• Economic and Environmental Geology
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• v.33 no.5
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• pp.405-415
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• 2000

This study was carried out to understand the formation of acid mine drainage (AMD) by pyrophyllite (so-called Napseok)-rainwater interaction (weathering), dispersion patterns of heavy metals, and patterns of mixing with non-polluted water in the Tongnae pyrophyllite mine. Based on the mass balance and reaction path modeling, using both the geochemistry of water and occurrence of the secondary minerals (weathering products), the geochemical evolution of AMD was simulated by computer code of SOLVEQ and CHILLER. It shows that the pH of stream water is from 6.2 to 7.3 upstream of the Tongnae mine. Close to the mine, the pH decreases to 2. Despite being diluted with non-polluted tributaries, the acidity of mine drainage water maintains as far as downstream. The results of modeling of water-rock interaction show that the activity of hydrogen ion increases (pH decreases), the goncentration of ${HCO_3}^-$ decreases associated with increasing $H^+$ activity, as the reaction is processing. The concentration of ${SO_4}^{2-}$first increases minutely, but later increases rapidly as pH drops below 4.3. The concentrations of cations and heavy metals are controlled by the dissolution of reactants and re-dissolution of derived species (weathering products) according to the pH. The continuous adding of reactive minerals, namely the progressively larger degrees of water-rock interaction, causes the formation of secondary minerals in the following sequence; goethite, then Mn-oxides, then boehmite, then kaolinite, then Ca-nontronite, then Mgnontronite, and finally chalcedony. The results of reaction path modeling agree well with the field data, and offer useful information on the geochemical evolution of AMD. The results of reaction path modeling on the formation of AMD offer useful information for the estimation and the appraisal of pollution caused by water-rock interaction as geological environments. And also, the ones can be used as data for the choice of appropriate remediation technique for AMD.

• Journal of Soil and Groundwater Environment
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• v.12 no.4
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• pp.35-53
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• 2007

Geochemical and isotope studies on the groundwater system of the Youngcheon area were carried out. Most groundwaters belong to Ca-$HCO_3$ and Ca-$SO_4$ types and some groundwaters belong to Na-$HCO_3$ type. Geochemical characteristics of these groundwaters were mainly affected by their basement rocks around the boreholes. High $SO_4$ content of groundwater is the result of reaction with sulfate or sulfide minerals in the host rock. Ca was originated from the carbonate minerals in the sedimentary rock. After the groundwater was saturated with calcite, the Na-$HCO_3$ type groundwaters were evolved by the reaction with plagioclase for a relatively long residence time. This explanation was supported by low tritium contents of Na-$HCO_3$ type groundwaters. ${\delt}a^{18}O$ and ${\delta}D$ data indicate that the groundwaters are of meteoric water origin and there was no difference between the various types of waters. Grondwaters from the boreholes BH-1, BH-9 and BH-12 showed the geochemical and isotopic characteristics of deep groundwater. Most borehole groundwaters except them did not show the systematic geochemical variations with sampling depth indicating that the shallow and deep groundwaters were mixed with each other throughout the study area. The results of water quality analysis indicate that the study area is highly contaminated by the introduction of agricultural sewage.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.5 no.4
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• pp.273-281
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• 2007

Hyperalkaline groundwater formed by groundwater-cement components and its reaction with bedrock in a nuclear waste repository were simulated by geochemical modeling. The result of groundwater-cement components reaction showed that the pH of water was 13.3 and the precipitated minerals were Brucite, Katoite, Calcium Silicate Hydrate(CSH1.1), Ettringite, Hematite, and Portlandite. The result of interaction between such minerals and groundwater sampled in Gyeongju area also showed that the pH of groundwater reached 12.4. Interaction between such hyperalkaline groundwater and granite was simulated by kinetic model during $10^3$ years. This result showed that the final pH of groundwater reached 11.2 and the variation of pH was controlled by dissolution/precipitation of silicate and CSH minerals. Groundwater quality was also determined by dissolution/precipitation of silicate, CSH, oxide minerals. Our results show that geochemical modeling of long-term hyperalkaline groundwater and rock interaction can contribute to the safety assessment of engineered barrier by predicting geochemical condition in repository site.

