• Korean Journal of Mineralogy and Petrology
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• v.34 no.2
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• pp.121-131
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• 2021

Magnesium (Mg) present in carbonate minerals as impurities has been used as a geochemical proxy to infer the environmental conditions where the minerals precipitated. The reliability of Mg geochemical proxies requires fundamental understanding of Mg incorporation into minerals based on accurate speciation of Mg ²⁺ in the crystal structure, which is determined mainly by application of X-ray absorption spectroscopy (XAS). However, high uncertainties are involved in interpreting the XAS spectra of minerals containing trace amount of Mg ²⁺. Because density function theory (DFT) can predict an XAS spectrum for a crystal structure, DFT calculations can reduce the uncertainties in the interpretation of the XAS spectrum. In this study, we calculated ab initio Mg K-edge absorption spectra of Mg silicates and (hydr)oxides based on DFT and analyzed the correlation between the calculated spectra and Mg structural parameters. Our ab initio Mg K-edge absorption spectra well reproduced the key features of the experimental spectra. The absorption-edge positions of the calculated spectra showed the weak positive correlation with the average Mg-O bond distance or Mg effective coordination number. The current study shows that DFT-based core-level spectroscopy method is a powerful tool in providing standard Mg K-edge spectra of diverse Mg minerals and determining the Mg chemical species within carbonate minerals.

• Economic and Environmental Geology
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• v.43 no.1
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• pp.21-31
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• 2010

Mine and leachate waters were collected from the Okdong mine for study on reaction with oxidizing agents such as NaOCl and $H_2O_2$. The pH and EC of the mine and leachate waters are 5.77, 831 uS/cm, and 6.38, 1920 uS/cm, respectively. The concentrations of Mg, Mn, and Zn are 23.25 mg/l, 14.90 mg/l, and 22.99 mg/l for the mine water and 98.75 mg/l, 3.38 mg/l, and 6.16 mg/l for the leachate water. The concentrations of Mg, Mn and Zn decreased after the reaction with the oxidizing agents and mine water. The concentrations of Mg, Mn and Zn rapidly decreased when oxidizing agents increased. The saturation indices that were computed by visual MINTEQ for initial mine and leachate water were undersaturated with Mg, Zn and Mn compounds. The precipitates after the reaction with the oxidizing agents are composed mainly of mangano-calcite[(Mn, Ca)$CO_3$] with small amount of calcite-magnesian and calcite.

• Journal of Soil and Groundwater Environment
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• v.7 no.2
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• pp.45-52
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• 2002

Water chemistry in the Munkyeong hot-spring expresses high values of EC(1,857 $mutextrm{s}$/cm), $HCO_3$(1,250 mg/l), $SO_4$(147.60 mg/l), Mg(43.05 mg/l), and Ca(279.43 mg/l). The precipitates of small quantity is formed in lower temperature, but much of in case apply heat by boiler. Although mineral that is settled from original ground water is most calcite, aragonite and calcite at the same time crystallized in boiler. The $CO_3$ is present predominantly as $HCO_3^{-}$ and $H_2$$CO_3$, $SO_4$, Mg and Ca are present as free ion. Ca is saturated with respect to carbonate such as aragonite and calcite but slightly undersaturated with respect to anhydrite and gypsum Al is saturated with diaspore and gibbsite. The precitptates are composed of carbonate such as calcite and aragonite and amorphous Fe-hydroxide.

• Journal of the Mineralogical Society of Korea
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• v.32 no.3
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• pp.151-162
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• 2019

Todorokite, a tunnel-structured manganese oxide, can contain cations within the relatively large nanopores created by the $3{\times}3$ Mn octahedra. Because todorokite is poorly crystalline and found as aggregates mixed with other phases of Mn oxides in nature, the coordination structure of cations in the nanopores is challenging to fully characterize in experiment. In the current article, we report the atomistic coordination structures of $Mg^{2+}$ ions in todorokite tunnel nanopores using the classical molecular dynamics (MD) simulations. In experiment, $Mg^{2+}$ is known to occupy the center of the nanopores. In our MD simulations, 60 % of $Mg^{2+}$ ions were located at the center of the nanopores; 40 % of the ions were found at the corners. All $Mg^{2+}$ located at the center formed the six-fold coordination with water molecules, just as the ion in bulk aqueous solution. $Mg^{2+}$ ions at the corners also formed the six-fold coordination with not only water molecules but also Mn octahedral surface oxygens. The mean squared displacements were calculated to examine the dynamic features of $Mg^{2+}$ ions in the one-dimensional (1D) nanopores. Our MD simulations indicate that the dynamic features of water molecules and the cations observed in bulk aqueous solution are lost in the 1D nanopores of todorokite.

