• Economic and Environmental Geology
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• v.55 no.3
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• pp.219-229
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• 2022

Bentonite is being considered as a candidate for buffer material in geological disposal systems for high-level radioactive wastes. In this study, the effect of cement-bentonite interactions on bentonite alteration was investigated by reviewing the literature on studies of cement-bentonite interactions. The major bentonite alteration by hyperalkaline fluids produced by the interaction of cementitious materials with groundwater includes cation exchange, montmorillonite dissolution, secondary mineral precipitation, and illitization. When the hyperalkaline leachate from the reaction of the cementitious material with the groundwater comes into contact with bentonite, montmorillonite, the main component of bentonite, is dissolved and a small amount of secondary minerals such as zeolite, calcium silicate hydrate, and calcite is produced. When montmorillonite is continuously dissolved, the physicochemical properties of bentonite may change, which may ultimately causes changes in bentonite performance as a buffer material such as adsorption capacity, swelling capacity, and hydraulic conductivity. In addition, the bentonite alteration is affected by various factors such as temperature, reaction period, pressure, composition of pore water, bentonite constituent minerals, chemical composition of montmorillonite, and types of interlayer cations. This study can be used as basic information for the long-term stability verification study of the buffer material in the geological disposal system for high-level radioactive wastes.

• Journal of the Mineralogical Society of Korea
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• v.22 no.3
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• pp.229-240
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• 2009

In Gosung, the symptoms similar to itai-itai disease from neighboring residents of the Samsanjeil mine have been social issues. Therefore, various researches on the behavior of heavy metals of the tailings impoundment of 280,000 ton in the Samsanjeil mine are required. In this paper, mineralogical and geochemical studies on the tailings at different depths in the Samsanjeil mine were investigated and the factors on the behavior of heavy metals were also studied. At two sampling sites (NN and SN), samples were collected at different depths down to 1 m. At NN sites, pH values decreased with depth, while those at SN sites did not show significant changes. XRD analysis showed that the main minerals in the tailings were quartz, microcline, muscovite, and chlorite with minor amount of gypsum. There were no noticeable changes in the mineral composition with depth. At NN sites, the amount of calcite was negligible, and jarosite, which usually occurs at acid soil or acid mine drainage at pH lower than 4, was identified. However, the samples at SN site contained relatively high contents of calcite with pyrite. Therefore, calcite seemed to buffer the acid and control pH at SN site. The contents of heavy metals in tailings were in the order of Cu > As > Zn > Pb > Co > Cr > Ni > Cd. The heavy metal concentrations in the tailings were closely related with pH changes. The concentrations of Cd and Co were much lower at NN site at which pH values are low than those at SN sites. Contrary to that, Cr and As which exist as oxyanions showed higher concentrations at SN sites. This result showed that the behaviors of heavy metals in our study area were controlled by pH which is influenced by the contents of calcite.

• Journal of the Korean Society of Groundwater Environment
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• v.5 no.4
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• pp.192-202
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• 1998

We investigated the geochemistry and environmental isotopes of granite-bedrock groundwater in the Yeongcheon diversion tunnel which is located about 300 m below the land surface. The hydrochemistry of groundwaters belongs to the Ca-HCO$_3$type, and is controlled by flow systems and water-rock interaction in the flow conduits (fractures). The deuterium and oxygen-18 data are clustered along the meteoric water line, indicating that the groundwater are commonly of meteoric water origin and are not affected by secondary isotope effects such as evaporation and isotope exchange. Tritium data show that the groundwaters were mostly recharged before pre-thermonuclear period and have been mixed with younger surface water flowing down rapidly into the tunnel along fractured zones. Based on the mass balance and reaction simulation approaches, using both the hydrochemistry of groundwater and the secondary mineralogy of fracture-filling materials, we have modeled the low-temperature hydrogeochemical evolution of groundwater in the area. The results of geochemical simulation show that the concentrations of Ca$\^$2＋/, Na$\^$＋/ and HCO$_3$and pH of waters increase progressively owing to the dissolution of reactive minerals in flow paths. The concentrations of Mg$\^$2＋/ and K$\^$＋/ frist increase with the dissolution, but later decrease when montmorillonite and illitic material are precipitated respectively. The continuous adding of reactive minerals, namely the progressively larger degrees of water/rock interaction, causes the formation of secondary minerals with the following sequence: first hematite, then gibbsite, then kaolinite, then montmorillonite, then illtic material, and finally microcline. During the simulation all the gibbsite is consumed, kaolinite precipitates and then the continuous reaction converts the kaolinite to montmorillonite and illitic material. The reaction simulation results agree well with the observed, water chemistry and secondary mineralogy, indicating the successful applicability of this simulation technique to delineate the complex hydrogeochemistry of bedrock groundwaters.

