• Economic and Environmental Geology
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• v.49 no.1
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• pp.13-22
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• 2016

The objectives of this study were to recover silica and iron oxides and $CO_2$ sequestration using serpentine via various acid dissolution and pH swing processes. Serpentine collected from Guhang-myeon in S. Korea were mainly composed of antigorite and magnetite consisting of $SiO_2$ (45.3 wt.%), MgO (41.3 wt.%), $Fe_2O_3$ (12.2 wt.%). Serpentine pulverized ($${\leq_-}75{\mu}m$$) and then dissolved in 3 different acids, HCl, $H_2SO_4$, $HNO_3$. Residues treated with acidic solution were recovered from the solution (step 1). And then the residual solution containing dissolved serpentine was titrated using $NH_4OH$. And pH of the solution increased up to pH=8.6 to obtain reddish precipitates (step 2). After recovery of the precipitates, the residual solution reacted with $CO_2$ and then pH increased up to pH=9.5 to precipitate white materials (step 3). The mineralogical characteristics of the original sample and harvested precipitates were examined by XRD, and TEM-EDS analyses. ICP-AES analysis was also used to investigate solution chemistry. The dissolved ions were Mg, Si, and Fe. The antigorite became noncrystralline silica after acid treatment (step 1). The precipitate at pH=8.6 was mainly amorphous iron oxide, of which size ranged from 2 to 10 nm and mainly consisting of Fe, O, and Si (step 2). At pH=9.5, nesquehonite [$Mg(HCO_3)(OH){\cdot}2(H_2O)$] and lasfordite [$MgCO_3{\cdot}H_2O$] were formed after reaction with $CO_2$ (step 3). The size of carbonated minerals was ranged from 1 to $6{\mu}m$. These results indicated that the acid treatment of serpentine and pH swing processes for the serpentine can be used for synthesis of other materials such as silica, iron oxides and magnesium carbonate. Also, This process may be useful for the precursor synthesis and $CO_2$ sequestration via mineral carbonation.

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

• Economic and Environmental Geology
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• v.54 no.2
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• pp.299-308
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• 2021

Fe(II) released from mining activities is precipitated as various Fe(III)-oxyhydroxides when exposed to an oxidizing environment including mine drainage. Ferrihydrite, one of the representative precipitated Fe(III) minerals, is easy to adsorb heavy metals and other pollutants due to the large specific surface area caused by very low crystallinity. Ferrihydrite is transformed to thermodynamically more stable goethite in the natural environment. Hence, information on the transformation of ferrihydrite to goethite and the related mobility of heavy metals in the acid mine drainage is important to predict the behaviors of those elements during ferrihydrite to goethite transition. The behaviors of heavy metals during the transformation of ferrihydrite to goethite were investigated for core samples collected from an AMD treatment system in the Heungjin-Taemaek coal mine by using X-ray diffraction (XRD), chemical analysis, and statistical analysis. XRD results showed that ferrihydrite gradually transformed to goethite from the top to the bottom of the core samples. Chemical analysis showed that the relative concentration of As was significantly high in the core samples compared with that in the drainage, indicating that As was likely to be adsorbed strongly on or coprecipitated with iron oxyhydroxide. Correlation analysis also indicated that As can be easily removed from mine drainage during iron mineral precipitation due to its high affinity to Fe. The concentration ratio of As, Cd, Co, Ni, and Zn to Fe generally decreased with depth in the core samples, suggesting that mineral transformation can increase those concentrations in the drainage. In contrast, the concentration ratio of Cr to Fe increased with depth, which can be explained by the chemical bond of iron oxide and chromate, and surface charge of ferrihydrite and goethite.

• Korean Journal of Mineralogy and Petrology
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• v.33 no.4
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• pp.349-359
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• 2020

The Ulsan Fault Zone (UFZ) of NNW trend is developed in the Gyeongsang Basin, the southeastern part of the Korean Peninsula, and the Quaternary faults have been found around the UFZ. The faults generally thrust the Bulguksa igneous rocks of Late Cretaceous-Early Tertiary upon the Quaternary deposits or are developed within the Quaternary deposits. They mainly show the reverse-slip sense of top-to-the west movement. The lines connecting the their outcrop sites show a zigzag-form which is similar to the orientation of their fault surfaces which show the various trends, like (W)NW, N-S, (E)NE, ENE trends. The E-W trending dextral strike(-slip) fault is found in the Quaternary deposits of the Singye-ri valley. It cuts the N-S trending reverse fault and are cut by the N-S trending thrust fault again. Two types of at least two times of Quaternary tectonic movements related to the formation of neotectonic fault zone in the Singye-ri valley are considered from such the geometric and kinematic characteristics of Quaternary faults. One is the reverse faulting of N-S trend by the E-W directed 1st compression and associated the strike-slip tear faulting of E-W trend, and then the thrust faulting of N-S trend by the E-W directed 2nd compression. The other is the reverse faulting of N-S trend, and then the dextral strike-slip faulting of E-W trend by the NW-SE directed compression, and then the thrust faulting of N-S trend. In this paper is suggested the development history of Singye-ri neotectonic fault zone on the basis of the various orientations of Quaternary fault surfaces around the UFZ, and the zigzag-form connecting line of their outcrop sites, and the compressive arc-shaped lineaments which convex to the west reported recently in the Yangsan Fault Zone.

