• Economic and Environmental Geology
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• v.36 no.3
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• pp.177-189
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• 2003

The main purposes of this study are to utilize mineralogical studies such as optical microscope, XRD and SEM/EDS analyses to characterize the oxidation of sulfide minerals and the mechanisms controlling the movement of dissolved metals from waste rocks at the abandoned Seobo mine. Mineralogical research of the waste rocks confirms the presence of anglesite, covellite, goethite, native sulfur and nsutite as secondary minerals, suggesting that these phases control the dissolved concentrations of As, Cu, Fe, Mn, Pb and Zn. The dissolved metals are precipitated, adsorbed and/or coprecipitated with(or within) Fe(Mn)-hydroxides and Mn(Fe)-hydroxides. The main phases of secondary mineral, Fe-hydroxide, can be classified as amorphous or poorly crystalline and more crystallized phases(e.g. goethite) by crystallinity. Amorphous or poorly crystalline Fe-hydroxide has relatively high As contents(9-24 wt.%). This poorly crystalline Fe-hydroxide changes toward more crystallized phase(e.g. goethite) which contains relatively low As(0.6-7.7 wt.%). These results are mainly due to the progressive release of As with the crystallization evolution of the As-trapping poorly crystalline Fe-hydroxides. It is also attributed to the differences of specific surface areas between the poorly crystalline Fe-hydroxides and well crystallized phases. The dissolved metals from waste rocks at Seobo mine area are naturally attenuated by a series of precipitation(as Fe, Mn, Cu, Pb), coprecipitation(Fe, Mn) and adsorption(As, Cu, Pb, An) reactions. The results of mineralogical researches permit to assess the environmental impacts of mine waste rocks in the areas, and can be used as a useful data to lay available mine restoration plan.

• Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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• 2003.04a
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• pp.132-136
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• 2003

폐광된 광산에 방치된 폐광석에 함유되어 있는 황화광물이 분해되어 다른 광물에 흡착되거나, 산화환경에 안정한 형태의 2차 광물로 침전 혹은 공침 되는가에 대한 연구는 광산복 원을 결정하는데 직접적인 지구화학적 자료로 활용될 수 있다. 따라서 이번 연구에서는 청양광산에 방치된 폐광석을 대상으로 XRD, SEM/EDS연구를 이용하여 산화작용으로 인한 황화광물 주변에 침전된 2차 광물에 대한 광물학적 연구를 수행하였다. 광물학적 연구 결과, 산화환경에서 황화광물의 산화작용으로 인하여 용출된 중금속 이온과 철과 망간 이온들은 침전(Fe, Mn, Pb), 공침 (Fe, Mn, As, Pb) 및 흡착(As, Cu, Pb, Zn) 등의 화학반응을 통하여 다시 고정화됨으로서, 현장에서 자연적으로 정화되고 있는 것이 확인되었다.

• 한국해양학회지
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• v.22 no.3
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• pp.168-178
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• 1987

A study on the mineralogy and internal features have been carried out on a sample of ferromanganese crust from a Central Pacific seamout. The distribution of manganese mineral vernadite($\delta$-MnO$\sub$2/)in the different layers indicates typical hydrogenous origin under a continuous change of growth conditions during crustal firmation. Various internal structures are discerned within the crust which may be attributed to different growth conditions. The growth structure changes and the distinct break in the formation of the crust at about 2 depth are assumed to be the results of Miocene to mid-Pleistocene global palaeoceanographic events.

• Economic and Environmental Geology
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• v.19 no.2
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• pp.109-122
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• 1986

