• Ocean and Polar Research
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• v.36 no.4
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• pp.373-381
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• 2014

Korea contract Mn-nodule field in the NE equatorial Pacific is composed of seven sectors with average water depths of 4,513-5,025 m. Of the various factors controlling the properties of Mn-nodule, it seems that water depth is likely connected to the chemical composition and occurrence of nodules. To test whether such an assumption held in each sector, we reviewed previous research data accumulated since 1994 for one of the northern sectors (hereafter KR1) where there are stark contrasts in water depth. High-resolution seabed mapping clearly separates a northern part (KR1N) from a deeper southern part (KR1S), cutting across in the middle of the KR1. In addition, significant volcanic activities forming numerous seamounts are distinctive especially in KR1N. In terms of nodule occurrence, manganese nodules in KR1S are comparatively larger (2-4 cm) with a discoidal shape, while those in KR1N are generally small (<2 cm) with poly-lobate and irregular shapes. Nodules in KR1N also have lower Co, Cu, Mn and Ni, and higher Fe contents. The spatial separation in nodule characteristics might be caused by volcanic activities in KR1N rather than water depth contrast. During the formation of the seamounts in KR1N, rock fragments and volcanic ashes as new nuclei of the nodules would have been continuously generated. As a result, the nodules could not grow larger than 2 cm and display the shapes of a newbie (i.e., irregular and poly-lobate shapes). Moreover, significant Fe supply from volcanic activities probably decreases the Mn/Fe ratio, which may lead to the KR1 nodules being misinterpreted as a hydrogenic in origin compared to other sectors where a high Mn/Fe ratio is present.

• Journal of the Mineralogical Society of Korea
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• v.30 no.4
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• pp.219-227
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• 2017

Manganese (Mn) nodules in the Arctic Sea have been founded in the Kara Sea and Barents Sea, but mineral and chemical compositions have been rarely investigated. In this study, mineralogical and geochemical characteristics of Mn nodules obtained during the Arctic Expedition ARA07C in northern East Siberian Sea were identified, and then genesis of Mn nodules were estimated by using these characteristics. Main manganese oxide minerals constituting the manganese nodule were buserite, birnessite, and vernadite. The Mn nodules generally represent radiated and massive texture, and the layered texture was developed restrictively. The radiated texture, main feature of the manganese nodule in the East Siberian Sea, is mainly composed of cuspate-globular microstructure. Compared with the Mn nodules in Pacific and Indian Oceans, Mn nodules of the East Siberian Sea are abundant in Mn, but Fe is too scarce. There was no difference in the chemical composition and microstructures between outer and inner part of nodule. Therefore, nodules are most likely to have only one genesis during their growth, and all of nodules indicate the diagenetic in $Mn-Fe-(Cu+Ni+Co){\times}10$ ternary diagram. It is considered that the manganese nodules in the East Siberian Sea are characterized by high Mn contents because manganese contents in the Arctic Ocean were mainly resulted from river or coastal erosion and most of them are trapped in the Arctic Ocean.

• Korean Journal of Mineralogy and Petrology
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• v.34 no.4
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• pp.241-253
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• 2021

Manganese nodules have been found in the shallow water depth of the Arctic Ocean as well as in the abyssal plains of the Pacific and Indian Oceans, but detailed study for them were rarely investigated. Manganese nodules, collected from the East Siberian Sea through the Arctic Expedition using Araon ice braking vessel, have a high potential for Mn mineral resources because they have high Mn content with high Mn/Fe ratio. This study investigated the external form, size and weight, internal texture for the non-spherical manganese nodule, which has about 7 % of total nodule from the East Siberian Sea. This study also researched the relative Mn-oxide mineral composition using the peak area ratio of X-ray diffraction pattern and their chemical composition. All data obtained from non-spherical nodules were compared with the spherical ones. Ellipsoidal, platy and irregular types are common among 5 groups of non-spherical manganese nodule based on the external form, and major axis and weight have positive relationship. All non-spherical manganese nodules have core mainly composed of mud sediments. The average Mn oxide mineral contents in nodules are birnessite, buserite and todorokite in descending order. Although mineral composition does not show any correlation with the external form, kind of core or internal structure, todorokite and buserite contents tend to increase and birnessite content decrease from the surface to the core in the nodule. Non-spherical manganese nodules have higher Mn content and Mn/Fe ratio than those from the shallow water depth of the Arctic Sea and even in the deep-sea of the Pacific and Indian Ocean. Although non-spherical nodule is larger and heavier, and has lower Mn content and Mn/Fe ratio than spherical nodule, there are not any differences in mineral composition and internal structure between them. Almost all manganese nodules collected from the East Siberian Sea are attributed to diagenetic process, because they are higher than 5 in Mn/Fe ratio.

