• Economic and Environmental Geology
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• v.42 no.5
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• pp.479-486
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• 2009

In natural environments, manganese (Mn) exists in the valence of +2, +3, and +4 and plays a pivotal role as a strong oxidant or reductant in the geochemical cycles of elements. Especially, Mn forms varying (oxyhydr)oxides. The oxidation state of structural Mn is characteristic to each oxide and is one of the most important factors controlling its geochemical behaviors such as solubility, sorption capacity, and redox potential. Therefore, it is important to elucidate processes governing Mn oxidation state in predicting the fate and transport of many redox sensitive elements in the environment. X-ray photoelectron spectroscopy (XPS) is a very useful method to determine the oxidation state of various elements in solid phases. In this study, the oxidation states of structural Mn in MnO, $Mn_2O_3$, $MnO_2$ were assessed based on the binding energy spectra of $Mn2p_{3/2}$ and Mn3s using XPS and were compared with those reported elsewhere. $Mn2p_{3/2}$ binding energies were determined as 640.9, 641.5, 641.8 eV for MnO, $Mn_2O_3$, $MnO_2$, respectively, which indicates that the binding energy increased with increasing Mn oxidation state. It was also noted that Ar etching may cause changes in electronic structure configuration on surface of the original sample.

• Journal of the Mineralogical Society of Korea
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• v.13 no.2
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• pp.73-83
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• 2000

다덕 광산 폐석내 섬아연석과 함망간탄산염 광물의 풍화현상과 그에 따른 중금속의 거동을 조사 하였다. 섬아연석은 풍화초기에 극미립 산화철의 망상구조 집합체로 교대되었으며, 후기에는 자연황이 용해중인 섬아연석과 산화철 집합체 사이에 침전되었다. 산화철 집합체에는 As가 다량 함유되어 있다. 능망간석와 함망간 방해석은 함아연산화망간의 망상구조 집합체로 교대되었으며, 함망간방해서과 함아연산화망간 사이에는 스미소나이트가 침전되었다. 선택적 용해외 X선회절분석을 이용하여 감정한 결과, 함아연산화망간은 헤테롤라이트/하이드로헤테롤라이트인 것으로 판명되었다. Zn의 일부는 규산과 결합하여 입간 공극에 월레마이트로 침전되었다. 풍화 초기에 형성되는 극미립 산화철 및 함아연산화망간의 치밀한 망상 집합체는 풍화용액의 순환을 차단하여, 모광물의 풍화 반응을 지체시키는 지화학적 장벽 역할을 하였다. 이에 따라 망상구조 내에 조성된 국지적 미환경하에서 풍화중간산물들이 침전되었다. 이상의 연구 결과로 다음과 같은 사항을 추론할 수 있다. 섬아연석의 Fe와 함망간탄산염의 Mn은 각각 산화철과 산화망간으로 침전되어 산성화에 기여하였다. 폐광석 더미내 As의 활동도는 저결정질 산화철에의 흡착에 의해 조절되며, Zn의 활동도는 미소환경조건에 따라 하이드로헤테롤라이트/헤테롤라이트, 스미소나이트, 월레마이트 등의 다양한 이차광물의 용해도에 의하여 조절된다.

• Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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• 2005.04a
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• pp.94-98
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• 2005

강변여과방식의 시험 취수가 진행 중에 있는 범람원지역의 산화-환원 반응을 밝히기 위해 10개의 간이 관측정을 설치하여 수질 모니터링을 수행하였다. 분석 결과 하천수에 인접한 지역에서 강한 환원환경이 생성되는 것을 확인하였으며, 이는 하천수 내 용존 유기 탄소가 인근 범람원 지역에 퇴적 산화되어 나타난 결과였다. 즉 퇴적된 용존 유기 탄소가 감소하면서 용존 산소와 질산성 질소는 감소시키지만, 이러한 환경변화가 수처리 시 문제가 될 수 있는 용존 망간의 농도를 증가시키게 되며, 따라서 향후 이 지역에 대한 추가적인 분석과 함께 집수정으로 통해 유출되는 용존 망간에 대한 대책이 필요한 것으로 조사되었다.