• Economic and Environmental Geology
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• v.36 no.2
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• pp.103-109
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• 2003

The mineralogy of material left after evaporation of acid mine drainage water is generally dependent on the chemical composition of the source water. The residues formed by the evaporation of acid mine water in the Dong-hae coal mine area consists mainly of gypsum (CaSO$_4${\circ}$2$H_2O$) with mine. amounts of alunogen (Al$_2$(SO$_4$)$_3$${\circ}$17$H_2O$) and hexahydrite (MgSO$_4$${\circ}$<.TEX>6$H_2O$). Gypsum was identified from both of the bottom precipitates and the evaporation residues of acid mine water. Alunogen, an aluminum sulfate hydrate, was also formed by evaporation and occurred as needle-like crystals. Aluminum is derived from chemical dissolution of alumine-silicate mineral such as pyre-phyllite, illite and chlorite in wasted rocks. Hexahydrite in evaporation residues occured as needle-like, fibrous, and acicular crystals and was associated with gypsum and alunogen.

• Economic and Environmental Geology
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• v.42 no.1
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• pp.1-8
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• 2009

The Haman mineralized area is located within the Cretaceous Gyeongsang Basin along the southeastern part of the Korean peninsula. Almost all occurrences in the Haman area are representative of copper-bearing polymetallic hydrothermal vein-type mineralization. Within the area are a number of fissure-filling hydrothermal veins which contain tourmaline, quartz and carbonates with Fe-oxide, base-metal sulfide and sulfosalt minerals. The Gunbuk, Jeilgunbuk and Haman mines are each located on such veins. The ore and gangue mineral paragenesis can be divided into three distinct stages: Stage I, tourmaline + quartz + Fe-Cu ore mineralization; Stage II, quartz + sulfides + sulfosalts + carbonates; Stage III, barren calcite. Equilibrium thermodynamic data combined with mineral paragenesis indicate that copper minerals precipitated mainly within a temperature range of $350^{\circ}C$ to $250^{\circ}C$. During early mineralization at $350^{\circ}C$, significant amounts of copper ($10^3$ to $10^2\;ppm$) could be dissolved in weakly acid NaCl solutions. For late mineralization at $250^{\circ}C$, about $10^0$ to $10^{-1}\;ppm$ copper could be dissolved. Equilibrium thermodynamic interpretation indicates that the copper in the Haman-Gunbuk systems could have been transported as a chloride complex and the copper precipitation occurred as a result of cooling accompanied by changes in the geochemical environments ($fs_2$, $fo_2$, pH, etc.) resulting in decrease of solubility of copper chloride complexes.

• Economic and Environmental Geology
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• v.35 no.3
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• pp.257-271
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• 2002

One of the main interests in relation to heavily contaminated gully-pot sediment in urban area is the short term mobility of heavy metals, which depends on the pH of acidic rainwater and on the buffering effects of carbonate minerals. The buffering effects of carbonates are determined by titration (acid addition). Leaching experiments are carried out in solutions with variable initial HN03 contents for 24h. The gully-pot sediment appears to be predominantly buffered by calcite and dolomite. In case of sediment samples, which highly contain carbonates, pH decreases more slowly with increasing acidity. On the other hand, for the sediment samples, which less contain carbonate minerals, pH rapidly drops until it reaches about 2 then it decreases slowly. The leaching reactions are delayed until more acid is added to compensate for the buffering effects of carbonates. The Zn, Cu, Pb and Mn concentrations of leachate rapidly increase with decreased pH, while Cd, Co, Ni, Cr and Fe dissolutions are very slow and limited. The solubility of heavy metals depends not only on thc pH values of leachatc but also on the speciation in which metals are associated with sediment particles. In slightly to moderately acid conditions, Zn, Cd, Co, Ni and Cu dissolutions become increasingly important. As deduced from leaching runs, the relative mobility of heavy metals at pH of 5 is found to be: Zn > Cd > Co > Ni > Cu » Pb > Cr, suggesting that moderately acid rainwater leach Zn, Cd, Co, Ni and Cu from thc contaminated gully-pot sediment, while Pb and Cr would remain fixed. The buffering effects of Ca- and Mg-carbonates play an important role in delaying as well as limiting the leaching reactions of heavy metals from highly contaminated gully-pot sediment. The extent of such a secondary environmental pollution will thus depends on how well the metals in sediment can be leached by somewhat acidic rain water. Changes in the physicochemical environments may result in the severe environmental pollution of heavy metals. These results are to be taken into account in the management of contaminated sediments during rainstorms.

