• Economic and Environmental Geology
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• v.50 no.6
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• pp.545-554
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• 2017

Birnessite is one of the dominant Mn (oxyhydr)oxide phases commonly found in soil and deep ocean environments. It typically occurs as nano-sized and poorly crystalline aggregates in the natural environment. It is well known that birnessite participates in a wide variety of bio/geochemical reactions as a reactive mineral phase with structural defects, cation vacancies, and mixed valences of structural Mn. These various bio/geochemical reactions control not only the fate and transport of inorganic and organic substances in the environment, but also the formation of diverse Mn (oxyhydr)oxides through birnessite transformation. This review assessed and discussed about the phase transformation of birnessite under a wide range of environmental conditions and about the potential geochemical factors controlling the corresponding reactions in the literature. Birnessite transformation to other types of Mn (oxyhydr)oxides were affected by dissolved Mn(II), dissolved oxygen, solution pH, and co-existing cation (i.e., $Mg^{2+}$). However, there still have been many issues to be unraveled on the complex bio/geochemical processes involved in the phase transformation of birnessite. Future work on the detail mechanisms of birnessite transformation should be further investigated.

• Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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• 2003.09a
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• pp.583-586
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• 2003

부산 동래지역 지열수에 대한 지화학적 진화과정을 밝히기 위하여 지열수, 지하수 및 해수에 대한 수리화학 특성과 이들의 연관성을 고찰하였다. 또한 심부환경에서의 지화학 특성을 규명하기 위하여 각종 이온지질온도계와 다성분 지질온도계를 적용하였으며, 동위원소특성과 함께 지화학 모델링을 통하여 심부환경에서의 온천수의 지화학특성을 밝히고자 하였다. 동래 지열수의 수리화학적 특성은 해수의 영향을 받아 높은 이온함량을 보이며 Na-Cl형을 보여준다. 지열수는 주변 지하수와의 크게 혼합된 양상을 나타낸다. 지화학 모델링에 따르면 지열수는 심부에서 약 5% 영향을 받은 것으로 추정된다. 즉, 심부로 순환하는 지열수가 해수와 혼합되며, 이들이 지열에 의해 가열되면서 광물의 용해 및 침전, 이온 교환반응 등 물-암석 반응을 거치면서 심부지열수를 형성하였으며, 지열수가 천부환경으로 상승하는 과정에서 동래지역 주변 천부지하수와 다양하게 혼합되면서 현재 동래온천수의 화학조성을 갖는 온천수를 형성하는 것으로 지열수의 진화 과정을 설명할 수 있다.

• Economic and Environmental Geology
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• v.34 no.3
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• pp.255-269
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• 2001

The geochemical studies on groundwater in the borehole, which is straddled by multi-packer (MP) system, were carried out from a volcanic terrain in the Yeosu area. The pH of groundwater collected from selected sections in the MP-installed borehole is much higher (up to 9.6) than that of the borehole groundwater (7.0-7.9) collected using conventional pumping technique. Hydrochemistry shows that the groundwater has a typical chemical change with increasing sampling depth, suggesting that the groundwater is evolved through water-rock interaction along the fracture-controlled flow paths. The groundwater from the deeper part (138-175 m below the surface) in borehole KI is characterized by the Ca-C11 type with high Ca (up to 160 mg/L) and Cl (up to 293 mg/L) contents, probably reflecting seawater intrusion. The groundwater also has high sodium and sulfate contents compared to the waters from other boreholes. These observed groundwater chemistry is explained by the cation exchange, sulfide oxidation, and mixing process with seawater along the flow path.

• Economic and Environmental Geology
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• v.44 no.2
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• pp.123-133
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• 2011

The lab scale experiments to investigate the geochemical reaction among supercritical $CO_2$-mineral-brine which occurs at $CO_2$ sequestration sites were performed. High pressurized cell system (l00 bar and $50^{\circ}C$) was designed to create supercritical $CO_2$ in the cell, simulating the sub-surface $CO_2$ storage site. From the high pressurized cell experiment, the surface changes of Ca-feldspar, amphibole (tremolite) and olivine, resulted from the supercritical $CO_2$-mineral-brine reaction, were observed and the dissolution of minerals into the brine was also investigated. The mineral slabs were polished and three locations on the surface were randomly selected for the image analysis of SPM and the surface roughness value (SRV) of those locations were calculated to quantify the change of mineral surface for 30 days. At a certain time interval, SPM images and SRVs of the same mineral surface were acquired. The secondary minerals precipitated on the mineral surfaces were also analyzed on SEM/EDS after the experiment. From the experiments, the average SRV of Ca-feldspar increased from 2.77 nm to 20.87 nm for 30 days, suggesting that the dissolution of Ca-feldspar occurs in active when the feldspars contact with supercritical $CO_2$ and brine. For the amphibole, the average SRV increased from 2.54 nm to 8.31 nm and for the olivine from 0.77 nm to 11.03 run. For the Ca-feldspar, $Ca^{2+}$, $Na^+$, $Fe^{2+}$, $Si^{4+}$, $K^+$ and $Mg^{2+}$ were dissolved in the highest order and $Si^{4+}$, $Ca^{2+}$, $Fe^{2+}$ and $Mg^{2+}$ for the amphibole. Fe (or Mg) - oxides were precipitated as the secondary minerals on the surfaces of amphibole and olivine after 30 days reaction. Results suggested that $Ca^{2+}$, $Fe^{2+}$ and $Mg^{2+}$ rich minerals would be significantly weathered when it contacts with the supercritical $CO_2$ and brine at $CO_2$ sequestration sites.

