• 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.

• Journal of the Mineralogical Society of Korea
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• v.2 no.1
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• pp.1-7
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• 1989

The terrestrial Ca-buserite has been found from Dongnam mine, Korea. It occurs in close association with rancieite in the manganese oxide ores which were formed by supergene weathering of hydrothermal rhodochrosite in veins. A study on this mineral using X-ray diffraction, infrared, polarizing and electron microscopes and dehydration experiment shows that the natural cabuserite (10$\AA$ phase) is more or less unstable, transforming partly to rancieite (7.5 $\AA$ phase) in the natural environment, and upon heating, its 10 $\AA$ line shifts to 7.5$\AA$ at 70-9$0^{\circ}C$. The Ca-buserite is the hydrate of rancieite.

• 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.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.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.

• Proceedings of the Mineralogical Society of Korea Conference
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• 2002.05a
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• pp.56-57
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• 2002

• 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.

• Korean Journal of Mineralogy and Petrology
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• v.36 no.1
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• pp.33-40
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• 2023

Todorokite is a manganese oxide mineral containing Mg²⁺ in a tunnel structure in which MnO₆ octahedra share corners. In order to investigate the suitability and efficiency of high temperature-treated todorokite as a material for adsorption and fixation of Cs, Cs was ion exchanged and the amount of leached Cs from todorokite was measured. The todorokite used in this study was synthesized by transforming Na-birnessite to Mg-buserite and used as a precursor. After high temperature treatment, Cs exchanged todorokite changed to birnessite and hausmannite as the temperature increased. The amount of leached Cs was investigated for Cs exchanged todorokite which was reacted with distilled water and 1 M NaCl solution at different reaction times. In general, for the samples reacted with 1 M NaCl solution, the fixation of Cs was quite effective, although the amount of leached Cs was greater due to the ion exchange reaction with Na. As the treatment temperature increased, the amount of leached Cs increased and then decreased again, which was related to the mineral phases formed at each temperature. As birnessite was formed, the amount of leached Cs increased, but as birnessite decreased, that decreased again. As the mineral phase changed to hausemanite, the amount of Cs decreased rapidly. The results of our study show that Cs exchanged todorokite can be used as a material that effectively fixes Cs and prevents its diffusion by high temperature treatment.

• Journal of the Mineralogical Society of Korea
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• v.13 no.4
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• pp.205-220
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• 2000

북동태평양 C-C지역의 우리나라 광구에서 산출되는 망간단괴의 내부조직을 크게 주상조직 층상대, 첨상조직 층상대, 첨상조직 괴상대, 첨상조직 다공질대 및 괴상조직 괴상대로 구분하였다. 주상조직 층상대에서는 버나다이트(vernadite)가 가장 우세하게 산출되며, 첨상조직 층상대에서는 부서라이크(buserite)가 함께 산출된다. 첨상조직 괴상대는 부서라이트의 산출이 두드러지며, 부분적으로 토도로카이트(todorokite)가 수반된다. 첨상조직 다공질대는 첨상체 또는 구상체로 이루어지며 부분적으로 괴상조직으로 교대되는데 주로 토도로카이트와 부서라이트로 구성되어 있다. 괴상조직을 갖는 괴상대에서는 토도로카이트와 버네사이트(birnessite)가 부서라이트와 함께 산출된다. 각 조직대별로 미세조직을 이루는 엽리들에 대해 전자현미분석을 실시하였다. 엽리의 화학조성을 구성하는 요인은 상관계수 군집분석에 의해 Mn-K의 Mn군, Cu-Ni-Zn-Mg(Ca-Na)의 Cu-Ni-Mg군 Fe-Co-Ti(Ca-P)의 Fe군과 Si-Al의 Si군 등 네 개군으로 구분된다. 각 조직대는 세 개 또는 네 개의 군으로 구성되며 이들 각군은 단괴에서 산출되는 광물과 밀접한 관계를 가진다. Mn군은 토도로카이트, Cu-Ni-Mg군은 부서라이트, Fe군은 함코발트수산화철광물, 그리고 Si군은 규산염광물에서 주로 기인하는 것으로 생각된다. 엽리의 화학조성은 이들 광물의 조합과 구성광물의 화학조성에 따라 지배되고 한 조직대내에서도 여러종류의 조합을 보이는데 이는 각 조직대의 엽리들의 성인과 밀접한 관련이 있는 것으로 생각된다.

• Economic and Environmental Geology
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• v.52 no.6
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• pp.509-517
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• 2019

The birnessite (7Å manganate, δ-MnO₂) which is a manganese oxide and comprises manganese nodules, is a major manganese mineral on the earth surface and a precursor in the synthesis of todorokite. In this study birnessite was synthesized by three different methods: Feng et al. (2004) and Luo et al. (1998) based on redox reaction and Ma et al. (1999) based on reduction reaction. 12 birnessite samples were synthesized by different combinations of Na⁺ and K⁺ cations based on the base (OH^-) and permanganate (MnO₄^-) reagents in the synthesis. The mineral compositions of synthesized birnessite were identified by XRD, and the two cation ratio in the mineral was measured by ICP. The products obtained after hydrothermal treatment of Mg-buserite, by the precursor of birnessite, was examined by XRD, and then phase transition to todorokite and their characteristics were compared. Our results show that the byproducts and the characteristics of phase transition by each synthetic method have different trends. Hausmannite (γ-Mn₃O₄) and feitknechtite (β-MnOOH) were formed by both methods in the redox reaction mechanism. By Feng et al. (2004)'s method, manganite (γ-MnOOH) phase only appeared when cation was predominantly Na⁺. Two birnessite samples synthesized by redox reaction mechanism showed phase transition to todorokite (10Å manganate, OMS-1) when both NaOH and KMnO₄ were used together. However, single-phase birnessite was formed by Ma et al. (1999)'s method, and phase transition was confirmed only for the sample when the cation was only composed of Na⁺.