• Korean Journal of Mineralogy and Petrology
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• v.33 no.1
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• pp.19-28
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• 2020

Ranciéte is a hexagonal phyllomanganate mineral containing random Mn(IV) vacancies with hydrated Ca²⁺ cations charged balanced as interlayer cations. Its Mn²⁺ analogue is called takanelite, and ranciéite and takanelite are regarded as end-members of a solid solution series of (Ca²⁺,Mn²⁺)Mn₄O₉·nH₂O. Because the minerals are found as very small particles associated with other minerals, the crystal structures of the solid solution series have yet to be defined. In this research, we conducted classical molecular dynamics (MD) simulations of ranciéite and takanelite by varying the Mn²⁺/Ca²⁺ interlayer cation ratio to find relations between the interlayer cations and mineral structures. MD simulation results of chalcophanite group minerals are compared with experimental results to verify our method applied. Then, lattice parameters of ranciéite and takanelite models are presented along with detailed interlayer structures as to the distribution and coordination of cations and water molecules. This study shows the potentials of MD simulations in entangling complicated phyllomanganates structures.

• 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 the Mineralogical Society of Korea
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• v.16 no.4
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• pp.333-339
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• 2003

A new mineral, Zn analogue of rancieite (Chimooite), has been discovered at the Dongnam mine, Korea. It occurs as compact subparallel fine­grained flaky or acicular aggregates in the massive manganese oxide ores which were formed by supergene oxidation of rhodochrosite­sulfide ores in the hydrothermal veins trending NS­N25E and cutting the Pungchon limestone of the Cambrian age. The flakes of chimooite are 0.2 mm for the largest one, but usually less than 0.05 mm. The acicular crystals are elongated parallel to and flattened on (001). This mineral shows gradation to rancieite constituting its marginal part, thus both minerals are found in one and the same flake. Color is bluish black, with dull luster and brown streak in globular or massive aggregates. Cleavage is perfect in one direction. The hardness ranges from 2.5 to 4. Under reflected light it is anisotropic and bireflectant. It shows reddish brown internal reflection. Chemical analyses of different parts of both minerals suggest that rancieite and chimooite constitute a continuous solid solution series by cationic substitution. The empirical chemical formula for chimooite has been calculated following the general formula, $R_2_{x}$ M $n^{4+}$$_{9­x}$ $O_{18}$ $.$n$H_2O$ for the 7 $\AA$ phyllomanganate minerals, where x varies from 0.81 to 1.28 in so far studied samples, thus averaging to 1.0. Therefore, the formula of Zn­rancieite is close to the well­known strochiometric formula $_Mn_4^{4+}$ $O_{9}$ $.$4$H_2O$. The mineral has the formula (Z $n_{0.78}$N $a_{0.15}$C $a_{0.08}$M $g_{0.01}$ $K_{0.01}$)(M $n^{4+}$$_{3.98}$F $e^{3+}$$_{0.02}$)$_{4.00}$ $O_{9}$ $.$3.85$H_2O$, thus the ideal formula is (Zn,Ca)M $n^{4+}$$_4$ $O_{9}$ $.$3.85$H_2O$. The mineral has a hexagonal unit ceil with a=2.840 $\AA$ c=7.486 $\AA$ and a : c = 1 : 2.636. The DTA curve shows endothermic peaks at 65, 180, 690 and 102$0^{\circ}C$. The IR absorption spectrum shows absorption bands at 445, 500, 1630 and 3400 c $m^{1}$. The mineral name Chimooite has been named in honour of late Prof, Chi Moo Son of Seoul National University.ity.versity.ity.y.

• Journal of the Mineralogical Society of Korea
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• v.2 no.2
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• pp.90-99
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• 1989

Manganese deposits ar the Dongnam mine occur as vein in the Pungchon limestone of Ordovician age. Manganese ore veins consist of the hydrothermal manganese carbonate ores in the deeper part and the supergene manganese oxide ores in the shallow part. Manganese carbonate ores consist mainly of rhodochrosite, with minor amount of proxmangite, garnet, calcite, quartz, pyrite, galena and sphalerite. Manganese oxide ores consist of rancieite, buserite, birnessite, vernadite, todorokite, pydrolusite, nsutite, hydrohetaerosite and goethite. Manganese oxide minerals were formed in the following sequences; 1) rhodochrosite ${\rightarrow}$ vernadite ${\rightarrow}$ birnessite ${\rightarrow}$ nsutite ${\rightarrow}$ pyrolusite, 2) pyroxmangite ${\rightarrow}$ birnessite, 3) Buserite ${\rightarrow}$ ransieite. Todorokite, buserite and hydrohetaerolite were precipitated from solution in the later stage. The natural analogue of synthetic buserite has been discovered from the mine. It has been disclosed that buserite transforms to rancicite by dehydration, and that distinction between buserite and todorokite is possible by X-ray diffraction studies combined with dehydration experiment. Minerals identified from the mine have been characterized using various methods including polarizing microscopy, X-ray diffraction, thermal analysis, infrared spectroscopy, X-ray diffraction, thermal analysis, infrared spectroscopy, elecrton microscopy and dehydration experiment.

• Journal of the Mineralogical Society of Korea
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• v.5 no.2
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• pp.102-108
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• 1992

The natural (Ca, Mg)-buserite has been identified from the manganese oxideores of the Janggun mine, Korea, which have been formed by supergene weathering of sedimentary-metamorphic rhodochrosite. It occurs together with rancieite forming one very fine-grained buserite-rancieite flake. This (Ca, Mg)-buserite-rancieite occurs as microcystalline flaky crystals. It precipitated around the fine-grained takanelite aggregate. Electron microprobe analyses give the formula ($Ca_{.08}Mg_{.07}Mn_{.05}^{2+})Mn_{.89}^{4+}O_2{\cdot}1.46H_2O$ for (Ca, Mg)-buserite. The dehydration experiments by relative humidity control and heating as well as rehydration experiment by relative humidity control show that (Ca, Mg)-buserite dehydrates completely at 90$^{\circ}C$ and rehydrates up to 27% of the original state. The dehydration at 26% RH (corresponding to heating to about 40$^{\circ}C$) is characterized by thedecrease in the decrease in the intensity of 9.86${\AA}$ peak with slight shifting to 9.60${\AA}$. It is due to the loss of weakly bound water molecules in the interlayer. The dehydration from 40$^{\circ}C$ to 90$^{\circ}C$ is characterized by the gradual shifting of 001 peak from 9.6${\AA}$ to 7.42${\AA}$. It is due to the loss of weakly bound water molecules in the interlayer.

• 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.