• Journal of the Mineralogical Society of Korea
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• v.18 no.4 s.46
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• pp.259-266
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• 2005

X-ray diffraction (XRD), Electron microprobe analyses (EPMA) and heating experiments were used for mineralogical characterization of natural buserites collected from the Janggun and Dongnam mines. They are closely associated with $7-{\AA}$ phase (usually rancieite) in manganese oxide ores of the supergene oxidation zones of manganese carbonate deposits. Electron microprobe analyses give the average formula $(Ca_{0.78}Mg_{0.64}Mn^{2+}\;_{0.45})Mn^{4+}\;_{8.03}O_{18}\cdot13.2H_{2}O\;and\;(Zn_{0.81}Ca_{0.77}Mg_{0.26})Mn^{4+}\;_{8.00}O_{18}\cdot10.9H_{2}O$ for buserite from the Janggun and the Dongnam mine, respectively. The basal reflection of buserite from the Janggun mine shifts continuously from $9.86\;{\AA}\;at\;40^{\circ}C\;to\;7.60\;{\AA}\;at\;90^{\circ}C$, but the buserite from the Dongnam mine shows tendency of decreasing intensity in the $9.67^{\circ}C$ peak and of increasing intensity in the $7.53\;{\AA}$ peak in the range of $40\∼90^{\circ}C$, showing no gradual shifting of peaks.

• Economic and Environmental Geology
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• v.56 no.1
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• pp.55-63
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• 2023

Variations in geochemical and mineralogical properties of the ferromanganese(Fe-Mn) crust reflect environmental changes. In the present study, geochemical and mineralogical analyses, including micro X-ray fluorescence and X-ray diffraction, were utilized to reconstruct the paleo-ocean environment of western Pacific Magellan seamount cluster. Samples of the Fe-Mn crust were collected using an epibenthic sledge from the open seamount XX (151° 51.12' 7.2" E and 16° 8.16' 9.6" N, 1557 meters below sea level) in the Western Pacific Magellan Seamount. According to the structure and phosphating status, the Fe-Mn crust of the OSM-XX can be divided into the following: phosphatizated (L4-L5), massive non-phosphatizated (L3), and porous non-phosphatizated (L1-L2) portions. All ferromanganese layers contain vernadite, and owing to the presence of carbonate fluorapatite (CFA), the phosphatizated portion (L4-L5) is rich in Ca and P. The massive non-phosphatizated section (L3) contains high Mn, Ni, and Co, whereas the porous non-phosphatizated portion (L1-L2), which comprises detrital quartz and feldspar, is rich in Fe. Variations in properties of the Fe-Mn crust from the OSM-XX reflect changes in the nearby marine environment. The formation of this crust started at approximately 51.87 Ma, and precipitation of the CFA during the global phosphatization event that occurred at approximately 36-32 Ma highlights an elevated sea level and low temperature during the associated period. The high Mn, Ni, and Co concentrations and elevated Mn/Fe ratios of samples from the massive phosphatizated portion indicate that the oxygen minimum zone (OMZ) was enhanced, and reducing conditions prevailed during the crust formation. The high Fe and low Mn/Fe ratios in the porous portion indicate a weak OMZ and dominantly oxidizing conditions. These data reflect environmental changes following the end of the Mi-1 glacial period in the Miocene-Oligocene boundary. Subsequently, Mn/Fe and Co/Mn ratios increased slightly in the outermost part of Fe-Mn crust because of the enhanced bottom current and OMZ associated with the continued cooling from approximately 9 Ma. However, the reduced carbonate dissolution rate in the Pacific Ocean from approximately 6 Ma decreased the growth rate of the Fe-Mn crust.

• Journal of Korea Soil Environment Society
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• v.1 no.2
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• pp.51-60
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• 1996

Removal of Mn-EDTA complex and fluoride by use of hematite and ferrite, which are the by-product to be disposed of as industrial wastes, was investigated. For the comparison of removal rate, Na-bentonite known as excellent absorbent of inorganic contaminants was included in the experiments. As the results of batch mode experiments, for manganese, ferrite-A revealed 48∼65% of removal capacity, ferrite-B 46∼57%, hematite 17∼26%, while Na-bentonite showed 10∼23% of removal, depending on the initial concentration. Meanwhile, in case of fluoride : hematite revealed 53 ∼63% of removal : ferrite-A 54∼63 %, while ferrite-B did 20∼38 %. From the results, it can be postulated that the capacity of hematite and ferrite to attenuate inorganic pollutants, especially when they form complex ions, is superior to that of Na-bentonite. Consequently, the mixing of such oxide minerals with Na-bentonite will reinforce the function of Na-bentonite, especially in the undergroud liner aspect.