• The Journal of Engineering Geology
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• v.8 no.3
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• pp.247-259
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• 1998

Groundwater quality of the natural mineral water was investigated in hydrochemical aspects in order to ensure that mineral water meets stringent health standards. There exist 20 mineral water plants in the Daebo granite and 4 mineral water plants in the Bulguksa granite, respectively. Both granite areas show some differences in water chemistry. The pH, EC, hardness, total ionic contents in groundwater of the Daebo granite area are higher relative to those of the Bulguksa granite area. The content of major cations is in the order of Ca>Na>Mg>K, while that of major anions shows the order of $HCO_3>SO_4$>Cl>F. The fact that the $Ca-Na-HCO_3$ type is most predominant among water types may reflect that the dissolution of plagioclase that is most abundant in granitic rocks plays a most important role in groundwater chemistry. Representative correlation coefficients between chemical species are variable depending on geology. In the Daebo granite area, $Ca-HCO_3(0.84),{\;}Mg-HCO_3(0.81),{\;}SiO_2-Cl(0.74),{\;}Na-HCO_3(0.70)$ show relatively good correlationships. In the Bulguksa granite area, fairly good correlationships are found among some components such as K-Mg(0.93), $K-HCO_3(0.92)$, Mg-Cl(0.92), $Cl-HCO_3(0.91)$, and K-F(0.90). According to saturation index, most chemical species are undersaturated with respect to major minerals, except for some silica phases. Groundwater is slightly undersaturated with respect to calcite, whereas it is still greatly undersaturated with respect to dolomite, gypsum and fluorite. Based on the phase equilibrium it is clear that groundwater is mostly in equilibrium with kaolinite and becomes undersaturated with respect to feldspars, evolved from the stability area of gibbsite during water-rock interaction. While the activity of silica increases, there is no remarkable increase in the acivities of alkali ions and pH, which indicates that some amounts of silicic acid dissolved from silica phases as well as feldspars were provided to groundwater. It is concluded that chemical evolution of groundwater in granite aquifers may continue to proceed with increasing pH.

• The Journal of the Petrological Society of Korea
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• v.16 no.2 s.48
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• pp.47-58
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• 2007

This study examines the distribution of basement rocks in Gyochon-ri, Muan-eup, Muan-gun, Jeonnam where ground subsidence occurred in June 2005, and traces corrosion of limestone. Mica schist and rhyolite are distributed in the surface of the study area, but thick limestone layer with large and small caverns are distributed underground. A horizon of limestone with maximum width of 300 m and 4 km of length was found along the detour which is in the north of pound subsidence. Such identification of limestone presence would be very useful to predict potential ground subsidence. Limestone in this area was disturbed by fold and fault due to severe shearing deformation. Small caverns were frequently found in anticline part of folds formed in limestone layer. Schists with different thicknesses were intercalated in the limestone with shearing deformation and consist of sheet silicate minerals (chlorite and mica) and quartz. In sections of weathered specimen, it is shown that biotite of schist part was altered into chlorite and corrosion of calcite around the schist followed. This suggest that ground water permeated between intercalated sheet silicate minerals and corrosion of limestone began. And small caverns were generated where active corrosion occurred. This study suggests that because of many reasons (for instance, reclamation of the Bulmu reservior and excess pumping), cavern water level was lowered and cave sediments were removed, and it caused ground subsidence to occur.

• Economic and Environmental Geology
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• v.25 no.4
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• pp.417-433
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• 1992