• Resources Recycling
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• v.23 no.4
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• pp.69-74
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• 2014

Slags generated in the smelting reduction of deep sea manganese nodule could be utilized as an additional materials for making Fe-Si-Mn alloys by mixing with cokes and re-smelting at an arc furnace. In this re-melting process slag is also generated, and the secondary slag is treated as waste. In this survey, recycling of the waste slag of Mn nodule was studied. It is tried to utilize the waste slag as ceramic materials or construction materials. However, it is difficult to use the waste slag directly as an additional material to ceramics such as portland cement or castable refractory material due to the much difference of chemical compositions. As an altercation road constructing material is considered, and toxicity on the soil of the waste slag was tested according to Korean Standard for testing permissible amount of toxic substances. The test result was satisfied with the requirements on the standard. So, it should be suggested that the waste slag of the Mn nodule could be utilized as constructing materials such as road filler or base materials.

• Korean Journal of Microbiology
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• v.45 no.4
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• pp.411-415
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• 2009

Some microorganisms are capable of leaching Mn(II) from nonsulfidic manganese ores indirectly via nonenzymatic processes. Such reductive dissolution requires organic substrates, such as glucose, sucrose, or galactose, as a source of carbon and energy for microbial growth. This study investigated characteristics of Mn(II) leaching from manganese nodules by using heterotrophic Bacillus sp. strain MR2 provided with corn starch as a less-expensive substrate. Leaching of Mn(II) at 25.6 g Mn(II) $kg^{-1}$ nodule $day^{-1}$ was accompanied with cell growth, but part of the produced Mn(II) re-adsorbed onto residual $MnO_2$ particles after 24 h. Direct contact of cells to manganese nodule was not necessary as a separation between them with a dialysis tube produced similar amount [24.6 g Mn(II) $kg^{-1}$ nodule $day^{-1}$]. These results indicated an involvement of extracellular diffusible compound(s) during Mn(II) leaching by strain MR2. In order to optimize a leaching process we tested factors that influence the reaction, and the most efficient conditions were $25\sim35^{\circ}C$, pH 5~7, inoculum density of 1.5~2.5% (v/v), pulp density of 2~3 g/L, and particle size <75 ${\mu}m$. Although Mn(II) leaching was enhanced as particle size decrease, we suggest <212 ${\mu}m$ as a proper size range since more grinding means more energy consumption The results would help for the improvement of bioleaching of manganese nodule as a less expensive, energy-efficient, and environment-friendly technology as compared to the existing physicochemical metal recovery technologies.

• Korean Journal of Mineralogy and Petrology
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• v.35 no.4
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• pp.409-421
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• 2022

Achieving a highly resolved spatial distribution of Mn-bearing minerals and elements in the natural ferromanganese nodules can provide detailed knowledge of the temporal variations of geochemical conditions affecting the formation processes of nodules. While a recent study utilizing Raman spectroscopy has reported the changes in the manganate mineral phases with growth for spherical nodules from the Arctic Sea, the distributions of minerals and elements in the nodules from the shallow Arctic Sea with non-spherical forms have not yet fully elucidated. Here, we reported the micro-laser Raman spectra with varying data acquisition points along three different profiles from the center to the outermost rim of the non-spherical ferromanganese nodules collected from the East Siberian Sea (~73 m). The elemental distributions in the nodule (such as Mn, Fe, etc.) were also investigated by energy dispersive X-ray spectroscopy (EDS) analysis to observe the internal structure and mineralogical details. Based on the microscopic observation, the internal structures of a non-spherical nodule can be divided into three different regions, which are sediment-rich core, iron-rich substrate, and Mn-Fe layers. The Raman results show that the Mn-bearing mineral phases vary with the data acquisition points in the Mn-Fe layer, suggesting the changes in the geochemical conditions during nodule formation. In addition, we also observe that the mineral composition and structural characteristics depend on the profile direction from the core to the rim. Particularly, the Raman spectra obtained along one profile show the lack of Fe-(oxy)hydroxides and the noticeably high crystallinity of Mn-bearing minerals such as birnessite and todorokite. On the other hand, the spectra obtained along the other two profiles present the presence of significant amount of amorphous or poorly-ordered Fe-bearing minerals and the low crystallinity of Mn-bearing minerals. These results suggest that the diagenetic conditions varied with the different growth directions. We also observed the presence of halite in several layers in the nodule, which can be evidence of the alteration of seawater after nodule formation. The current results can provide the opportunity to obtain detailed knowledge of the formation process and geochemical environments recorded in the natural non-spherical ferromanganese nodule.