• Journal of Korean Society of Environmental Engineers
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• v.31 no.7
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• pp.473-482
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• 2009

In this study, iron and manganese coated sand (IMCS) was prepared by mixing Joomoonjin sand with solutions having different molar ratio of manganese ($Mn^{2+}$) and iron ($Fe^{3+}$). Mineral type of IMCS was analyzed by X-ray diffraction spectroscopy. Removal efficiency of arsenic through As(III) oxidation and As(V) adsorption by IMCS having different ratio of Mn/Fe was evaluated. The coated amount of total Mn and Fe on all IMCS samples was less than that on sand coated with iron-oxide alone (ICS) or manganese-oxide alone (MCS). The mineral type of the manganese oxide on MCS and iron oxides on ICS were identified as ${\gamma}-MnO_2$ and mixture of goethite and magnetite, respectively. The same mineral type was appeared on IMCS. Removed amount As(V) by IMCS was greatly affected by the content of Fe rather than by the content of Mn. Adsorption of As(V) by IMCS was little affected by the presence of monovalent and divalent electrolytes. However a greatly reduced As(V) adsorption as observed in the presence of trivalent electrolyte such as $PO_4\;^{3-}$. As(III) oxidation efficiency by MCS in the presence of NaCl or $NaNO_3$ was two times greater than that in the presence of $PO_4\;^{3-}$. Meanwhile a greater As(III) oxidation efficiency was observed by IMCS in the presence of $PO_4\;^{3-}$. This was explained by the competitive adsorption between phosphate and arsenate on the surface of IMCS.

• Journal of the Korean GEO-environmental Society
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• v.12 no.2
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• pp.15-22
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• 2011

In this study, the effect of surface coating on iron-sulfide mineral for preventing the product acid mine drainage(AMD) was progressed by oxidation process of sulfide minerals abandoned mine Area. Three abandoned mines, Yongdong coal mine, Sil Lim mine, and Il Koang mine were selected as a sulfide mineral resource due to higher contamination rate. Six coating agents, apatite, limestone, mangnite, dolomite, bentonite, and cement were used for preventing the AMD with $H_2O_2$ and NaClO as a oxidizing agent helping for oxidizing process on sulfide minerals. Experimental results showed that sulfide mineral surface was coated effectively. Cement has a higher ability of preventing AMD when the ratio of cement to mineralis 1:1 and experimental condition is maintaining 4Days.

• Journal of the Mineralogical Society of Korea
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• v.3 no.1
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• pp.34-43
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• 1990

Crystal-chemical study of hexagonal 7$\AA$ phyllomanganate minerals reveals that they have hexagonal layer structures with variable c dimensions which depend on the nature of interlayer cations and content of water molecules between edge-sharing [MnO6] octahedral layers. Approximately one out of nine octahedral sites is statistically vacant, leading to the general unit cell formula R2xMn4+1-xO2.nH2O, where R=Ca, Mn2+, Mg, K, Na;x=0.09-0.14 ; n-0.37-0.84. Z=1. The minerals of this formula fall under the name of rancieite group. It includes Ca-diminant (rancieite), Mn2+-dominant (takanelite), Na-dominant (birnessite), and Mg-dominant members. Minerals of the rancieite group occur predominantly in two different hydration states, i.e., n shows the values around 0.35 and 0.75. It is suggested that minerals of higher hydration state be called as species(i.e., rancieite, etc.) and those of lower hydration state be called as dehydrated varieties(i.e., dehydrated rancieite,etc.).

• Journal of the Mineralogical Society of Korea
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• v.10 no.2
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• pp.82-96
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• 1997

Buserties are known to have layer structures with variable C dimension which depended on the nature interlayer catious and contents of water molecular between edge-sharing [MnO6] octabedral layers. Na-, Ca-, Mg-, and Zn-buserties were synthesized in the laboratory and studied for to know the structural states of water molecules and the role of catious in the buserite structures. With lowering the relative humidity(RH), Ca-buserite begins to dehydrate at 27% RH and proceeds further very slowly. Mg- and Zn- buserite also slow dehydration above 2% RH. With gradual ineveasing temperature Ca- and Zn-buserite show abrupt shifting of 10$\AA$ peak (10$\AA$-phare) toward 7$\AA$ peak. All of 7$\AA$-phare are further dehydrated to 5$\AA$-phare by further increasing temperature. It suggests that interlayer catious play a crucial role in the dehydration behavious of buserites. Simulation of one-dimensional X-ray diffraction patterns of buserties show that buserites have three layers of water molecules of different types: the very loosely bound and tightly bend waters, instead of two layers that was regarded by previous authers. The very loosely bound water is sited I open space of the interlayer, the loosely bound water is bound on the tightly bound water by hydrogen bond, and the tightly bond water in coodinately bound on the interlayer catious.

