• Economic and Environmental Geology
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• v.42 no.5
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• pp.479-486
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• 2009

In natural environments, manganese (Mn) exists in the valence of +2, +3, and +4 and plays a pivotal role as a strong oxidant or reductant in the geochemical cycles of elements. Especially, Mn forms varying (oxyhydr)oxides. The oxidation state of structural Mn is characteristic to each oxide and is one of the most important factors controlling its geochemical behaviors such as solubility, sorption capacity, and redox potential. Therefore, it is important to elucidate processes governing Mn oxidation state in predicting the fate and transport of many redox sensitive elements in the environment. X-ray photoelectron spectroscopy (XPS) is a very useful method to determine the oxidation state of various elements in solid phases. In this study, the oxidation states of structural Mn in MnO, $Mn_2O_3$, $MnO_2$ were assessed based on the binding energy spectra of $Mn2p_{3/2}$ and Mn3s using XPS and were compared with those reported elsewhere. $Mn2p_{3/2}$ binding energies were determined as 640.9, 641.5, 641.8 eV for MnO, $Mn_2O_3$, $MnO_2$, respectively, which indicates that the binding energy increased with increasing Mn oxidation state. It was also noted that Ar etching may cause changes in electronic structure configuration on surface of the original sample.

• The Sea:JOURNAL OF THE KOREAN SOCIETY OF OCEANOGRAPHY
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• v.4 no.3
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• pp.198-207
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• 1999

Five core sediments acquired from the Lake Shihwa are analyzed for variations of sedimentary environment and heavy metal pollution after the Shihwa seawall construction. The depositional environment of the study area is divided into anoxic, oxic and mixed suboxic conditions based on the C/N ratio and C/S ratios of organic matters. Controlling factors for redox condition are the water depth and the difference in industrial effluents supply. Correlations among geochemical elements (Mn, U, Mo) show a distinctive difference and thus can be used as an indicator of redox condition. The content of Al, Ti are dependent on the sediment characteristics, and the contents of heavy metals (Cr, Ni, Cu, Zn, and Pb) indicate heavy metal pollution. The concentrations of heavy metals are higher near Shiswa-Banwol industrial complexies than the central part of Lake Shihwa. Especially, the accumulation of the heavy metal at the surface sediments near Shihwa-Banwol industrial complex are two to eight times higher than in the center of Lake Shihwa.

• Economic and Environmental Geology
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• v.34 no.1
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• pp.71-88
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• 2001

The Geochemica] and isotope studies on the $CO_2$-rich water from the Shinchon area were carried out. The Shinchon $CO_2$-rich water belongs to Ca(Na)-$HCO_3$ type showing very high $P_{CO_{2}}$ ( $10^{-0.35}$ ~ $10^{0.29}$ atm) and TDS (835-3,144 mg/L). The results of geochemical and isotope analysis indicate that $CO_2$ gas is originated from the deep seated source such as mantle or magmatic gases. The $CO_2$-rich water was evolved by interaction with deep-seated granite and major water-rock interaction was dissolution of p]agioclase resulting high Na content of $CO_2$-rich water. Precipitation and dissolution of secondary calcite might be accompanied with the dissolution of plagioclase maintaining Na/Ca ratio. High contents of K and $SO_4$ indicate that the geochemical characteristics of $CO_2$-rich water were partially affected by interaction with upper sedimentary rock during uprising to surface. N03 and tritium contents suggest that the $CO_2$-rich water was mixed with low $CO_2$ groundwater at some locations. The oxygen-hydrogen isotopes show that all water samples were derived from meteoric waters and the $CO_2$-rich water was isotopically re-equilibrated with lighter $CO_2$ gas. Although some carbon isotope data show isotopically heavy values, carbon isotope data indicate that the $CO_2$ gas was possib]y derived by deep source.

• Economic and Environmental Geology
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• v.46 no.4
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• pp.359-373
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• 2013

Shale is considered as a source rock for conventional oil and gas exploration and development because shale is fine-grained detrital sedimentary rock which can preserve the organic matter better. Shale has a good sealing capacity for the petroleum trap due to its low permeability. Commercial recoveries of gas from shale in the North America based on the development of technologies of horizontal drilling and hydraulic fracturing reveal that shale also function as a effective reservoir rock. Geochemical techniques to evaluate generation potential of the hydrocarbons from organic matter in the source rocks can be applied for the exploration of the shale gas resources. To evaluate shale gas resources, it is important to understand various geochemical processes and shale characteristics controlling generation, storage and estimation of shale gas reserves. In this paper, the generation mechanism of the oil and gas from organic matter is reviewed, and geochemical techniques which can be applied for the evaluation and characterization of shale gas are introduced.

