• 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.

• Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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• 2002.04a
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• pp.118-121
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• 2002

The kinetics and stoichiometry of the reduction of hexavalent chromium (Cr(Ⅵ)) with ferrous iron (Fe(II)) were examined in systems with and without aquifer solids. Cr(Ⅵ) reduction was rapid in the absence of solids, but demonstrated slower and more complex kinetics in the presence of aquifer solids. The aquifer solids removed Fe(II) from solution and a portion of the reducing capacity of Fe(II) was transferred to the aquifer solids. The solid phases were then able to continue to remove Cr(Ⅵ). This suggests in-situ treatment of Cr(Ⅵ) by Fe(II) injection would be feasible in the aquifer environment. In general, re-oxidation of reduced chromium by molecular oxygen was not observed in our systems over time periods of nearly one year.

• Journal of Soil and Groundwater Environment
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• v.13 no.1
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• pp.24-31
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• 2008

Sulfate reducing bacteria (SRB) is universally distributed in the sediment, especially in marine environment. SRB reduce sulfate as electron acceptor to hydrogen sulfide in anaerobic condition. Hydrogen sulfide is reducing agent enhancing the reduction of the organic and inorganic compounds. With SRB, therefore, the degradability of organic contaminants is expected to be enhanced. Ferrous iron reduced from the ferric iron which is mainly present in sediment also renders chlorinated organic compounds to be reduced state. The objectives of this study are: 1) to investigate the reduction of TCE by hydrogen sulfide generated by tht growth of SRB, 2) to estimate the reduction of TCE by ferrous iron generated due to oxidation of hydrogen sulfide, and 3) to illuminate the interaction between SRB and ferrous iron. Mixed bacteria was cultivated from the sludge of the sewage treatment plant. Increasing hydrogen sulfide and decreasing sulfate confirmed the existence of SRB in mixed culture. Although hydrogen sulfide lonely could reduce TCE, the concentration of hydrogen sulfide produced by SRB was not sufficient to reduce TCE directly. With hematite as ferric iron, hydrogen sulfide produced by SRB was consumed to reduce ferric ion to ferrous ion and ferrous iron produced by hydrogen sulfide oxidation decreased the concentration of TCE. Tests with seawater confirmed that the activity of SRB was dependent on the carbon source concentration.

• 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.

• Progress in Superconductivity and Cryogenics
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• v.21 no.2
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• pp.15-21
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• 2019

In the mine exploration sites, sustainable treatment system of mine water with energy saving and minimized chemical additives is required. Since most of the mine water contains highly-concentrated ferrous ion, it is necessary to study on the removal method of iron ions. We propose the system consisting of two processes; precipitation process by air oxidation using solid catalyst-modified magnetite and separation process combining gravitational sedimentation and magnetic separation using a permanent magnet. Firstly, in the precipitation process (a former process of the system), we succeeded to prepare solid catalyst-modified magnetite. Air oxidation using solid catalyst-modified magnetite using $Fe_2(SO_4)_3$ as a starting material showed high iron removal capability. Secondly, in the separation process (latter process of the system), solid catalyst-modified magnetite using $Fe_2(SO_4)_3$ as a starting material can be separated by a superconducting bulk magnet and a permanent magnet.

• Resources Recycling
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• v.16 no.3 s.77
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• pp.19-26
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• 2007

The bottom ash of municipal solid waste incineration generated during incineration of municipal solid waste in metropolitan area consists of ceramics, glasses, ferrous materials, combustible materials and food waste and so on. Although the ferrous material was separated by the magnetic separation before the incineration process, of which content accounts for about $3{\sim}11%$ in bottom ash. The formation of a $Fe_3O_4-Fe_2O_3$ double layer(similar to pure Fe) on the iron surface was found during air-annealing in the incinerator at $1000^{\circ}C$. A strong thermal shock, such as that takes place during water-cooling of bottom ash, leads to the breakdown of this oxidation layer, facilitating the degradation of ferrous metals and the formation of corrosion products and it existed as $Fe_2O_3,\;Fe_3O_4\;and\;FeS_2$. So, many problems could occur in the use of bottom ash as an aggregate substitutes in construction field. Therefore, in this study, the separation of ferrous materials from municipal solid waste incineration bottom ash was investigated. In the result, the ferrous product(such as $Fe_2O_3,\;Fe_3O_4,\;FeS_2$ and iron) by magnetic separator at 3800 gauss per total bottom ash(w/w.%) accounted for about 18.7%, and 87.7% of the ferrous product was in the size over 1.18 mm. Also the iron per total bottom ash accounted for about 3.8% and the majority of it was in the size over 1.18 mm.