Mn-Pb-Zn-Ag deposits of the Janggun mine are hosted in the Cambro-Ordovician Janggun limestone mostly along the contacts of the Jurassic Chunyang granite. The deposits are represented by several ore pipes and steeply dipping lenticular bodies consisting of lower Pb-Zn-Ag sulfide ores and upper manganese carbonate and oxide ores. The former consists mainly of arsenic, antimony, silver, manganese, and tin-bearing sulfides, whereas the latter are characterized by hypogene rhodochrosite, and superficial manganese oxides including todorokite, nsutite, pyrolusite, cryptomelane, birnesite and janggunite. Origin of the upper manganese ore deposits has been a controversial subject among geologists for this mine: hydrothermal metasomatic vs. syngenetic sedimentary origin. Syngenetic advocators have proposed a new sedimentary rock, rhodochrostone, which is composed mainly of rhodochrosite in mineralogy. In the present study, carbon, oxygen and sulfur isotopic compositions were analayzed obtaining results as follows: Rhodochrosite minerals, (Mn, Ca, Mg, Fe) $CO_3$, from hydrothermal veins, massive sulfide ores and replacement ores in dolomitic limestone range in isotopic value from -4.2 to -6.3‰ in ${\delta}^{13}C$(PDB) and +7.6 to +12.9‰ in ${\delta}^{18}O$(SMOW) with a mean value of -5.3‰ in ${\delta}^{13}C$ and +10.7‰ in ${\delta}^{18}O$. The rhodochrosite bearing limestone and dolomitic limestone show average isotopic values of -1.5‰ in ${\delta}^{13}C$ and +17.5‰ in ${\delta}^{18}O$, which differ from those of the rhodochrosite mentioned above. This implies that the carbon and oxygen in ore fluids and host limestone were not derived from an identical source. ${\delta}^{34}S$ values of sulfide minerals exhibit a narrow range, +2.0 to +5.0‰ and isotopic temperature appeared to be about $288{\sim}343^{\circ}C$. Calculated initial isotopic values of rhodochrosite minerals, ${\delta}^{18}O_{H_2O}=+6.6$ to +10.6‰ and ${\delta}^{13}C_{CO_2}=-4.0$ to -5.1 ‰, strongly suggest that carbonate waters should be deep seated in origin. Isotopic data of manganese oxide ores derived from hypogene rhodochrosites suggest that the oxygen of the limestone host rock rather than those of meteoric waters contribute to form manganese oxide ores above the water table.

• Economic and Environmental Geology
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• v.47 no.4
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• pp.431-439
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• 2014

The purposes of this research were to investigate the enrichment of metal-reducing bacteria from KURT groundwater and the identification of the microbial diversity by 16S rRNA as well as to examine microbial Fe(III)/Mn(IV) reduction and to analyze morphological features of interactions between microbes and precipitates and their mineralogical composition. To cultivate metal-reducing bacteria from groundwater sampled at the KURT in S. Korea, different electron donors such as glucose, acetate, lactate, formate, pyruvate and Fe(III)-citrate as an electron accepter were added into growth media. The enriched culture was identified by 16S rRNA gene sequence analysis for the diversity of microbial species. The effect of electron donors (i.e., glucose, acetate, lactate, formate, pyruvate) and electron acceptors (i.e., akaganeite, manganese oxide) on microbial iron/manganese reduction and biomineralization were examined using the 1st enriched culture, respectively. SEM, EDX, and XRD analyses were used to determine morphological features, chemical composition of microbes and mineralogical characteristics of the iron and manganese minerals. Based on 16S rRNA gene analysis, the four species, Fusibacter, Desulfuromonas, Actinobacteria, Pseudomonas sp., from KURT groundwater were identified as anaerobic metal reducers and these microbes precipitated metals outside of cells in common. XRD and EDX analyses showed that Fe(III)-containing mineral, akaganeite (${\beta}$-FeOOH), reduced into Fe(II)/Fe(III)-containing magnetite ($Fe_3O_4$) and Mn(IV)-containing manganese oxide (${\lambda}-MnO_2$) into Mn(II)-containing rhodochrosite ($MnCO_3$) by the microbes. These results implicate that microbial metabolism and respiratory activities under anaerobic condition result in reduction and biomineralization of iron and manganese minerals. Therefore, the microbes cultivated from groundwater in KURT might play a major role to reduce various metals from highly toxic, mobile to less toxic, immobile.