• Ocean and Polar Research
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• v.36 no.4
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• pp.367-371
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• 2014

In early 1990s, the Korean government has launched a deep-sea research program to secure the stable long-term supply of strategic metallic minerals including Cr, Cu and Ni. Through the pioneering surveys, Korea registered $150,000km^2$ of Mn-nodule field in the Clarion-Clipperton area, the NE equatorial Pacific to the international sea-bed authority (ISA) in 1994. Following the ISA exploration code, the final exclusive exploration area of $75,000km^2$ was assigned in 2002, based on results of eight-year researches of chemico-physical properties of nodules, bottom profiles and sediment properties. Since that time, environmental studies, mining technical developments including robot miner and lifting system and establishment of smelting systems were accompanied with the detailed geophysical studies to decipher the priori mining area until 2009. Major points of the recent Korea Mn-nodule program are deployed on a commercial scale until 2015. In order to meet the goals, we developed a 1/5 scaled robot miner compared to commercial one in 2012 and performed a mining test at the water depth of 1,370 m in 2013. In addition, detailed 25,000 scaled mining maps in the priori area, which can provide operation roots of the miner, will be prepared and an environmental-friendly mining strategy will be pursued based on the environmental impact test and environmental monitoring.

• Economic and Environmental Geology
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• v.45 no.5
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• pp.477-486
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• 2012

High-resolution bathymetry and physico-chemical properties of manganese nodules were explored to identify the relationship between morphological features and nodule occurrences in the KR1, one of the Korean contract nodule fields located in the NE Pacific. The high-resolution seabed mapping showed that the southwestern sector of the KR1 (KR1-1) was relatively deeper than the northeastern sector (KR1-2) which is occupied by small-scale seamounts. In terms of nodule occurrence, manganese nodules in the KR1-1 were comparatively larger (2-4 cm) with rough surface (t-type) and discoidal shapes (D-type), while those in the KR1-2 were generally small (<2 cm) with smooth surface (s-type) and irregular shapes (I-type). In addition, the nodules in the KR1-1 had higher contents of Cu, Mn and Ni. Such connections of water depths to nodule appearances and metal contents are commonly observed in the Pacific nodule fields. On the other hand, the nodules in the KR1-2 tend to be controled by morphological features. The seamounts in the KR1-2 might continuously provide rock fragments as new nuclei of manganese nodules. As a result, the nodules could not grow over than 2 cm and showed the shapes of a newbie (i.e., smooth surface and irregular shapes). As a result, our observations indicate that occurrence features of manganese nodules could be subjected to water depths and seabed morphology simultaneously.

• Economic and Environmental Geology
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• v.44 no.6
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• pp.475-483
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• 2011

Quantitative estimate of manganese nodules based on the operation of a free fall grab (FFG) needs to be corrected because of its less retrieval ability. Previously, the correction parameter of the nodule abundance collected by FFG was calculated based on the image analysis of the photos of bottom sediment in the northern sector of the nodule exploration area of Korea in the NE equatorial Pacific. However, nodules in the southern sector are commonly covered by sediment, which may prevent the use of the correction parameter estimated by photographic techniques. In this study, we attempted dual nodule sampling at the same location by different equipments (i.e. box corer (BC) and FFG) to examine the previous correction parameter of nodule abundance for FFG operation. During the exploration cruises in 2007 to 2009, Mn-nodules were collected from 40 stations both by BC and FFG in the southern sector. The correlation analysis between BC and FFG operations revealed that the BC collected nodules 1.43 times larger than FFG. Our result suggests that the correction parameter of 1.43 can be applied for collection of FFG data to estimate Mn-nodule distribution in the southern sector. The obtained parameter is similar to the previous parameter (1.42~1.45) calculated by the image analysis method, indicating an usefulness of new correction parameter suggested by this study.

• Korean Journal of Metals and Materials
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• v.47 no.3
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• pp.188-194
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• 2009

Recently, new extraction technology for manganese nodule has been developed as alternative noble metallic resources. It is important to understand thermodynamic behaviors of phosphorus in low basic slag system from the viewpoint of the refining processing optimization. Thermodynamic behaviors of phosphorus in the $FeO-MnO-CaO-SiO_2-MgO_{satd.}$ slag system were investigated at 1723 K with various oxygen potential and slag composition of low basicity. The experimental results for dependence of phosphorus on oxygen potential and slag basicity indicated that the dissolution mechanism of phosphorus into slag of low basicity could be derived as follows; $[P]+5/4O_2+(O^{2-})=({PO_{3.5}}^{2-})$ Present experimental results implied that stability of phosphorus in slag would be depended on both of $O^{2-}$ (basicity) and content of $Ca^{2+}$ in molten slag. The thermodynamic effect of FeO, MnO and $Na_2O$ on low basicity on phosphate capacity was discussed.