• 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.

• Economic and Environmental Geology
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• v.46 no.3
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• pp.221-234
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• 2013

Laboratory experiments for the reaction with supercritical $CO_2$ under the $CO_2$ sequestration condition were performed to investigate the mineralogical and geochemical weathering process of the sandstones and mudstones in the Pohang basin. To simulate the supercritical $CO_2$-rock-groundwater reaction, rock samples used in the experiment were pulverized and the high pressurized cell (200 ml of capacity) was filled with 100 ml of groundwater and 30 g of powdered rock samples. The void space of the high pressurized cell was saturated with the supercritical $CO_2$ and maintained at 100 bar and $50^{\circ}C$ for 60 days. The changes of mineralogical and geochemical properties of rocks were measured by using XRD (X-Ray Diffractometer) and BET (Brunauer-Emmett-Teller). Concentrations of dissolved cations in groundwater were also measured for 60 days of the supercritical $CO_2$-rock-groundwater reaction. Results of XRD analyses indicated that the proportion of plagioclase and K-feldspar in the sandstone decreased and the proportion of illite, pyrite and smectite increased during the reaction. In the case of mudstone, the proportion of illite and kaolinite and cabonate-fluorapatite increased during the reaction. Concentration of $Ca^{2+}$ and $Na^+$ dissolved in groundwater increased during the reaction, suggesting that calcite and feldspars of the sandstone and mudstone would be significantly dissolved when it contacts with supercritical $CO_2$ and groundwater at $CO_2$ sequestration sites in Pohang basin. The average specific surface area of sandstone and mudstone using BET analysis increased from $27.3m^2/g$ and $19.6m^2/g$ to $28.6m^2/g$ and $26.6m^2/g$, respectively, and the average size of micro scale void spaces for the sandstone and mudstone decreased over 60 days reaction, resulting in the increase of micro pore spaces of rocks by the dissolution. Results suggested that the injection of supercritical $CO_2$ in Pohang basin would affect the physical property change of rocks and also $CO_2$ storage capacity in Pohang basin.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.16 no.3
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• pp.281-290
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• 2018

In order to understand the long-term behavior of radionuclides in granite environments, geochemical behavior characteristics of uranium in granitic host rock of KURT (KAERI Underground Research Tunnel) were investigated by dissolution experiment with different reaction time and solutions. In the dissolution experiment, significantly increased dissolution levels of uranium from granite powder samples were identified during the reaction time of 0~10 days for reaction solutions ($UD-CO_3$ and UD-Bg) containing a large amount of $CO_3{^{2-}}$. On the other hand, significantly increased dissolution levels of uranium were also identified for reaction solutions containing Na and Ca after 60 days. Dissolution of uranium continuously increased in reaction solutions of $UD-CO_3$ ($44.61{\mu}g{\cdot}L^{-1}$), UD-Bg ($41.01{\mu}g{\cdot}L^{-1}$), UD-Na ($26.87{\mu}g{\cdot}L^{-1}$), UD-Ca ($20.26{\mu}g{\cdot}L^{-1}$), UD-CaSi ($17.03{\mu}g{\cdot}L^{-1}$), and UD-Si ($10.47{\mu}g{\cdot}L^{-1}$) in the experimental period of ~270 days. However, after day 270, dissolution of uranium showed a decreasing tendency. This is thought to have occurred because existing uranium in granite samples reached the limit of dissolution by interaction with reaction solutions. Concentrations of dissolved uranium and points of maximum concentration value were found to differ depending on the $CO_3{^{2-}}$ presence in the mixed reaction solution and on the geochemical type of the water. It is estimated that differences in the reaction rate between the granite sample and the reaction solution are due to the influence of dissolved ions in the reaction solution.