• Journal of Soil and Groundwater Environment
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• v.13 no.2
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• pp.62-69
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• 2008

In this study physicochemical characteristics and stability of various manganese coated sands (MCS) prepared with different methods were evaluated. In addition, removal efficiencies of As(III) by each MCS were compared. Four different MCSs were used; B-MCS prepared by baking method, W&D-MCS prepared by wetting and dry method, NMCS prepared during the water treatment process and Birm which is a commercial MCS widely used for the removal iron and manganese. The manganese content in each MCS was following order: Birm (63,120 mg/kg) > N-MCS (10,400 mg/kg) >W&D-MCS (5,080 mg/kg) > B-MCS (2,220 mg/kg). Birm showed the least solubility (% basis) in acidic conditions. As(III) oxidation efficiency of B-MCS was continuously increased as the solution pH decreased. While As(III) oxidation efficiency of N-MCS and Birm was minimum around neutral pH. The increased As(III) oxidation efficiency above neutral pH for N-MCS and Birm could be due to the competitive adsorption of $Mn^{2+}$, which was produced from reduction of $MnO_2$, onto the surface of aluminum and manganese oxides.

• Korean Chemical Engineering Research
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• v.46 no.3
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• pp.498-505
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• 2008

The selective catalytic oxidation of ammonia was carried out in the presence of natural manganese ore (NMO) and manganese as catalysts using a homemade 1/4" reactor at $10,000hr^{-1}$ of space velocity. The inlet ammonia concentration was maintained at 2,000 ppm, with an air balance. The manganese catalyst resulted in a substantial ammonia conversion, with adsorption activation energies of oxygen and ammonia of 10.5 and 22.7 kcal/mol, respectively. Both $T_{50}$ and $T_{90}$, defined as the temperatures where 50% and 90% of ammonia, respectively, are converted, decreased significantly when alumina-supported manganese catalyst was applied. Increasing the manganese weight percent by 15 wt% increased the lower temperature activity, but 20 wt% of manganese had an adverse effect on the reaction results. An important finding of the study was that the manganese catalyst benefits from a strong sulfur tolerance in the conversion of ammonia to nitrogen.

• Journal of Soil and Groundwater Environment
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• v.7 no.3
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• pp.95-102
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• 2002

Manganese oxide/ hydrogen peroxide($MnO_2$/${H_2}{O_2}$) reactions were investigated as an alternative to Fenton-like reaction to reduce chlorinated organic compounds in groundwater This system showed high degradation of CT with low ${H_2}{O_2}$concentration($\leq$294mM) at neutral condition, and CT degradation increased with increasing pH values. The rate of CT degradation was not so much dependent on increase in $MnO_2$concentration since increase in production of oxygen during the reaction obstructed reaction of ${H_2}{O_2}$ on the surface of $MnO_2$. These results show that $MnO_2$catalyzed Ponton-like reaction could be a potential alternative method for treating chlorinated organic compounds in groundwater.

• Journal of Korean Society of Environmental Engineers
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• v.29 no.5
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• pp.571-576
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• 2007

Manganese-Coated Sand(MCS) prepared with three different methods were applied in the treatment of soluble $Mn^{2+}$ in batch and column experiments. In the bench-scale MCS preparation, the coating efficiency of manganese on the surface of sand increased as the dosage of initial Mn(II) increased. The removed amount of the soluble $Mn^{2+}$ by MCS increased as the solution pH increased, following a typical anionic-type adsorption. The removed amounts of the soluble $Mn^{2+}$ through adsorption was quite similar over the entire pH range, without depending on the contents of Mn on the surface of sand as well as coating methods. When NaClO was used an oxidant, the removed amount of the soluble $Mn^{2+}$ by MCS increased as the concentration of NaClO increased, This trend might be explained by the increased removal efficiency through coating of manganese oxides produced from oxidation of the soluble $Mn^{2+}$ by NaClO on the surface of MCS. From the bench-scale column experiments, the breakthrough of $Mn^{2+}$ occurred after 4,100 bed volume without presence of NaClO while 1.6-times delayed breakthrough of $Mn^{2+}$ was observed in the presence of NaClO. This result also supports that the removal efficiency of the soluble $Mn^{2+}$ could be enhanced by using NaClO.

