• 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.

• Korean Journal of Mineralogy and Petrology
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• v.35 no.1
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• pp.13-24
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• 2022

The Arctic Ocean is very sensitive to global warming and Arctic Ocean sediments provide a records of terrestrial climate change, analyzing their composition helps clarify global warming. The gravity core sediment ARA07C-St02B was collected at the East Siberian margin during an Arctic expedition in 2016 on the Korean ice-breaking vessel ARAON, and its provenance was estimated through sedimentological, mineralogical and geochemical analysis. The core sediment was divided into four units based on sediment color, sand content and ice-rafted debris content. Units 1 and 3 had higher sand and ice-rafted debris contents than units 2 and 4, and contained a brown layer, whereas units 2 and 4 were mainly composed of a gray layer. Correlation analysis using the adjacent core sediment ARA03B-27 suggested that the sediment units were deposited during marine isotope stage 1 to 4. The bulk mineral, clay mineral, and geochemical compositions of units including a brown layer differed from units including a gray layer. Bulk and clay mineral compositions indicated that coarse and fine sediments had a different origin. Coarse sediments might have been deposited mostly by the East Siberian Coastal Current from the Laptev Sea and the East Siberian Sea or by the Beaufort Gyre from the Chukchi Sea, whereas fine sediments might have been transpoted mostly by currents from the East Siberian Sea, the Chukchi Sea and the Beaufort Sea. Some of the coarse sediments in unit 1 and fine sediments in unit 3 might have been deposited by iceberg ice, sea ice or current from the Beaufort Sea and the Canada Archipelago. Investigating the geochemical composition of the potential origins will elucidate the origin and transportation of the study area's core sediments.

• 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.

• Economic and Environmental Geology
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• v.56 no.1
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• pp.1-11
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• 2023

In this study, we explore the morphological and geochemical characteristics for 440 manganese nodules collected from two different water depths [ARA12B-St52 (150 m, n = 239) and ARA12B-St58i (73 m, n = 201)] on the continental shelf of the East Siberian Sea from the ARA12B expedition in 2021. We also discussed the variations in the characteristics of manganese nodules with varying water depths in the Arctic Sea. The sizes of the nodules are generally greater than 3 cm at both sites. However, there is an obvious difference in the morphology with water depths. For the nodules collected at 150 m, brown-black colored tabular, tube, and ellipsoidal shapes with a rough surface texture are dominant. On the other hand, yellow-brown tabular shapes with a smooth surface texture are common for the nodules collected at 73 m. Furthermore, the slope of trend line between size and weight is significantly different at both sites: particularly, the slopes of nodules at 150 and 73 m are 1.60 and 0.84, respectively. This indicates the difference in the internal structure, porosity, and constituting elements between both nodules. Micro X-ray Flourescence (µ-XRF) results clearly demonstrate that the internal textures and chemical compositions are different with water depths. The nodules at 150 m are composed of a thick Mn-layer and a thin Fe-layer centered on the nucleus, while the nodules at 73 m are alternately grown with thin Mn- and Fe- layers around the nucleus. The average chemical compositions obtained by µ-XRF are 40.6 wt% Mn, 5.2 wt% Fe, and 7.9 Mn/Fe ratio at 150 m, and 10.3 wt% Mn, 19.0 wt% Fe, and 0.6 Mn/Fe ratio at 73 m. The chemical compositions of the nodules at 150 m are similar to those of nodules from the Peru Basin in the Pacific Ocean, while the compositions of the nodules at 73 m are similar to those of nodules from the Cook Islands or the Baltic Sea. The observed morphological and geochemical characteristics of the nodules show a clear difference at the two sites, which indicates that the aqueous conditions and formation processes of the nodules in the Arctic Sea vary with the water depths.