• Korean Journal of Materials Research
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• v.18 no.4
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• pp.218-221
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• 2008

A $Fe(OH)_2$ suspension was prepared by mixing iron sulfate and a weak alkali ammonia solution. Following this, iron oxides were synthesized by passing pure oxygen through the suspension (oxidation). The effects of different reaction temperatures ($30^{\circ}C$, $50^{\circ}C$, $70^{\circ}C$) and equivalent ratios ($0.1{\sim}10.0$) on the formation of iron oxides were investigated. An equilibrium phase diagram was established by quantitative phase analysis of the iron oxides using the Rietveld method. The equilibrium phase diagram showed a large difference from the equilibrium phase diagram of Kiyama when the equivalent ratio was above 1, and single $Fe_3O_4$ phase only formed above an equivalent ratio 2 at all reaction temperatures. Kiyama synthesized iron oxide using iron sulfate and a strong alkali NaOH solution.

• Journal of Environmental Health Sciences
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• v.23 no.1
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• pp.34-42
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• 1997

A laboratory experiments were performed to investigate the treatment of photographic processing wastewater by chemical oxidation and biological treatment system. The effect of reaction conditions such as hydrogen peroxide dosage, ferrous sulfate dosage and pH on the COD removal in Fenton oxidation were investigated. The optimal dosage of hydrogen peroxide was 2.58 M and 3.87 M for the developing and fixing process wastewater, respectively. The Fenton oxidation was most efficient in the pH range of 3-5 and the optimal condition for initial reaction pH was 5 for a developing process wastewater. With iron powder catalyst, the COD for a developing process wastewater was removed in lower pH than with ferrous sulfate catalyst. The removal efficiency of COD for refractory compounds such as Diethyleneglycol, Benzylalcohol, Hydroxylamine Sulfate, Ammonium Thiosulfate, Ammonium Ferric EDTA and Disodium EDTA in the photogaphic wastewater was found than 90% except Potassium Carbonate. When the photographic processing wastewater after pretreatment by Fenton oxidation was treated with batch activated sludge process, the addition of $KH_2PO_4$ as a phosphorous compound improved the removal efficiency of COD. During the continuous biological treatment of developing and fixing process wastewater after pretreatment by Fenton oxidation, the effluent COD concentration less than 100 mg/l was obtained at 0.425 and 0.25 kgCOD/m$^3$.d, respectively.

• Environmental Engineering Research
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• v.25 no.1
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• pp.36-42
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• 2020

Fenton process is one of the most effective advanced oxidation processes for the removal of pollutants from wastewater. In this study, while ferrous iron was used in conventional Fenton process (CFP); nano-sized iron(II, III) oxide was experienced in modified Fenton process (MFP) as a new catalyst alternative. In order to enhance their oxidation efficiencies, both CFP and MFP were combined with ultrasonication at 53 kHz fixed frequency. Thus, the influences of both catalyst iron species and ultrasonication on color and chemical oxygen demand (COD) removals from synthetic textile wastewater including Maxilon Red GRL 200% dyestuff were investigated experimentally. While the COD and color removal rates were found as 72.5% and 69.7% via CFP; they were 87% and 75.8% by ultrasonicated CFP, respectively. The color and COD removals were 40.6% and 64.8% via MFP, and 49.9 and 73.1% by ultrasonicated MFP, respectively. Therefore, it was found that the simultaneously usage of ultrasonication with CFP and MFP was improved the COD and color removal efficiencies and oxidation rates even at lower H₂O₂ dosages, compared to individual CFP and MFP. Moreover, the color and COD removal kinetics were also modelled mathematically and compared in the study.

• Bulletin of the Korean Chemical Society
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• v.24 no.7
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• pp.981-985
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• 2003

Fluorine-19 NMR solution measurements have been made for various phenyl-fluorinated iron porphyrin complexes. Large chemical shifts for phenyl fluorine signals of iron(III) and iron(II) are observed, and these signals are sensitive to electronic structure. The chemical shift differences in ortho-phenyl fluorine signals between high-spin ferric and low-spin ferric tetrakis(pentafluorophenyl)porphyrins are approximately 40 ppm, whereas the differences are approximately 7 ppm between high- and low-spin states of ferrous tetrakis(pentafluorophenyl)porphyrin complexes. Analysis of fluorine-19 isotropic shifts for the iron(III) tetrakis(pentafluorophenyl) porphyrin using fluorine-19 NMR indicates there is a sizable contact contribution at the ortho-phenyl fluorine ring position. Large phenyl fluorine-19 NMR chemical shift values, which are sensitive to the oxidation and spin states, can be utilized for identification of the solution electronic structures of iron(III) and iron(II) porphyrin complexes.