• Korean Journal of Mineralogy and Petrology
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• v.35 no.3
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• pp.313-331
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• 2022

Natural or native abiotic molecular hydrogen (H₂) is a major component in natural gas, however yet its importance in the global energy sector's usage as clean and renewable energy is underestimated. Here we review the occurrence and geological settings of native hydrogen to demonstrate the much widesprease H₂ occurrence in nature by comparison with previous estimations. Three main types of source rocks have been identified: (1) ultramafic rocks; (2) cratons comprising iron (Fe²⁺)-rich rocks; and (3) uranium-rich rocks. The rocks are closely associated with Precambrian crystalline basement and serpentinized ultramafic rocks from ophiolite and peridotite either at mid-ocean ridges or within continental margin(Zgonnik, 2020). Inorganic geological processes producing H₂ in the source rocks include (a) the reduction of water during the oxidation of Fe²⁺ in minerals (e.g., olivine), (b) water splitting due to radioactive decay, (c) degassing of magma at low pressure, and (d) the reaction of water with surface radicals during mechanical breaking (e.g., fault) of silicate rocks. Native hydrogen are found as a free gas (51%), fluid inclusions in various rock types (29%), and dissolved gas in underground water (20%) (Zgonnik, 2020). Although research on H₂ has not yet been carried out in Korea, the potential H₂ reservoirs in the Gyeongsang Basin are highly probable based on geological and geochemical characteristics including occurrence of ultramafic rocks, inter-bedded basaltic layers and iron-copper deposits within thick sedimentary basin and igneous activities at an active continental margin during the Permian-Paleogene. The native hydrogen is expected to be clean and renewable energy source in the near future. Therefore it is clear that the origin and exploration of the native hydrogen, not yet been revealed by an integrated studies of rock-fluid interaction studies, are a field of special interest, regardless of the presence of economic native hydrogen reservoirs in Korea.

• 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.3
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• pp.355-365
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• 2022

Precipitation and phase transition of iron minerals in mine drainage greatly affect the behavior of trace elements. However, the precipitation of ferrihydrite, one of the major iron minerals precipitated in drainage, and the related behavior of trace elements have hardly been studied. In this study, the effects of pH change and time on mineral precipitation characteristics in mine drainage from the Munkyeong coal mine were investigated, and the behavioral changes of trace elements related to the precipitation of these minerals were studied. In the case of precipitated mineral phases, goethite was observed at pH 4, and 2-line ferrihydrite mixed with small amount of 6-line ferrihydrite was mainly identified at pH 6 or higher. In addition, it was observed that the precipitation of calcite additionally increased as the pH increased in the samples at pH 6 or higher. The occurrence of goethite was probably due to the phase change of initially precipitated ferrihydrite within a short time under the influence of low pH. Our results showed that the concentration of trace elements was strongly influenced by pH and time. With increasing time, Fe concentration in the drainage showed a abrupt decrease due to the precipitation of iron minerals, and the concentration of As existing as oxyanions in the drainage, also decreased rapidly like Fe regardless of the pH values. This decrease in As concentration was mainly due to co-precipitation with ferrihydrite, and also partly to surface adsorption on goethite at low pH in drainage. Contrary to this observation, the concentration of other trace elements, such as Cd, Co, Zn, and Ni was greatly affected by the pH regardless of the mineral species. The lower the pH value, the higher the concentration of these trace elements were observed in the drainage, and vice versa at higher pH. These results indicate that the behavior of trace elements present as cations is more greatly affected by the mineral surface charge influenced by the pH values than the type of the precipitated mineral.

