• 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 Geotechical Society Conference
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• 2000.11a
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• pp.435-442
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• 2000

Batch test and column test were performed to develop the design factors for permeable reactive barriers(PRBs) against ammonium and heavy metals, Clinoptilolite, a kind of natural zeolites having excellent cation exchange capacity(CEC), was choosen for the reacting materials through the ion-exchange mechanism. In the batch test, the reactivity of clinoptilolite for ammonium, lead, and copper was examined varying the initial concentration of contaminants(ammonium: 20, 40, 80 ppm, heavy metals: 10, 20, 40 ppm) and the particle size of clinoptilolites(0-0.15, 0.42-0.85, 1-1.25 mm). The reactivity is increasing as the initial concentration decrease and particle size decrease. In the column test, the permeability and the reactivity of the specimens were examined using flexible-wall permeameter. Specimens were made of clinoptilolite and Jumunjin-sand with 20 : 80 weight ratio varying particle size of clinoptilolite. The maximum permeability(1${\times}$10$\^$-4/-5${\times}$10$\^$-5/cm/s) was achieved in the specimen made of 0.42-0.85 mm clinoptilolite and sand.

• Journal of the Korean Geotechnical Society
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• v.24 no.6
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• pp.17-25
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• 2008

Permeable reactive barriers (PRBs) technology can be applied to contaminated groundwater remediation. It is necessary to select adequate reactive material according to contaminant characterization. In groundwater. In this research, the reaction between reactive material and heavy metal contaminants was estimated through batch test. Reactive material was slag, which has been produced in Gwangyang power plant, and heavy metal contaminants were cadmium, lead and copper. Batch test consisted of two testes: 1) sorption equilibrium test and 2) sorption kinetic test. Sorption equilibrium test was performed for estimating slag sorption capacity against contaminants. And sorption kinetic test was performed for slag sorption rate with contaminants species, contaminants initial concentration and sulfate. Sorption capacity and sorption rate were affected by contaminant species. Sorption rate increased with increasing initial concentration in lead and copper but decreased with increasing initial concentration in cadmium. Sorption rate increased in existing sulfate. In low concentration, film diffusion was domain mechanism, and in high concentration, particle diffusion was domain mechanism.

• Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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• 2003.09a
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• pp.168-171
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• 2003

This research was conducted to assess the performance of the mixed reactive materials with sand, iron filings, and HDTMA-bentonite for trichloroethylene (TCE) and chromate removal under controlled groundwater flow conditions. TCE and chromate removal rates with the mixtures of iron filing/HDTMA-bentonite were highest among four columns due to reduction by iron filings and sorption by HDTMA-bentonite. The greater capacity of the mixed iron filing/HDTMA-bentonite compared HDTMA-bentonite was due to an enhanced chromate reduction in addition to chromate sorption. The presence of chromate caused greater inhibition of TCE removal in the column with iron filings, while the presence of TCE caused less inhibition of TCE. Also, nitrate caused the decrease in TCE removal relative to chloride. Nitrate ions may also significantly affect TCE reduction rates by competing for electrons with the chlorinated compounds. The anion and co-existed contaminants competing effects should be considered when designed permeable reactive barriers (PRBs) composed of zero valent iron for field applications to remediate TCE and chromate.

• KSCE Journal of Civil and Environmental Engineering Research
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• v.32 no.1B
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• pp.85-91
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• 2012

Permeable Reactive Barriers (PRBs) using zero valent iron (ZVI, $Fe^0$) is a promising technology for in-situ remediation of trichloroethylene (TCE) forming dense non aqueous phase liquid (DNAPL). The objective of this study is to develop an enhanced treatment method of trichloroethylene-contaminated groundwater using ZVI packed bed with direct current (D.C.). A column experiment was performed to investigate degradation efficiency of TCE that was performed in three different combination of control (only sand), ZVI column (ZVI:sand, packing ratio 1:2(v/v)) and bipolar column (ZVI:sand=1:2(v/v) with electric current) in the test columns. As the results of this study, the degradation efficiency of TCE was improved with simultaneous application of both bipolar column compared to that used ZVI column. Because ZVI particles are isolated and individual particles act like small electrodes. In this experiment, it was indicated a basic material for application of bipolar packed bed as electro-PRBs that was effective degradation of TCE.

• Proceedings of the Korean Geotechical Society Conference
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• 2003.03a
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• pp.185-188
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• 2003