• 한국해양학회지
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• v.29 no.4
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• pp.338-356
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• 1994

Sediment samples from the continental shelf of the South Sea of Korea are analysed to determine the concentration of Al, Fe, Mn, cu, Ni, Zn, Co, Cr and Pb. among these samples, fine-grained sediments were also analysed by a sequential extraction technique to know geochemical forms of the metals in this environments. The total concentration of Al, Fe, Cr, Ni, Cu and Zn in bulk sediments decreased gradually with the increase of distance from the coastal zone. This distribution patterns are well coincide with grain size distribution. However, the patterns of Mn, co and Pb do not follow such and overall distribution. The concentration of Pb, particularly, did not show any features in areal distribution, which may be result from different pathways to the sediments, compared to the other metals. the speculation data show that a considerable amount of Cd, Mn and Co are bounded in the carbonate fraction, accounting for 42.8%, 40.3% and 30.6%, respectively. Cu, Zn, Mn and Fe are largely associated to oxide fraction with proportions of 34.4%, 23.1%, 15.5% and 13.7%, respectively. However, the metals in residual fraction account for more than 50% of the total metal concentration, except for Mn. These observations emphasize that residual fraction in the dominant component controlling the elemental concentration.quartz and glauconite grains.Accordingly,these sediments are interpreted as an extension part of transgressive sand deposit that are widely distributed on the continental shalf floor of southern Yellow Sea.

• Korean Journal of Mineralogy and Petrology
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• v.36 no.3
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• pp.167-183
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• 2023

The Janggun Pb-Zn deposit consists of Mn orebody, Pb-Zn orebody and Fe orebody. The Mn orebody composed of manganese carbonate orebody and manganese oxide orebody on the basis of their mineralogy and genesis. The geology of this deposit consists of Precambrian Weonnam formation, Yulri group, Paleozoic Jangsan formation, Dueumri formation, Janggum limestone formation, Dongsugok formation, Jaesan formation and Mesozoic Dongwhachi formation and Chungyang granite. This manganese carbonate orebody is hydrothermal replacement orebody formed by reaction of lead and zinc-bearing hydrothermal fluid and Paleozoic Janggum limestone formation. The wallrock alteration that is remarkably recognized with Pb-Zn mineralization at this hydrothermal replacement orebody consists of mainly rhodochrositization with minor of dolomitization, pyritization, sericitization and chloritization. Carbonates formed during wallrock alteration on the basis of paragenetic sequence are as followed : Ca-dolomite (Co type, wallrock) → ankerite and Ferroan ankerite (C1 type, early stage) → ankerite (C2 type) → sideroplesite (C3 type) → sideroplesite and pistomesite (C4 type, late stage). This means that Fe and Mn elements were enriched during evolution of hydrothermal fluid. Therefore, The substitution of elements during wallrock alteration beween dolomitic marble (Mg, Ca) and lead and zinc-bearing hydrothermal fluid (Fe, Mn) with paragenetic sequence is as followed : 1)Fe ↔ Mn and Mn ↔ Mg, Ca, Fe elements substitution (ankerite and Ferroan ankerite, C1 type, early stage), 2)Fe ↔ Mn, Mn ↔ Mg, Ca and Mg ↔ Ca elements substitution (ankerite, C2 type), 3)Fe ↔ Mn, Fe ↔ Ca and Mn ↔ Mg, Ca elements substitution (sideroplesite, C3 type), and 4)Fe ↔ Mg, Fe ↔ Mn and Mn ↔ Mg, Ca elements substitution (sideroplesite and pistomesite, C4 type, late stage)

• Korean Journal of Mineralogy and Petrology
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• v.33 no.3
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• pp.143-152
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• 2020

Birnessite is a layered manganese oxide mineral with ~7 Å of d-spacing. Because of its high cation exchange capacity, birnessite greatly impacts the chemical compositions of ground water and fluids in sediment pores. Understanding the cation exchange mechanisms requires atomistic investigations of the crystal structures and coordination environments of hydrated cations in the interlayer. In this study, we conducted classical molecular dynamics (MD) simulations, an atomistic simulation method of computational mineralogy, for triclinic Na-birnessite and K-birnessite whose chemical formula are from previous experiments. We report our MD simulation results of the crystal structures, coordination environments of Na⁺ and K⁺, and the polytypes of birnessite and compare them with available experimental results. The simulation results well reproduced experimental lattice parameters and provided atomic level information for the interlayer cation and water molecule sites that are difficult to distinguish in X-ray experiments. We also report that the polytype of the Mn octahedral sheets is identical between Na- and K-birnessite, but the cation positions differ from each other, demonstrating a correlation between the coordination environment of the interlayer cations and the crystal lattice parameters. This study shows that MD simulations are very promising in elucidating ion exchange reactions of birnessite.