• Economic and Environmental Geology
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• v.40 no.1 s.182
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• pp.29-45
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• 2007

Biogeochemical characteristics involving redox processes in groundwater from a riverine alluvial aquifer was investigated using multi-level monitoring wells (up to 30m in depth). Anaerobic conditions were predominant and high Fe ($14{\sim}37mg/L$) and Mn ($1{\sim}4mg/L$) concentrations were observed at 10 to 20 m in depth. Below 20 m depth, dissolved sulfide was detected. Presumably, these high Fe and Mn concentrations were derived from the reduction of Fe- and Mn-oxides because dissolved oxygen and nitrate were nearly absent and Fe and Mn contents were considerable in the sediments. The depth range of high Mn concentration is wider than that of high Fe concentration. Dissolved organics may be derived from the upper layers. Sulfate reduction is more active than Fe and Mn reduction below 20 m in depth. Disparity of calculated redox potential from the various redox couples indicates that redox states are in disequilibrium condition in groundwater. Carbonate minerals such as siderite and rhodochrosite may control the dissolved concentrations of Fe(II) and Mn(II), and iron sulfide minerals control for Fe(II) where sulfide is detected because these minerals are near saturation from the calculation of solubility equilibria.

• Journal of the Mineralogical Society of Korea
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• v.22 no.4
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• pp.331-342
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• 2009

Groundwater samples were collected from the bedrock aquifers related with Okcheon metasedimentary rocks. Arsenic (As) concentrations in the samples varied between 0.0051 and 0.887 mg/L, with an average of 0.0248. Cations and anions of groundwaters had no relationship with As contents as well as with spatial distribution of geology in the area. Pyrite, chalcopyrite and arsenopyrite in the core samples of the monitoring wells were identified in thin section, X-ray diffraction (XRD) and electron probe microscope analysis (EPMA). It was suggested that these minerals are responsible for the As in groundwater. The groundwater showed saturations with respect to calcite $(CaCO_3)$, dolomite (CaMg$(CO_3)_2$) and Magnesite $(MgCO_3)$. $HAsO_4{^{2-}}$ activities in the groundwater samples were close to $Ca_3(AsO_4)_2(c)$ and $Mn_3(AsO_4)_2(c)$ solubility isotherms, indicating that the maximum As contents in groundwater are secondly controlled by the precipitation and dissolution of carbonate minerals due to alkaline and oxic nature of the groundwater (pe+pH>10).

• Journal of the Mineralogical Society of Korea
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• v.30 no.1
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• pp.21-29
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• 2017

Surface soils on Barton Peninsula, King George Island, West Antarctica were investigated to acquire the mineralogical and geochemical data of soil in Antarctica. Multiline of techniques for example, X-ray diffraction (XRD), transmission electron microscopy (TEM)-electron energy loss spectroscopy (EELS), and wet chemistry analysis were performed to measure the composition of clay minerals, Fe-oxidation states, cation exchange capacity, and total cation concentration. Various minerals in sediments such as smectite, illite, chlorite, kaolinite, quartz and plagioclase were identified by XRD. Fe-oxidation states of bulk soils showed 20-40% of Fe(II) which would be ascribed to the reduction of Fe in clays as well as Fe-bearing minerals. Moreover, redox states of Fe in smectite structure was a ~57% of Fe(III) consistent to the values for the bulk soils. The cation exchange capacity of bulk soils ranged from 100 to 300 meq/kg and differences were not significantly measured for the sampling locations. Total cations (Mg, K, Na, Al, Fe) of bulk soils varies, contrast to the heavy metals (Co, Ni, Cu, Zn, Mn). These results suggested that composition of bed rocks influenced the distribution of elements in soil environments and soils containing clay compositions may went through the bio/geochemical alteration.

