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

• 한국해양학회지
• /
• v.23 no.3
• /
• pp.110-122
• /
• 1988

Between the Clarion and Clipperton fracture zones of the Northeastern Pacific, nodules and crusts were collected from abyssal plain and hills by the Korea Ocean Research and Development Institute in December, 1983 aboard the R/V KANA KEOKI of the Hawaii Institute of Geophysics. Mineralogical and geochemical data of bulk nodules are obtained and compared with analyses of other studies. Mechanisms of nodule formation are discussed based on these data. Generally, the nodules of the KONOD-1 site are composed of todorokite and ${\delta}-MnO_2$. The contents of Mn, Fe, Ni, and Cu of the bulk nodules are variable and the average contents of metals are slightly lower (Mn, 21.40%; Ni, 0.9%; Cu, 0.8%) than those of nodules from other abyssal plains between the Clarion and Clipperton fracture zones. High Mn/Fe (average 3.9; maximum 5.9) and Cu/Ni (average 0.8; maximum 1.0) ratios are similar to the nodules that were formed diagenetically in the northeast Pacific. The chemical characteristics of the KONOD-1 nodules reflect their sedimentary environments; nodules with higher diagenetic signatures occur in areas of thin Quaternary siliceous ooze, and nodules of lower diagenetic influence occur in topographically irregular abyssal hill areas.

• Journal of the Mineralogical Society of Korea
• /
• v.13 no.4
• /
• pp.205-220
• /
• 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
• /
• v.14 no.1
• /
• pp.27-33
• /
• 1981

The manganese nodule from the Blake Plateau consists mainly of microcrystalline to cryptocrystalline todorokite, with minor quartz, clays, carbonates and phillipsite. The nodule in cross section shows concentric layers, core structure, unconformity and fissure-filling structure megascopically, and colloform, fragmental and diagenetic textures microscopically. A new classification of colloform textures which are applicable to any nodule of any source shows that the colloform textures consist of three basic textural units: banded, cuspate and globular. They occur independently or in combination with each other to form various types of textures. The presence of three predominant textural types suggests that there are three different major modes of nodule growth which are controlled by physical and chemical environments.

• 한국해양학회지
• /
• v.25 no.4
• /
• pp.189-204
• /
• 1990

In the KODOS (Korea Deep Ocean Study)-89 area, western part of clarion-Clipperton fracture zones in the northeastern equatorial Pacific, magnate nodules and sediments were sampled during the 'Farnella' cruise in Oct., 1989. Bulk chemical and mineralogical analyses have been made on a suit of ferromanganese nodules and sediments to study the origin and distribution pattern of the nodules. The nodules are classified into three groups based on their origin: diagenetic nodules with high Mn/Fe ratio, Cu, Ni, Zn, Mg, todorokite contents and rough surface texture; hydrogenetic nodules with high Fe, Co, vernadite contents and smooth surface texture; and transitional nodules with intermediate characters between diagenetic and hydrogenetic nodules. Study area is divided into four zones according to the origin and abundance of nodules: far north area where nodules are hydrogenetic and intermediate in abundance; north area where nodules are diagenetic and low in abundance; south area where nodules are diagenetic and intermediate in abundance; seamount area where nodules are hydrogenetic and high in abundance. distribution pattern of manganese nodules in the KODOS-89 area seems to be controlled by latitudinal variation of productivity in water column and sea bottom morphology.

• Resources Recycling
• /
• v.15 no.4 s.72
• /
• pp.3-12
• /
• 2006

The feasibility for the employment of manganese nodule as an adsorbent for $SO_{2}$ gas has been investigated. The specific surface area of manganese nodule particle, which used in the experiments, was ca. $221.5m^{2}/g$ and the content of sulfur in manganese nodule was observed to significantly increase after $SO_{2}$ was adsorbed on it. The EPMA for the distilled water-washed and methanol-washed manganese nodule particle after $SO_{2}$ adsorption showed that its sulfur content was slightly decreased to 14.7% and 13.1% respectively, from 15.4% before washing. The XRD analysis of manganese nodule showed that todorokite and birnessite, which are manganese oxides, and quartz and anorthite were the major mineralogical components and weak $MnSO_{4}$ peaks were detected after $SO_{2}$ was adsorbed on manganese nodule. For an comparative investigation, limestone was also tested as an adsorbent for $SO_{2}$, however, no peaks for $CaSO_{4}$ were found by XRD analysis after the adsorption of $SO_{2}$. As the size of adsorbent increased, time for breakthrough was decreased and the adsorbed amount of $SO_{2}$ was also diminished. The $SO_{2}$ adsorption was hindered when its flow rate became high and the adsorption capacity of manganese nodule was observed to be superior to that of limestone. In addition, the mixture of manganese nodule and limestone did not show an increase in the adsorption of $SO_{2}$. Finally, as the temperature was raised, the adsorbed amount of adsorbate on manganese nodule was found to be decreased.

• Korean Journal of Mineralogy and Petrology
• /
• v.34 no.4
• /
• pp.241-253
• /
• 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
• /
• v.36 no.4
• /
• pp.303-312
• /
• 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.

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

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