• The Journal of the Petrological Society of Korea
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• v.11 no.3_4
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• pp.182-199
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• 2002

We attempted to show the evolution of the magma and the geochemical characteristics of dikes and dike swarms by using the petrographic and geochemical data from 287 dikes, SE Korea. The dikes can be divided into mafic, intermediate, and felsic dikes in the field. And each of them is subdivided into three groups, two groups, and two groups, respectively. The group (I) among the mafic dikes most pervasively occurs and are distributed in both sides of the Yeonil Tectonic Line (YIL), which petrographic and geochemical characteristics are the same. These facts thus, strongly support the results of the previous studies which showed that they were intruded contemporaneously and that YTL was a main tectonic line which restricted the crustal clockwise rotation during the Early Miocene. The geochemical characteristics are discriminated according to the seven groups divided petrographically. The mafic, intermediate and felsic dikes belong to basalt and basaltic andesite, andesite and facile, and rhyolite, respectively, and the magmas mostly belong to calc-alkaline series. The geochemical data indicate that there were the fractional crystallizations of olivine, clinopyroxene, and plagioclase in the mafic dikes. And the content of characteristic elements and tectonic discrimination diagrams show that the dikes were formed from the magma related to the subduction of plate and that the tectonic setting was related to orogenic volcanic arc.

• 한국석유지질학회:학술대회논문집
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• autumn
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• pp.56-62
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• 2001

울릉분지 남서부 해역에서 채취한 두 개의 피스톤 코어 (piston core) 시료를 이용하여 퇴적학 및 지화학적 특성을 연구하였다. 코어는 제4기말의 이질 퇴적물로 대부분 구성되어 있고, 테프라 (tephra layer)와 사질 퇴적물이 일부 협재되어 나타난다. 기존 확인된 울릉분지의 테프라를 이용하여 층서 대비를 한 결과, 두 코어는 대양보다는 높은 퇴적률 (10-12cm/kyr)을 갖는다. 이는 코어가 약 4만 4천년 전의 기록부터 시작하고 있음을 의미한다. 동위원소 층서 2 (마지막 빙기) 중에 형성된 구간에서는 저탁류의 영향을 많이 받은 여러 종류의 퇴적상들이 교호하여 나타난다. 코어의 하부 구간에서는 가스의 방출에 의하여 형성된 것으로 사료되는 수평균열이 다수 관찰된다. 두 코어에서 측정된 유기탄소 (organic carbon) 함량은 평균 $1.8\% $(0.1-4.5\%)$으로 열린 바다 (open sea) 퇴적물의 유기탄소 함량보다 높다. 이는 Termination I 시기 때 해수면 상승으로 인해 산소가 다소 결핍된 환경으로 전이되면서 유기탄소의 양이 증가하였음을 보여주는 것으로 해석된다.

• Economic and Environmental Geology
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• v.56 no.1
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• pp.55-63
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• 2023

Variations in geochemical and mineralogical properties of the ferromanganese(Fe-Mn) crust reflect environmental changes. In the present study, geochemical and mineralogical analyses, including micro X-ray fluorescence and X-ray diffraction, were utilized to reconstruct the paleo-ocean environment of western Pacific Magellan seamount cluster. Samples of the Fe-Mn crust were collected using an epibenthic sledge from the open seamount XX (151° 51.12' 7.2" E and 16° 8.16' 9.6" N, 1557 meters below sea level) in the Western Pacific Magellan Seamount. According to the structure and phosphating status, the Fe-Mn crust of the OSM-XX can be divided into the following: phosphatizated (L4-L5), massive non-phosphatizated (L3), and porous non-phosphatizated (L1-L2) portions. All ferromanganese layers contain vernadite, and owing to the presence of carbonate fluorapatite (CFA), the phosphatizated portion (L4-L5) is rich in Ca and P. The massive non-phosphatizated section (L3) contains high Mn, Ni, and Co, whereas the porous non-phosphatizated portion (L1-L2), which comprises detrital quartz and feldspar, is rich in Fe. Variations in properties of the Fe-Mn crust from the OSM-XX reflect changes in the nearby marine environment. The formation of this crust started at approximately 51.87 Ma, and precipitation of the CFA during the global phosphatization event that occurred at approximately 36-32 Ma highlights an elevated sea level and low temperature during the associated period. The high Mn, Ni, and Co concentrations and elevated Mn/Fe ratios of samples from the massive phosphatizated portion indicate that the oxygen minimum zone (OMZ) was enhanced, and reducing conditions prevailed during the crust formation. The high Fe and low Mn/Fe ratios in the porous portion indicate a weak OMZ and dominantly oxidizing conditions. These data reflect environmental changes following the end of the Mi-1 glacial period in the Miocene-Oligocene boundary. Subsequently, Mn/Fe and Co/Mn ratios increased slightly in the outermost part of Fe-Mn crust because of the enhanced bottom current and OMZ associated with the continued cooling from approximately 9 Ma. However, the reduced carbonate dissolution rate in the Pacific Ocean from approximately 6 Ma decreased the growth rate of the Fe-Mn crust.

