• 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.

• Journal of the Mineralogical Society of Korea
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• v.23 no.2
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• pp.161-170
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• 2010

Many microbes, including both bacteria and fungi, produce manganese (Mn) oxides by oxidizing soluble Mn(II) to form insoluble Mn(IV) oxide minerals, a kinetically much faster process than abiotic oxidation. These biogenic Mn oxides drive the Mn cycle, coupling it with diverse biogeochemical cycles and determining the bioavailability of environmental contaminants, mainly through strong adsorption and redox reactions. This mini review introduces recent findings based on quantum mechanical density functional theory that reveal the detailed mechanisms of toxic metal adsorption at Mn oxide surfaces and the remarkable role of Mn vacancies in the photochemistry of these minerals.

• 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.

• Resources Recycling
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• v.26 no.4
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• pp.34-41
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• 2017

The effect of Mn(II) concentration on the anodic reactions occurring on a Pb-Ag electrode in sulfuric acid solutions has been studied by potentiostatic oxidation in the potential range of 1.8 to 2.0 V. High oxidation potentials and low initial concentrations of Mn(II) resulted in higher concentrations of soluble Mn(III) ions which were obtained from spectrophotometric analysis of the solution after oxidation. $MnO_2$ was deposited on the electrode by electrochemical oxidation of Mn(II) at 1.8 and 1.9 V, while it was formed by disproportionation of Mn(III) at 2.0 V. No $PbO_2$ was formed in the presence of Mn(II) during potentiostatic oxidation treatment for two hours at 1.8 V. Chemical reduction of $PbO_2$ with Mn(II) led to a decrease in the amount of $PbO_2$ as Mn(II) concentration increased at 1.9 and 2.0 V.

• 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.

• Economic and Environmental Geology
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• v.15 no.4
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• pp.205-219
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• 1982

The Eosangcheon manganese ore deposits occur as supergene weathering deposits along quartz porphyry dikes developed in the Ordovician Heungweolri dolomite and Samtaesan limestone formations. The manganese ores are composed of manganese oxide minerals and associated other minerals. Rancieite and todorokite are abundantly found, and birnessite, nsutite, pyrolusite and chalcophanite are found in minor quantities. Associated other minerals are calcite, gypsum, goethite, lepidocrosite, quartz, and sericite. Microscopic, chemical, X-ray powder diffraction, infrared absorption spectroscopic and differential thermal analyses have been made for manganese oxide minerals and associated other minerals. The relationship of birnessite and rancieite was studied by means of X-ray powder diffraction and infrared absorption spectroscopic analyses. It is assumed that these minerals are closely related to each other in crystal structure, but separate species. The manganese oxide minerals were formed mainly by replacement, precipitation from solution, and recrystallization in the supergene weathering environment. The trend of formation of manganese oxide minerals is: (Rhodochrosite)-(todorokite)-(birnessite, rancieite)-(nsutite, pyrolusite, chalcophanite).

• 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.

• Economic and Environmental Geology
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• v.17 no.4
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• pp.273-282
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• 1984

The Buncheon manganese ore deposits occur in vein along the fault of $N20^{\circ}E$, cutting the foliation of Yulri Series. The deposits consist of primary manganese silicate ores in the deeper part and superficial manganese oxide ores near the surface. The spatial distribution of manganese oxide ores with respect to the manganese silicate ores suggests that the manganese oxide ores are the supergene oxidation product of the manganese silicate ores. Manganese silicate ores consist mainly of fine-to coarse-grained pyroxmangite with minor rhodochrosite, quartz, sulfides and chlorite. Manganese oxide ores are composed of supergene manganese oxides such as nsutite, birnessite, manganite and todorokite, and other associated minerals. Paragenetic sequence of formation of the manganese minerals are as follows: $\array{{rhodochrosite{_{\rightarrow}^o}todorokite{_{\searro}^o}}\\pyroxmangite{_{\line(10){90}}^o}{\nearro}}birnessite{_{\rightarrow}^o}nsutite{_{\rightarrow}^s}manganite$ In order to elucidate the mineralogy of the manganese minerals, microscopic, X-ray, IR spectroscopic, and thermal studies were made for manganese and associated minerals.

• 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.

• 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.