• Economic and Environmental Geology
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• v.55 no.5
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• pp.531-540
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• 2022

Various iron minerals that precipitate in acid mine drainage have a great influence on the concentration change and mobility of trace elements in the drainage during phase transition to other minerals as well as the precipitation process. This study investigated the change of mineral properties and the behaviors of trace elements influenced by pH and time for the precipitates collected from the acid mine drainage treatment system of the Dalsung mine, where schwertmannite is mainly precipitated. However, the main mineral precipitated in the drainage was goethite, suggesting schwetmannite has already undergone a phase transition to goethite to some extent, and it was observed that at higher pH, the peak width at half maximum of XRD peak was narrower. This can be interpreted as the transformation of small amount of amorphous schwetmannite to goethite or an increase in the crystallinity of goethite, and it showed that the higher the pH, the greater this change was. The concentration of Fe was also greatly affected by the pH values, and as the pH increased, the concentration of Fe in the drainage decreased. With increasing time, the Fe concentration increased and then decreased, which can be interpreted to indicate the dissolution of schwertmannite and precipitation of goethite. This mineral change probably resulted in the rapid increase of the concentration of S at initial stage, but its concentration was stabilized later. The concentration of S is also related to the stability of schwetmannite, showing a high concentration at a low pH at which schwertmannite is stable and a low concentration at a high pH at which goethite is stable. The trace elements present as cations in the drainage also showed a close relationship with the pH, generally the lower the pH, the higher the concentration, due to the solubility changes by the pH, and the precipitation and the changes in mineral surface charge at high pH. On the other hand, in the case of As, existing as an anion, although it showed a high concentration at low pH, its concentration increased with time at all pH values, which is probably related to the concentration of Fe which can be coprecipitated in the drainage, and the increase of As concentration with time is also considered to be related to the decrease in schwertmannite rather than the mineral surface charge.

• Korean Journal of Mineralogy and Petrology
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• v.36 no.1
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• pp.55-72
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• 2023

This study aims to identify the fault zone architecture and geometric and kinematic characteristics of the Yeongdeok Fault, based on the geometry and kinematic data of various structural elements obtained by detailed field survey and anisotropy of magnetic susceptibility (AMS) of the fault rocks. The Yeongdeok Fault extends from Opo-ri, Ganggu-myeon, Yeongdeok-gun to Gilgok-ri, Maehwa-myeon and Bangyul-ri, Giseong-myeon, Uljin-gun, and cuts various rock types from the Paleo-proterozoic to the Mesozoic with a range of 4.6-5.0 km (4.77 km in average) of right-lateral offset or forms the rock boundaries. The fault is divided into four segments based on its geometric features and shows N-S to NNW strikes and dips of an angle of ≥ 54° to the east at most outcrops, even though the outcrops showing the westward dipping (a range of 54°-82°) of fault surface increase as it goes north. The Yeongdeok Fault shows the difference in the fault zone architecture and in the fault core width ranging from 0.3 to 15 m depending on the bedrock type, which is interpreted as due to differences in the physical properties of bedrock such as ductility, mineral composition, particle size, and anisotropy. Combining the results of paleostress reconstruction and AMS in this and previous studies, the Yeongdeok Fault experienced (1) sinistral strike-slip under NW-SE maximum horizontal principle stress (σ_Hmax) and NE-SW minimum horizontal principle stress (σ_Hmin) in the late Cretaceous to early Cenozoic, and then (2) dextral strike-slip under NE-SW maximum horizontal principle stress (σ_Hmax) and NW-SE minimum horizontal principle stress (σ_Hmin) in the Paleogene. It is interpreted that the deformation caused by the Paleogene dextral strike-slip movement was the most dominant, and the crustal deformation was insignificant thereafter.

• Korean Journal of Mineralogy and Petrology
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• v.36 no.2
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• pp.117-124
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• 2023

X-ray diffraction analysis, X-ray fluorescence analysis, thermal differential and thermos gravimetric analysis, cation exchange capacity analysis, and Cesium (Cs), Strontium (Sr) adsorption experiments were performed to investigate the physical and chemical properties of natural zeolite from Guryongpo in Korea. As a result of X-ray diffraction analysis, minerals such as mordenite, heulandite, clinoptilolite, and illite are contained, and as a result of X-ray fluorescence analysis, elements such as SiO₂, Al₂O₃, CaO, K₂O, MgO, Fe₂O₃ and Na₂O are contained, and the cation exchange capacity was 148.6 meq/100 g. As a result of thermal differential and thermos gravimetric analysis, it was confirmed that the thermal stability was excellent up to 600 ℃. As a result of the adsorption equilibrium experiment over time, the equilibrium was reached within 30 min. for Cesium (Cs) and within 8 hr. for Strontium (Sr), and the adsorption rates of Cesium (Cs) and Strontium (Sr) were 80% and 18%, respectively. As a result of the single-component isothermal adsorption experiment, in conformed to the Langmuir model, and the maximum Cesium (Cs) adsorption amount was 131.5 mg/g, which was high, while the Strontium (Sr) maximum adsorption amount was 29.5 mg/g, which was low. In the case of the natural zeolite used in this study, the content of minerals including 8-rings such as clinoptilolite, heulandite, and mordenite is high, showing high selectivity for Cesium (Cs).