• Korean Journal of Remote Sensing
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• v.25 no.5
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• pp.423-434
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• 2009

The Arctic environment is sensitive to change of sea-ice distribution. The increase and decrease of sea ice work to an index of globe warming progress. In order to predict the progress of hereafter earth global warming, continuous monitoring regarding a change of the sea ice area in the Arctic should be performed. The remote sensing based on an artificial satellite is most effective on the North Pole. The sea ice observation using a passive microwave sensor has been continued from 1970's. The determination of sea ice extent and ice type is one of the great successes of the passive microwave imagers. In this paper, to investigate the seasonal and inter-annual variation of sea-ice distribution we used here the sea ice data from July 2002 to May 2009 around the Arctic within $60^{\circ}N$ for the AMSR-E 12.5km sea-ice concentration, a passive microwave sensor. From an early analysis of these data, the arctic sea-ice extent has been steadily decreasing at a rate of about 3.1%, accounting for about $2{\times}10^5\;km^2$, which was calculated for the sea-ice cover reaching its minimum extent at the end of each summer. It is also revealed that this trend corresponds to a decline in the multi-year ice that is affected mainly by summer sea surface and air temperature increases. The extent of younger and thinner (first-year) ice decreased to the 2007 minimum, but rapidly recovered in 2008 and 2009 due to the dramatic loss in 2007. Seasonal variations of the sea-ice extent show significant year-to-year variation in the seasons of January-March in the Barents and Labrador seas and August-October in the region from the East Siberian and Chukchi seas to the North Pole. The spatial distribution of multi-year ice (7-year old) indicates that the perennial ice fraction has rapidly shrunk recently out of the East Siberian, Laptev, and Kara seas to the high region of the Arctic within the last seven years and the Northeast Passage could become open year-round in near future.

• 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.

• Korean Journal of Mineralogy and Petrology
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• v.36 no.4
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• pp.303-312
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• 2023

The determination of the oxidation states of metal elements in manganese nodules sheds light on the understanding of the formation mechanism of nodules, providing insights into the paleo-environmental conditions such as the redox potential of the aqueous system. This study aims to reveal the oxidation states and chemical bonding of manganese in the natural polymetallic nodules, utilizing conventional X-ray photoelectron spectroscopy (XPS). Specifically, shallow manganese nodules from the Siberian Arctic Sea, effectively recording mineralogical variations, were used in this study. Detailed analysis of XPS Mn 2p spectra showed changes in the manganese oxidation state from the center to the outer parts of the nodules. The central part of the nodules showed a higher Mn⁴⁺ content, approximately 67.9%, while the outermost part showed about 63% of Mn⁴⁺ due to an increase in the Mn³⁺+Mn²⁺. The decrease in the Mn oxidation state with the growth is consistent with the previously reported mineralogical variations from todorokite to birnessite with growth. Additionally, the O 1s spectra presented a predominance of Mn-O-H bonds in the outer layers compared to the center, suggesting hydration by water in the layered manganates of outer layers. The results of this study demonstrate that XPS can be directly applied to understand changes in paleo-environmental conditions such as the redox states during the growth of manganese nodules. Finally, future studies using high-resolution synchrotron-based XPS experiments could achieve details in oxidation states of manganese and trace metal elements.

• Korean Journal of Mineralogy and Petrology
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• v.34 no.1
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• pp.15-29
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• 2021

In the Arctic Ocean, the distribution of sea ice and ice sheets changes as climate changes. Because the distribution of ice cover influences the mineral composition of marine sediments, studying marine sediments transported by sea ice or iceberg is very important to understand the global climate change. This study analyzes marine sediment samples collected from the Arctic Ocean and infers the provenance of the sediments to reconstruct the paleoenvironment changes of the western Arctic. The analyzed samples include four gravity cores collected from the Araon mound in the Chukchi Plateau and one gravity core collected from the slope between the Araon mounds. The core sediments were brown, gray, and greenish gray, each of which corresponds to the characteristic color of sediments deposited during the interglacial/glacial cycle in the western Arctic Ocean. We divide the core sediments into three units based on the analysis of bulk mineral composition, clay mineral composition, and Ice Rafted Debris (IRD) as well as comparison with previous study results. Unit 3 sediments, deposited during the last glacial maximum, were transported by sea ice and currents after the sediments of the Kolyma and Indigirka Rivers were deposited on the continental shelf of the East Siberian Sea. Unit 2 sediments, deposited during the deglacial period, were from the Kolyma and Indigirka Rivers flowing into the East Siberian Sea as well as from the Mackenzie River and the Canadian Archipelago flowing into the Beaufort Sea. Unit 2 sediments also contained an extensive amount of IRD, which originated from the melted Laurentide Ice Sheet. During the interglacial stage, fine-grained sediments of Unit 1 were transported by sea ice and currents from Northern Canada and the East Siberian Sea, but coarse-grained sediments were derived by sea ice from the Canadian Archipelago.