• Economic and Environmental Geology
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• v.41 no.2
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• pp.183-199
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• 2008

This study is focused on characterization of the physio-chemical and mineralogical properties, investigation of their vertical changes in the tailing profile of the Guryoung mining area, classification of the profile into distinct zones, and condition conceptual model of physio-chemical conditions and phases-water relationships controlling the element behaviors in the tailings. The upper part of the groundwater is characterized by the high contents of $Fe_2O_3$ and $SO_3$ for whole rock analysis, low pH, and the occurrence of jarosite, schwertmannite and Fe-oxyhydroxide as the secondary mineral phases. The tailing profile can be divided into the covering soil, jarosite zone, Fe-sulfate zone, Fe-oxyhydroxide and gypsum-bearing pyrite zone, calcite-bearing pyrite zone, soil zone, and weathered zone on the based of the geochemical and mineralogical characteristics. The profile can be sampled into the oxidized zone and the carbonate-rich primary zone with the dramatic changes in pH and the secondary mineral phases. The conceptual model proposed for the tailing profile can be summarized that the oxidation of pyrite is the most important reaction controlling the changes in pH, the dissolution of the primary silicates and carbonates, the precipitation of secondary mineral phases, acid-neutralizing, and heavy metal behaviors through the profile.

• Economic and Environmental Geology
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• v.49 no.5
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• pp.371-380
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• 2016

This study aims to identify the mineraloical and petrographical characteristics of caprock from drilling cores of Pohang basin as a potential $CO_2$ storage site. Experiments and modeling were conducted in order to investigate the geochemical and mineralogical caprock effects of carbon dioxide. A series of autoclave experiments were conducted to simulate the interaction in the $scCO_2$-caprock-brine using a high pressure and temperature cell at $50^{\circ}C$ and 100 bar. Geochemical and mineralogical alterations after 15 days of $scCO_2$-caprock-brine sample reactions were quantitatively examined by XRD, XRF, ICP-OES investigation. Results of mineralogical studies, together with petrographic data of caprock and data on the physicochemical parameters of brine were used for geochemical modeling. Modelling was carried out using the The Geochemist's Workbench 11.0.4 geochemical simulator. Results from XRD analysis for caprock sample showed that major compositional minerals are quartz, plagioclase, and K-feldspar, and muscovite, pyrite, siderite, calcite, kaolinite and montnorillonite were included on a small scale. Results from ICP-OES analysis for brine showed that concentration of $Ca^{2+}$, $Na^+$, $K^+$ and $Mg^{2+}$ increased due to dissolution of plagioclase, K-feldspar and muscovite. Results of modeling for the period of 100 years showed that the recrystallization of kaolinite, dawsonite and beidellite, at the expense of plagioclase and K-feldspar is characteristic. Volumes of newly precipitation minerals and minerals passing into brine were balanced, so the porosity remained nearly unchanged. Experimental and modeling results indicate the interaction between caprock and $scCO_2$ during geologic carbon sequestration can exert significant impacts in brine pH and solubility/stability of minerals.

• Economic and Environmental Geology
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• v.54 no.1
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• pp.69-76
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• 2021

This study is to identify the mineralogical properties of caprock samples from drilling cores of the Pohang basin, which is the research area for the demonstration-scale CO2 storage project in Korea. The interaction of water-rock-gas that can occur due to CO2 injection was identified using geochemical modeling. Results of mineralogical studies, together with petrographic data of caprock and data on the physicochemical parameters of pore water were used for geochemical modeling. Modelling was carried out using the The Geochemist's Workbench 14.0.1 geochemical simulator. Two steps of modeling enabled prediction of immediate changes in the caprocks impacted by the first stage of CO2 injection and the assessment of long-term effects of sequestration. Results of minerlaogical analysis showed that the caprock samples are mainly composed of quartz, K-feldspar, plagioclase and a small amount of pyrite, calcite, kaolinite and montmollonite. After the injection of carbon dioxide, the porosity of the caprock increased due to the dissolution of calcite, and dawsonite and chalcedony were precipitated as a result of the dissolution of albite and k-feldspar. In the second step after the injection was completed, the precipitation of dawsonite and chalcedony occurred as a result of dissolution of calcite and albite, and the pH was increased due to this reaction. Results of these studies are expected to be used as data to quantitatively evaluate the efficiency of mineral trapping capture in long-term storage of carbon dioxide.