zero valent iron (Fe⁰), pyrrhotite and pyrite. And then, the microwave heating samples were dissolved in the aqua regia solution, and Fe precipitates were obtained as a Fe-chlorides by adding of NaCl salt in the aqua regia solution. The Fe recovery rates in the Fe-chloride precipitates showed differences depending on the experimental mixture conditions, and Fe grades of the end products are 49.0 wt.%, 58.0 wt.% and 59.5 wt.% under mixture conditions of red mud, red mud + activated carbon, and red mud + activated carbon + elemental S, respectively. The Fe content of 56.0 wt.% is generally known as the grade value of Fe in a iron ore for iron production, and the Fe grades of microwave heating samples with adding activated carbon and elemental S in this study are higher than the grade value of 56.0 wt.%.

• Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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• 2000.05a
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• pp.52-55
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• 2000

The effects of environmental conditions, initial dissolved oxygen concentrations, pH, and the presence of electron carrier vitamin B$_{12}$ , on the reduction rate of TNT by Fe$^{0}$ was Quantitatively analyzed using a batch reactor. In all experiments, TNT reduction was best described with a first order reaction and the reduction rate decreased with the increase in the initial DO concentration. However, the specific reaction rate did not decrease linearly with the increase in the initial DO concentration. In the presence of HEPES buffer 0.2 and 2.0 mM(pH 5.7$\pm$0.2), the specific reaction rate increased more than 5.8 times, which showed reduction rate is rather significantly influenced by the pH of the solution. To test the possibility of reaction rate enhancement, well-known electron carrier(or mediator), vitamin B$_{12}$ has augmented besides Fe$^{0}$ . In the presence of 8.0 $\mu\textrm{g}$/L of vitamin B$_{12}$ , the specific reaction rate increased as much as 14.6 times. The results indicate that the addition of trace amount of vitamin B$_{12}$ can be a promising rate controlling option for the removal of organics using a Fe$^{0}$ filled permeable reactive barrier.

• Advances in environmental research
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• v.3 no.1
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• pp.29-43
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• 2014

Pharmaceutical wastewater effluents are well known for their difficult elimination by traditional biotreatment methods and their important contribution to environmental pollution due to its fluctuating and recalcitrant nature. OTC is one of the nonbiodegradable antibiotics that makes antibiotic-resistant, so it can make be high risk for environment. NZVI can be a good choice for removal of OTC in aqueous solution. Response surface methodology (RSM) was used to optimize the amounts of NZVI and OTC to be used at pH 3 and under 200 W, UV-A irradiation. The responses were removal percent of absorption at 290 and 348 nm, TOC and COD of OTC. In the optimum condition, Linear model was performed 155 ppm of OTC were removed by 1000 ppm NZVI after 6.5 hours and the removal efficiency of absorption at 290 and 348 nm, TOC and COD were 87, 95, 85 and 89 percent, respectively. In the similar process, there is no organic compound after 14 hours. The parameters ORP, DO and pH were investigated for 6:30 hours to study the type of NZVI reaction in process. In the beginning of reaction, oxidation was the dominant reaction after 3 hours, photocatalytic reaction was remarkable. The mechanism of OTC degradation is proposed by HPLC/ESI-MS and four by products were found. Also the rate constants (first order kinetic chain reaction model) were 0.0099, 0.0021, 0.0010, 0.0049 and $0.0074min^{-1}$, respectively.