오염된 지하수 정화에 있어 반응벽체(Permeable Reactive Barriers, PRBs)를 이용한 정화기법은 최근 가장 큰 관심을 모으고 있는 기술이다. 반응벽체의 적용에 있어 가장 중요한 사항은 오염물질의 특성을 고려하여 적절한 반응성을 가지는 충진물질을 선택하는 일이다. 지금까지 연구된 반응물질 중 제올라이트는 취득이 용이하고 가격이 저렴하여, 암모늄이나 중금속과 같은 양이온성 오염물질의 정화에 그 적용성을 인정받아왔다. 하지만 표면에 음전하를 띠는 제올라이트의 특성 때문에, 지하수내에서 음이온의 형태로 존재하는 Cr(VI) 등에는 반응성이 없는 것으로 알려져 왔다. 이에 본 연구에서는 제올라이트에 영가철을 결합한 ZanF란 물질을 개발하여 양이온성 중금속의 하나인 납과 음이온성 중금속의 하나인 Cr(VI)을 동시 제거하는 실험을 수행하였다. 실험결과 ZanF는 초기농도 2-15mmol를 가지는 납 오염용액에 대해 90% 이상의 제거율을 보였으며, 초기농도 0.1 mmol을 가지는 Cr(VI) 오염용액의 농도를 5시간 내에 검출한계 이하로 떨어뜨리는 탁월한 효과를 보였다. 실험결과를 토대로 ZanF는 납과 Cr(VI)으로 동시에 오염된 지하수 정화에 효과적으로 사용될 수 있으리라 기대된다.

• 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 Soil and Groundwater Environment
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• v.13 no.4
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• pp.54-61
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• 2008

Permeable reactive barriers (PRBs) technology has been focused in contaminated groundwater remediation. It is necessary to select adequate reactive material according to characteristics of contaminant in groundwater. In this research, the reaction between reactive material and heavy metal contaminants was estimated through column test. Reactive material was slag, which has been produced in Gwangyang power plant, and heavy metal contaminants were cadmium, lead and copper. Column test was performed in the condition of 1) single and multi contaminated solution and 2) different initial concentration of cadmium. Retardation factor of cadmium is 3.94 in multi contamination. But that of copper is 40.3 in single and 25 in multi. The difference of retardation between cadmium and copper is due to affinity, resulted from the difference of electronegativity. In multi-contamination, copper effluent concentration was above initial copper concentration and at the same time lead effluent concentration was decreased. This phenomenon was considered that lead extract copper sorbed in slag and then lead was sorbed to the vacant sorption site instead. And as the initial concentration was increased, the retardation factor of cadmium became decreased.

• Journal of the Mineralogical Society of Korea
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• v.26 no.2
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• pp.101-110
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• 2013

Due to the large specific surface area and great reactivity toward environmental contaminants, nanocrystalline mackinawite (FeS) has been widely applied for the remediation of contaminated groundwater and soil. Furthermore, nanocrystalline FeS is rather thermodynamically stable against anoxic corrosion, and its reactivity can be regenerated continuously by the activity of sulfate-reducing bacteria. However, nanocrystalline mackinawite is prone to either spread out along the groundwater flow or cause pore clogging in aquifers by particle aggregation. Accordingly, this mineral should be modified for the application of permeable reactive barriers (PRBs). In this study, coating methods were investigated by which mackinawite nanoparticles were deposited on the surface of alumina or activated alumina. The amount of FeS coating was found to significantly vary with pH, with the highest amount occurring at pH ~6.9 for both minerals. At this pH, the surfaces of mackinawite and alumina (or activated alumina) were oppositely charged, with the resultant electrostatic attraction making the coating highly effective. At this pH, the coating amounts by alumina and activated alumina were 0.038 and 0.114 $mmol{\cdot}FeS/g$, respectively. Under anoxic conditions, arsenite sorption experiments were conducted with uncoated alumina, uncoated activated alumina, and both minerals coated with FeS at the optimal pH for comparison of their reactivity. Uncoated activated alumina showed the higher arsenite removal compared to uncoated alumina. Notably, the arsenite sorption capacity of activated alumina was little changed by the coating with FeS. This might be attributed to the abundance of highly reactive hydroxyl functional groups (${\equiv}$AlOH) on the surface of activated alumina, making the arsenite sorption by the coated FeS unnoticeable. In contrast, the arsenite sorption capacity of alumina was found to increase substantially by the FeS coating. This was due to the consumption of the surface hydroxyl functional groups on the alumina surface and the subsequent occurrence of As(III) sorption by the coated FeS. Alumina, on the surface area basis, has about 8 times higher FeS coating amount and higher As(III) sorption capacity than silica. This study indicates that alumina is a better candidate than silica for the coating of nanocrystalline mackinawite.

• Journal of the Korean GEO-environmental Society
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• v.8 no.2
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• pp.41-48
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• 2007

Zevo-valent iron (ZVI) has been widely used in permeable reactive barriers for reducing organic contaminants, such as trichloroethylene (TCE). The rapid reaction time, however, leads to decrease in reactivity and availability of ZVI. Shewanella algae BrY, a strain of dissimilatory iron reducing bacteria, can reduce the oxidized Fe (III) to Fe (II) and reduced Fe (II) can be reused to reduce the contaminant. The effect of Shewanella algae BrY on the reduction of the oxidized ZVI column and further TCE removal in the contaminated groundwater were studied at different flow rates and TCE input concentrations in this study. High input concentration of TCE and flow rate increase the amount of input contaminant and make to lower the effect of reduction by Shewanella algae BrY. Specially, the fast flow rate inhibits the direct contact and implantation on the surface of iron. The reduction of oxidized iron reactive barrier by Shewanella algae BrY can decrease the decreation of duration of PRBs by the precipitation of oxidized iron produced by dechlorination of TCE.