• 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.32 no.3
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• pp.151-162
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• 2019

Todorokite, a tunnel-structured manganese oxide, can contain cations within the relatively large nanopores created by the $3{\times}3$ Mn octahedra. Because todorokite is poorly crystalline and found as aggregates mixed with other phases of Mn oxides in nature, the coordination structure of cations in the nanopores is challenging to fully characterize in experiment. In the current article, we report the atomistic coordination structures of $Mg^{2+}$ ions in todorokite tunnel nanopores using the classical molecular dynamics (MD) simulations. In experiment, $Mg^{2+}$ is known to occupy the center of the nanopores. In our MD simulations, 60 % of $Mg^{2+}$ ions were located at the center of the nanopores; 40 % of the ions were found at the corners. All $Mg^{2+}$ located at the center formed the six-fold coordination with water molecules, just as the ion in bulk aqueous solution. $Mg^{2+}$ ions at the corners also formed the six-fold coordination with not only water molecules but also Mn octahedral surface oxygens. The mean squared displacements were calculated to examine the dynamic features of $Mg^{2+}$ ions in the one-dimensional (1D) nanopores. Our MD simulations indicate that the dynamic features of water molecules and the cations observed in bulk aqueous solution are lost in the 1D nanopores of todorokite.

• Economic and Environmental Geology
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• v.50 no.3
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• pp.181-193
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• 2017

Mn-Fe phosphate mineral complexes included within the pegmatite are observed at Jurassic Cheolwon two-mica granite in Gyeonggi Massif, South Korea. The genetic evolution between the Cheolwon two-mica granite and pegmatite, and various trend of Mn-Fe phosphate minerals is made by later magmatic, hydrothermal, and weathering process based on mineralogical, geochemical analysis. The Cheolwon two-mica granite is identified as S-type granite, considering its chemical composition (metaluminous ~ peraluminous), post-collisional environment, low magnetic susceptibility, and existence of biotite and muscovite. The K-Ar age (ca. 153 Ma) of pegmatite is well coincident with age of the Cheolwon two-mica granite ($151{\pm}4Ma$). It indicates that these two rocks are originated from the same magma. Pegmatite indicates the LCT geochemical signature, and was classified as muscovite-rare element class / Li subclass / beryl type / beryl-columbite-phosphate subtype pegmatite. The triplite $\{(Fe^{2+}{_{0.4}},Mn_{1.6})(PO_4)(F_{0.9})\}$ is dominant phosphates in later magmatic stage which partly altered to leucophosphite $\{KFe^{3+}{_2}(PO_4)_2OH{\cdot}2H_2O\}$ and jahnsite $\{(Fe^{3+}{_{0.7}},Mn_{2.3})(PO_4)_2OH{\cdot}4H_2O\}$ by hydrothermal alteration. In particular, near fractures, the triplite has been separatelty replaced by the phosphosiderite ($Fe^{3+}PO_4{\cdot}2H_2O$) and Mn-oxide minerals during weathering stage.

• 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.

• Korean Journal of Soil Science and Fertilizer
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• v.32 no.4
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• pp.327-332
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• 1999

Manganese (Mn) oxides in soils have been a research subject since they react with nutrients and contaminants and Mn itself is an essential element for plant growth. Birnessite was synthesized in the presence of iron (Fe) in the precipitating solution. Influence of Fe, one of common elements in soils, on crytallinity, morphology, and chemical reactivity of birnessite was examined using X-ray diffraction (XRD), electron microscope, canon exchange capacity (CEC), and chromium (Cr) oxidation capacity. With increasing Fe concentration in the precipitating solution, crystallinity and crystal size decreased. Hexagonal plates of the birnessites formed at low Fe concentration were dominant and replaced more and more by aggregate of small particles with increasing the Fe concentration. There is no significant change in CEC with changing the Fe concentration. Chromium oxidation capacity of the birnessite increased with increasing the Fe concentration. Iron in the precipitating solution poisoned crystal growth by adsorption on the surface and increased nucleation. Since Fe is a common constituent under pedogenic environment and Fe and Mn oxides often coexist in Mn oxide nodules, the birnessite with small particle, low crystallinity, and high chemical reactivity is the form which is more likely to be formed in soils. The high CEC ($140cmol_ckg^{-1}$) and oxidation capacity of birnessite indicate that birnessite can be used in environment and agriculture.