• Journal of Applied Biological Chemistry
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• v.65 no.4
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• pp.457-462
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• 2022

Manganese (Mn) exists in various oxidation states and Mn(II) is the most mobile species of Mn, which is toxic to plants and limits their growth. Therefore, the purpose of this study was to reduce Mn toxicity by immobilizing Mn using various adsorbents including iron oxides and calcium compounds. Ferrihydrite, schwertmannite, goethite were synthesized, which was confirmed by X-ray diffraction. Hematite was purchased and used as Mn adsorbent. Calcium compounds such as CaNO₃, CaSO₄, and CaCO₃ were used to increase pH and oxidize Mn. For Mn adsorption, Mn(II) solution was reacted with four iron oxides, CaNO₃, CaSO₄, and CaCO₃ for 24 hours, filtered, and the remaining Mn concentrations in the solution were analyzed by inductively coupled plasma optical emission spectroscopy. The adsorption rate and adsorption isotherm were calculated. Among iron oxides, the adsorption rate was highest for hematite followed by ferrihyrite, but goethite and schwertmannite did not adsorb Mn. In the case of calcium compounds, the adsorption rate was high in the order of CaCO₃>CaNO₃>CaSO₄. In conclusion, treatment of CaCO₃ was the most effective in reducing Mn toxicity by increasing pH.

• Clean Technology
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• v.2 no.1
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• pp.60-68
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• 1996

The oxidation of carbon monoxide of low concentration on the natural manganese dioxide (NMD) has been investigated in a fixed bed reactor. The experimental variables were concentration of oxygen (500ppm~99.8%) and carbon monoxide (500ppm~10000ppm) and catalyst temperature ($50{\sim}750^{\circ}C$). The NMD(Natural Manganese Dioxide) has been characterized by temperature - program reduction(TPR) using 2.4% $CO/H_2$ as a reducing agent, thermogravimetric analysis (TGA), and reduction of NMD by 2.4% $CO/H_2$. It was found that the NMD catalyst activity on the unit area was greater than the $MnO_2$ catalyst for oxidation of CO at the same temperature. The thermal stability of oxidation activity was considered to be maintained when the NMD was heated to $750^{\circ}C$. The TGA, reduction by CO, and TPR of the NMD showed that the NMD had active lattice oxygen which was easily liberated on heating in the absence and low concentration of oxygen. The reaction order in CO is 0.701 between 500~3500ppm and almost zero between 3500~10000ppm of CO.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2004.07a
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• pp.485-488
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• 2004

1M, 2M 황산망간 수용액에서 25회 dipping하여 대기중 $450^{\circ}C$에서 1시간동안 열분해법으로 Mn 산화물을 형성시켜 Mn $oxide/IrO_2/Ti$ 전극을 제조하였다. 제조된 Mn $oxide/IrO_2/Ti$ 전극은 XRD를 통하여 MnO의 결정구조를 가지는 것을 확인하였다. 또한 전극 표면은 열분해법으로 발생하는 가스에 의해 미소 균열이 형성되어 있었다. dipping 횟수가 증가할수록 피복되는 Mn 산화물의 무게는 감소하였고, 이것은 $450^{\circ}C$에서의 계속적인 열처리에 의해 열분해되어 제거되는 가스로 인해 무게가 감소됨을 알 수 있었다. 황산망간 수용액의 농도가 높으면 형성되는 Mn 산화물의 무게도 증가하였다. 황산망간 수용액에서 25회까지 dipping을 한 후 전기비저항의 변화는 초기 Mn 산화물이 형성되는 경우에는 비저항이 증가하다가, 일정 횟수 이상에서는 감소함을 알 수 있었다. 또한 황산망간 수용액의 농도가 클수록 비저항이 증가하는 것으로 나타났다.