• Economic and Environmental Geology
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• v.42 no.5
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• pp.403-412
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• 2009

The objective of this study is to investigate the geochemical change of feldspar minerals by supercritical $CO_2$, which exists at $CO_2$ sequestration sites. High pressurized cell system (100 bar and $50^{\circ}C$) was designed to create supercritical $CO_2$ in the cell and the surface change and the dissolution of plagioclase and orthoclase were observed when the mineral surface reacted with supercritical $CO_2$ and water (or without water) for 30 days. The polished slab surface of feldspar was contacted with supercritical $CO_2$ and an artificial brine water (pH 8) in the experiments. The experiments for the reaction of feldspar with only supercritical $CO_2$ (without brine water) were also conducted. Results from the first experiment showed that the average roughness value of the plagioclase surface was 0.118 nm before the reaction, but it considerably increased to 2.493 nm after 30 days. For the orthoclase, the average roughness increased from 0.246 nm to 1.916 nm, suggesting that the dissolution of feldspar occurs in active when the feldspars contact with supercritical $CO_2$ and brine water at $CO_2$ sequestration site. The dissolution of $Ca^{2+}$ and $Na^+$ from the plagioclase occurred and a certain part of them precipitated inside of the high pressurized cell as the form of amorphous silicate mineral. For the orthoclase, $Al^{3+}$, $K^+$, and $Si^{+4}$ were dissolved in order and the kaolinite was precipitated. In the experiments without water, the change of the average roughness value and the dissolution of feldspar scarcely occurred, suggesting that the geochemical reaction of feldspars contacted with supercritical $CO_2$ at the environment without the brine water is not active.

• 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.55 no.6
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• pp.737-760
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• 2022

For the geological disposal of high-level radioactive wastes (HLW), an understanding of deep subsurface environment is essential through geological, hydrogeological, geochemical, and geotechnical investigations. Although South Korea plans the geological disposal of HLW, only a few studies have been conducted for characterizing the geochemistry of deep subsurface environment. To guide the hydrogeochemical research for selecting suitable repository sites, this study overviewed the status and trends in hydrogeochemical characterization of deep groundwater for the deep geological disposal of HLW in developed countries. As a result of examining the selection process of geological disposal sites in 8 countries including USA, Canada, Finland, Sweden, France, Japan, Germany, and Switzerland, the following geochemical parameters were needed for the geochemical characterization of deep subsurface environment: major and minor elements and isotopes (e.g., ³⁴S and ¹⁸O of SO₄^2-, ¹³C and ¹⁴C of DIC, ²H and ¹⁸O of water) of both groundwater and pore water (in aquitard), fracture-filling minerals, organic materials, colloids, and oxidation-reduction indicators (e.g., Eh, Fe²⁺/Fe³⁺, H₂S/SO₄^2-, NH₄⁺/NO₃^-). A suitable repository was selected based on the integrated interpretation of these geochemical data from deep subsurface. In South Korea, hydrochemical types and evolutionary patterns of deep groundwater were identified using artificial neural networks (e.g., Self-Organizing Map), and the impact of shallow groundwater mixing was evaluated based on multivariate statistics (e.g., M3 modeling). The relationship between fracture-filling minerals and groundwater chemistry also has been investigated through a reaction-path modeling. However, these previous studies in South Korea had been conducted without some important geochemical data including isotopes, oxidationreduction indicators and DOC, mainly due to the lack of available data. Therefore, a detailed geochemical investigation is required over the country to collect these hydrochemical data to select a geological disposal site based on scientific evidence.

• Journal of Soil and Groundwater Environment
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• v.21 no.6
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• pp.101-113
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• 2016

To properly manage and remediate groundwater contaminated with chlorinated hydrocarbons such as trichloroethylene (TCE), it is necessary to assess natural attenuation processes of contaminants in the aquifer along with investigation of contamination history and aquifer characterization. This study evaluated natural attenuation processes of TCE at an industrial site in Korea by delineating hydrogeochemical characteristics along the flow path of contaminated groundwater, by calculating reaction rate constants for TCE and its degradation products, and by using geochemical and reactive transport modeling. The monitoring data showed that TCE tended to be transformed to cis-1,2-dichloroethene (cis-1,2-DCE) and further to vinyl chloride (VC) via microbial reductive dechlorination, although the degree was not too significant. According to our modeling results, the temporal and spatial distribution of the TCE plume suggested the dominant role of biodegradation in attenuation processes. This study can provide a useful method for assessing natural attenuation processes in the aquifer contaminated with chlorinated hydrocarbons and can be applied to other sites with similar hydrological, microbiological, and geochemical settings.