• 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).

• 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 the Mineralogical Society of Korea
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• v.5 no.1
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• pp.1-5
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• 1992

The manganese oxide ores in the Taebaeg Mt. region have been formed by supergene weathering of the primary hydrothermal or sedimentary manganese ores. The supergenesis is controlled by the physical chemistry of the descending groundwater in the supergene zone. It includes the fundamental geological processes, such as dissolution, oxidation, transportation, precipitation, and crystallization and recrystallization. However, the fundamental mechanisms for the formation of various manganese oxide minerals are 1) replacement, 2) precipitation from solution, and 3) solid state crystallization and recrystallization. Various textures and structures of ores have been formed by these processes. Detailed paragenetic sequence of manganese oxide minerals in each ore deposit is summerized.

• Economic and Environmental Geology
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• v.19 no.4
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• pp.265-276
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• 1986

The Jangseong manganese deposits are supergene oxidation products of hydrothermal rhodochrosite. The manganese ore veins are developed in the Dongjeom Quartzite, and Dumudong Formation. The deposits consist of primary manganese carbonate ores in the deeper part and manganese oxide ores near the surface. The manganese carbonate ores are composed of rhodochrosite and small amounts of sulfides. The manganese oxide ores are composed of birnessite, nsutite, todorokite, chalcophanite, and pyrolusite. Microscopic, X-ray diffraction, infrared, thermal and EPMA analyses have been made for manganese oxide minerals and other associated minerals. The manganese minerals were formed in the following sequence. Rhodochrosite$\rightarrow$birnessite$\rightarrow$todorokite$\rightarrow$nsutite-pyrolusite. Thermochemical properties of chalcophanite were studied by methods of X-ray powder diffraction, infrared absorption spectroscopic analysis and dehydration experiments. Chalcophanite changes to $4.8{\AA}$ phase at $90{\sim}110^{\circ}C$. Chemical analyses show that the manganese oxide minerals generally have high concentration in Zn.

• 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.

• Ocean and Polar Research
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• v.44 no.2
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• pp.139-145
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• 2022

Manganese nodules were recovered within the deep subseafloor sediments (118.22 mbsf) at Site U1371 during International Ocean Discovery Program (IODP) expedition 329 from the South Pacific Gyre (SPG). Because most manganese nodules exist on the seabed surface, nodules present in deep sediments are uncommon. Therefore, the growth origin of manganese nodules was identified through mineralogical and geochemical analyses. The manganese nodule was divided into the concentric layer outside the manganese region and the inner part of the phosphatized region consisting of manganese oxide minerals and carbonate fluorapatite (CFA) minerals, respectively. The two-dimensional element distribution analysis of Mn, Co, Ni, Sr and Cu, Zn with low Mn/Fe ratio confirmed that manganese nodules were formed predominantly by a hydrogenetic process and a biogenic process in certain manganese layers. As a result, the manganese nodule was continuously precipitated in SPG environments of oligotrophic open paleoocean conditions and rapidly buried with siliceous ooze sediments when the SPG changed to a eutrophic environment. It has been confirmed that manganese nodules found within deep subseafloor sediments could be used as a new proxy for the reconstruction of paleooceanographic conditions.

• Korean Journal of Materials Research
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• v.12 no.11
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• pp.860-864
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• 2002

$Li^{+}$ extraction reactions with ion-exchange type lithium manganese oxide in an aqueous phase were examined using chemical and x-ray diffraction (XRD) analysis. In the process of extraction reaction, the lithium manganese oxide showed a topotactic extraction of $Li^{+ }$ in the aqueous phase mainly through an ion-exchange mechanism, and the $Li^{+}$ extracted samples indicated a high selectivity and a large capacity for $Li^{+}$ . The electronic structures and chemical bonding properties were also studied using a discrete variational (DV)-X$\alpha$ molecular orbital method with cluster model of (Li$Mn_{12}$ $O_{40}$ )$^{27-}$ for tetrahedral sites and ($Li_{7}$ Mn $O_{38}$ )$^{3}$ for octahedral site in $Li_{1.33}$ $Mn_{1.67}$ / $O_{4}$ respectively. Li in the manganese oxides is highly ionized in both sites, but the net charge of Li was greater for tetrahedral sites than octahedral. These calculations suggest that the tetrahedral sites have higher $Li^{+}$ $H^{+}$ exchangeability than the octahedral sites, and are preferable for the selective adsorption for L $i^{+}$ ions.s.

• Korean Journal of Materials Research
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• v.12 no.4
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• pp.274-278
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• 2002

Discrete-variational(DV)-$X{\alpha}$ method was applied to investigate the electronic structures of spinel- type manganese oxide which is well known to the high performance adsorbent or cathode material for lithium ion. The results of DOS(density of states) and Mulliken population analysis showed that Li was nearly fully ionized and interactions between Mn and O were strong covalent bond. The effective charge of Li and Mn was +0.77 and +1.44 respectively and the overlap population between Mn and O was 0.252 in $LiMn_2O_4$. These results from DV-X$\alpha$ method were well coincided with the experimental result by XPS analysis and supported the feasibility of theoretical interpretation for the $LiMn_2O_4$ compound.

• Korean Journal of Mineralogy and Petrology
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• v.33 no.4
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• pp.427-437
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• 2020

Manganese nodules, which are evaluated as potential metal resources, have been found in the Arctic Ocean as well as in the abyssal plains of the Pacific and Indian Oceans. Manganese nodules exhibit strong variations in the morphology, internal texture, chemical composition and mineralogy as they grow. The relationship between the texture and chemical elemental composition during the growth process is well documented, but the mineral composition variation during the growth process is not. Because the manganese oxide minerals in nodules are fine-grained and poorly crystalline, quantitative analysis for the mineral composition is challenging for the bulk nodule sample. This study investigated the internal texture and Mn-oxide mineral composition of manganese nodules obtained from the East Siberian Sea. Semi-quantitative analysis was attempted for three main Mn-oxide minerals constituting the manganese nodules (i.e., todorokite, buserite and birnessite) using the peak area ratio of X-ray diffraction analysis graphs. In the East Siberian Sea manganese nodules, birnessite is more abundant than buserite or todorokite, and no correlation is found between the mineral composition and the internal texture. Instead a correlation is found between the relative content of todorokite and the lamellae depth. The todorokite content tends to increase from the surface to the core of the nodules, which can be attributed to a recrystallization process or difference in the growth rate within the nodule. This study shows that semi-quantitative analysis of manganese oxide minerals using the peak area ratio is useful in the mineralogical study of manganese nodules.

• 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.