Lead-zinc-copper deposits of the Jeonheung and the Oksan mines around Euiseong area occur as hydrothermal quartz and calcite veins that crosscut Cretaceous sedimentary rocks of the Gyeongsang Basin. The mineralization occurred in three distinct stages (I, II, and III): (I) quartz-sulfides-sulfosalts-hematite mineralization stage; (II) barren quartz-fluorite stage; and (III) barren calcite stage. Stage I ore minerals comprise pyrite, chalcopyrite, sphalerite, galena and Pb-Ag-Bi-Sb sulfosalts. Mineralogies of the two mines are different, and arsenopyrite, pyrrhotite, tetrahedrite and iron-rich (up to 21 mole % FeS) sphalerite are restricted to the Oksan mine. A K-Ar radiometric dating for sericite indicates that the Pb-Zn-Cu deposits of the Euiseong area were formed during late Cretaceous age ($62.3{\pm}2.8Ma$), likely associated with a subvolcanic activity related to the volcanic complex in the nearby Geumseongsan Caldera and the ubiquitous felsite dykes. Stage I mineralization occurred at temperatures between > $380^{\circ}C$ and $240^{\circ}C$ from fluids with salinities between 6.3 and 0.7 equiv. wt. % NaCl. The chalcopyrite deposition occurred mostly at higher temperatures of > $300^{\circ}C$. Fluid inclusion data indicate that the Pb-Zn-Cu ore mineralization resulted from a complex history of boiling, cooling and dilution of ore fluids. The mineralization at Jeonheung resulted mainly from cooling and dilution by an influx of cooler meteoric waters, whereas the mineralization at Oksan was largely due to fluid boiling. Evidence of fluid boiling suggests that pressures decreased from about 210 bars to 80 bars. This corresponds to a depth of about 900 m in a hydrothermal system that changed from lithostatic (closed) toward hydrostatic (open) conditions. Sulfur isotope compositions of sulfide minerals (${\delta}^{34}S=2.9{\sim}9.6$ per mil) indicate that the ${\delta}^{34}S_{{\Sigma}S}$ value of ore fluids was ${\approx}8.6$ per mil. This ${\delta}^{34}S_{{\Sigma}S}$ value is likely consistent with an igneous sulfur mixed with sulfates (?) in surrounding sedimentary rocks. Measured and calculated hydrogen and oxygen isotope values of ore-forming fluids suggest meteoric water dominance, approaching unexchanged meteoric water values. Equilibrium thermodynamic interpretation indicates that the temperature versus $fs_2$ variation of stage I ore fluids differed between the two mines as follows: the $fs_2$ of ore fluids at Jeonheung changed with decreasing temperature constantly near the pyrite-hematite-magnetite sulfidation curve, whereas those at Oksan changed from the pyrite-pyrrhotite sulfidation state towards the pyrite-hematite-magnetite state. The shift in minerals precipitated during stage I also reflects a concomitant $fo_2$ increase, probably due to mixing of ore fluids with cooler, more oxidizing meteoric waters. Thermodynamic consideration of copper solubility suggests that the ore-forming fluids cooled through boiling at Oksan and mixing with less-evolved meteoric waters at Jeonheung, and that this cooling was the main cause of copper deposition through destabilization of copper chloride complexes.

• Journal of Korea Soil Environment Society
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• v.3 no.3
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• pp.93-107
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• 1998

Because of its stable quantity and quality, groundwater has long been a reliable source of drinking water for domestic users. Rapid economic growth and rising standards of living have in recent years put severe demands on drinking water supplies in Korea. Groundwaters that are currently being used for natural mineral water were hydrochemically evaluated and investigated in order to maintain their quality to satisfy strict health standards. There exist 15 natural mineral water plants in the Okcheon metamorphic belt. Characteristics of groundwaters are different from those of other areas in that electrical conductivity, hardness, contents of Ca, Mg and $HCO_3$are relatively high. The content of major cations is in the order of Ca>Mg, Na>K, whereas that of major anions shows the order of $HCO_3$>$SO_4$>Cl>F. The fact that the Ca-Mg-HCO$_3$type is mostly predominant among water types reflects that dissolution of carbonates that are abundantly present in the metamorphic rocks plays an important part in groundwater chemistry. Representative correlation coefficients between chemical species show Mg-$HCO_3$(0.92), Ca-$HCO_3$(0.88), Ca-Mg(0.80), Ca-Cl(0.78), Mg-$SO_4$(0.78), Ca-$SO_4$(0.71), possibly due to the effect by dissolution of carbonates, gypsum or anhydrite. Determinative coefficients between some chemical species represent a good relationship, especially for EC-(K+Na+Ca), Ca-$HCO_3$, Ca-Mg, indiacting that they are similar in chemical behaviors. According to saturation index, most chemical species are undersaturated with respect to major minerals, except for some silica phases. Groundwater is slightly undersaturated with respect to calcite and dolomite, whereas it is still greatly undersaturated with respect to gypsum, anhydrite and fluorite, Based on the Phase equilibrium in the systems $NA_2$O-$Al_2$$O_3$-$SiO_2$-$H_2$O and $K_2$O-$Al_2$$O_3$-$SiO_2$-$H_2$O, it is clear that groundwater is in equilibrium with kaolinite, evolved from the stability area of gibbsite during water-rock interaction. It is expected that chemical evolution of groundwater continue to proceed with increasing pH by reaction of feldspars, with calcite much less reactive.