• Journal of the Mineralogical Society of Korea
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• v.27 no.1
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• pp.17-30
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• 2014

Waste cement generated from recycling processes of waste concrete is a potential raw material for mineral carbonation. For the $CO_2$ sequestration utilizing waste cement, this study was conducted to obtain basic information on the aqueous carbonation methods and the characteristics of carbonate mineral formation. Cement paste was made with W:C= 6:4 and stored for 28 days in water bath. Leaching tests using two additives (NaCl and $MgCl_2$) and two aqueous carbonation experiments (direct and indirect aqueous carbonation) were conducted. The maximum leaching of $Ca^{2+}$ ion was occurred at 1.0 M NaCl and 0.5 M $MgCl_2$ solution rather than higher tested concentration. The concentration of extracted $Ca^{2+}$ ion in $MgCl_2$ solution was more than 10 times greater than in NaCl solution. Portlandite ($Ca(OH)_2$) was completely changed to carbonate minerals in the fine cement paste (< 0.15 mm) within one hour and the carbonation of CSH (calcium silicate hydrate) was also progressed by direct aqueous carbonation method. The both additives, however, were not highly effective in direct aqueous carbonation method. 100% pure calcite minerals were formed by indirect carbonation method with NaCl and $MgCl_2$ additives. pH control using alkaline solution was important for the carbonation in the leaching solution produced from $MgCl_2$ additive and carbonation rate was slow due to the effect of $Mg^{2+}$ ions in solution. The type and crystallinity of calcium carbonate mineral were affected by aqueous carbonation method and additive type.

• Journal of the Mineralogical Society of Korea
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• v.28 no.1
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• pp.39-49
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• 2015

Recently, carbon capture and storage (CCS) techniques have been globally studied. This study was conducted to use waste cement powder as an efficient raw material of mineral carbonation for $CO_2$ sequestration. Direct aqueous carbonation experiment was conducted with injecting pure $CO_2$ gas (99.9%) to a reactor containing $200m{\ell}$ reacting solution and the pulverized cement paste (W:C = 6:4) having particle size less than 0.15 mm. The effects of two additives (NaCl, $MgCl_2$) in carbonation were analyzed. The characteristics of carbonate minerals and carbonation process according to the type of additives and pH change were carefully evaluated. pH of reacting solution was gradually decreased with injecting $CO_2$ gas. $Ca^{2+}$ ion concentration in $MgCl_2$ containing solution was continuously decreased. In none $MgCl_2$ solution, however, $Ca^{2+}$ ion concentration was increased again as pH decreased. This is probably due to the dissolution of newly formed carbonate mineral in low pH solution. XRD analysis indicates that calcite is dominant carbonate mineral in none $MgCl_2$ solution whereas aragonite is dominant in $MgCl_2$ containing solution. Unstable vaterite formed in early stage of experiment was transformed to well crystallized calcite with decreasing pH in the absence of $MgCl_2$ additives. In the presence of $MgCl_2$ additives, the content of aragonite was increased with decreasing pH whereas the content of calite was decreased.

• Economic and Environmental Geology
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• v.40 no.3 s.184
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• pp.277-293
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• 2007

Seasonal and spatial variations in the concentrations of trace elements, pH and Eh were found in a creek watershed affected by mine drainage and leachate from several waste rock dumps within the As-Pb-rich Indae mine site. Because of mining activity dating back to about 40 years ago and rupture of the waste rock dumps, this creek was heavily contaminated. Due to the influx of leachate and mine drainage, the water quality of upstream reach in this creek was characterized by largest seasonal and spatial variations in concentrations of Zn(up to $5.830 mg/{\ell}$), Cu(up to $1.333 mg/{\ell}$), Cd(up to $0.031 mg/{\ell}$) and $SO_4^{2-}$(up to $173 mg/{\ell}$), relatively acidic pH values (3.8-5.1) and highly oxidized condition. The most abundant metals in the leachate samples were in order of Zn($0.045-13.909 mg/{\ell}$), Fe($0.017-8.730mg/{\ell}$), Cu($0.010-4.154mg/{\ell}$) and Cd($n.d.-0.077mg/{\ell}$), with low pH(3.1-6.1), and high $SO_4^{2-}$(up to $310 mg/{\ell}$). The mine drainage also contained high concentrations of Zn, Cu, Cd and $SO_4^{2-}$ and remained constantly near-neutral pH values(6.5-7.0) in all the year. While the leachate and mine drainage might not affect short-term fluctuations in flow, it may significantly influence the concentrations of chemicals in the stream. The abundance and chemistry of Fe-(oxy)hydroxide within this creek indicated that the Fe-(oxy)hydroxide formation could be responsible for some removal of trace elements from the creek waters. Spatial and seasonal variations along down-stream reach of this creek were caused largely by the influx of water from uncontaminated tributaries. In addition, the trace metal concentrations in this creek have been decreased nearly down to the background level at a short distance from the discharge points without any artificial treatments after hydrologic mixing in a tributary. The nonconservative(i.e. precipitation, adsorption, oxidation, dissolution etc.) and conservative(hydrologic mixing) reactions constituted an efficient mechanism of natural attenuation which reduces considerably the transference of trace elements to rivers.