• Journal of the Korean Society of Groundwater Environment
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• v.6 no.4
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• pp.159-170
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• 1999

The hydrogeochemical study on the $CO_2$-rich water in the Chojeong area was carried out. The $CO_2$-rich water of Ca-$HCO_3$type is characterized by low pH (5.0~5.8). high $CO_2$concentration ($Pco_2$＜$10^{0.31}$atm) and high TDS. The water chemistry indicates that the $CO_2$-rich water was probably evolved by the local suppy of deep seated $CO_2$gas resulting in the enhanced water/rock (granite) interaction under low pH conditions. High $NO_3$concentration indicates that the $CO_2$water was mixed and diluted with low $CO_2$groundwater in the vicinity of the area, in which the extensive groundwater abstraction occurred during the past years. The evoiution of the $CO_2$-rich water in the Chojeong area for the process of $CO_2$injection water/rock interaction and mixing processes was thermodynamically simulated by PHREEQC. Although the simulation was limited to water/plagioclase interaction, the results show the feasible explanation about the observed trend of pH and Ca and Na concentrations of the $CO_2$-rich water.

• 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.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.

• Economic and Environmental Geology
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• v.34 no.4
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• pp.329-343
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• 2001

The deep environment and geochemical evolution of the Bugok geothennal waters, located in the Kyeongnam Province, was re-interpreted based on the hydrochemical and isotopic data published by Yun et al. (1998). The geothermal waters of the Bugok area is geochemically divided into three groups; Geothennal water I, II and III groups. Groups I and II are geochemically similar; high temperature (55.2-77.2$^{\circ}$C) and chemically belonging to Na-S04 types. However, pH and Eh values are a little different each other and Group II water is highly enriched in S04 compared to Group I water. Group III water, occurring from peripheral sites of the central part of the geothennal waters, shows temperature range of 29.3 to 47.0$^{\circ}$C and belongs to $Na-HCO_3-S0_4$ types. The deep environment and geochemical evolution of the Bugok geothennal waters, showing the diversity of geochemistry, can be interpreted as follows; I) Descending to great depth of meteoric waters that originated at high elevation and reacting with sediments and/or granites in depth. The $S0_4$ concentration of the waters has been increased by the dissolution of sulfate minerals in sediments. 2) During the continuous descending, the waters has met with the reduction environment, producing the $H_2S$ gas due to sulfate reduction. The waters has been heated up to 130$^{\circ}$C and the extent of water-rock reaction was increased. At this point, pH of waters are increased, S04 concentration decreased and calcite precipitated, therefore, the waters show the $Na-S0_4$ type. 3) Ascending of the geothennal waters along the flow path of fluids and mixing with less-deeply circulated waters. The $S0_4$ concentration is re-increased due to the oxidation of $H_2S$ gas and/or sulfide minerals in sediments. During continuous ascending, these geothennal waters are mixed with shallow groundwater.

• Economic and Environmental Geology
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• v.47 no.4
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• pp.421-430
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• 2014

In this study, a series of autoclave experiments were conducted in order to investigate the geochemical and mineralogical effects of carbon dioxide on deep subsurface environments. High pressure and temperature conditions of $50^{\circ}C$ and 100 bar, which are representative environments for geological $CO_2$ sequestration, were created in stainless-steel autoclaves for simulating the interactions in the $scCO_2$-groundwater-mineral reaction system. Zeolite, a widespread mineral in Pohang Basin where many researches have been focused as a candidate for geological $CO_2$ sequestration, and groundwater sampled from an 800 m depth aquifer were applied in the experiments. Geochemical and mineralogical alterations after 30 days of $scCO_2$-groundwater-zeolite sample reactions were quantitatively examined by XRD, XRF, and ICP-OES investigations. The results suggested that dissolution of zeolite sample was enhanced under the acidic condition induced by dissolution of $scCO_2$. As the cation concentrations released from zeolite sample increase, $H^+$ in groundwater was consumed and pH increases up to 10.35 after 10 days of reaction. While cation concentrations showed increasing trends in groundwater due to dissolution of the zeolite sample, Si concentrations decreased due to precipitation of amorphous silicate, and Ca concentrations decreased due to cation exchange and re-precipitation of calcite. Through the reaction experiments, it was observed that introduction of $CO_2$ could make alterations in dissolution characteristics of minerals, chemical compositions and properties of groundwater, and mineral compositions of aquifer materials. Results also showed that geochemical reactions such as cation exchange or dissolution/precipitation of minerals could play an important role to affect physical and chemical characteristics of geologic formations and groundwater.