• Journal of the Mineralogical Society of Korea
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• v.22 no.3
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• pp.241-248
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• 2009

Kaolinite was synthesized from amorphous $SiO_2$ and $Al(OH)_3{\cdot}xH_{2}O$ as starting materials by hydrothermal reaction conducted at $250^{\circ}C$ and $30\;kg/cm^2$. The acidity of the solution was adjusted at pH 2. The synthesized kaolinite was characterized by XRD, IR, NMR, FE-SEM, TEM and EDS to clarify the formational process according to the reaction time from 2 to 36 hours. X-ray diffraction patterns showed after 2 h of reaction time, the starting material amorphous $Al(OH)_3{\cdot}xH_{2}O$ transformed to boehmite (AlOOH) and after the reaction time 5 h, the peaks of boehmite were observed to be absent thereby indicating the crystal structure is partially destructed. Kaolinite formation was identified in the product obtained after 10 h of reaction and the peak intensity of kaolinite increased further with reaction time. The results of TGA and DTA revealed that the principal feature of kaolinite trace are well resolved. TGA results showed 13 wt% amount of weight loss and DTA analysis showed that exothermic peak of boehmite observed at $258^{\circ}C$ was decreased gradually and after 10 h of reaction time, it was disappeared. After 5 h of the reaction time, the exothermicpeak of transformation to spinel phase was observed and the peak intensiy increased with reaction time. The results of FT-IR suggested a highly ordered kaolinite was obtained after 36 hours of reaction. It was identified by the characteristic hydroxide group bands positioned at 3,696, 3670, 3653 and $3620\;cm^{-1}$. The development of the hydroxyl stretching between 3696 and $3620\;cm^{-1}$, depends on the degree of order and crystalline perfection. TEM results showed that after 15 h reaction time, curved platy kaolinite was observed as growing of (001) plane and after 36 h, the morphology of synthetic kaolinite exhibited platy crystal with partial polygonal outlines.

• Journal of the Mineralogical Society of Korea
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• v.22 no.3
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• pp.207-216
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• 2009

Three distinct types of fluid inclusions in amethyst and quartz crystals are associated with metamorphic events in the Korea Amethyst deposit from Uljin-Gun, Gyeongbuk Province. The amethyst displays bimodal grain size distribution in fine-grained, strain-free equigranular quartz with coarse-grained quartz grains with kink bands and undulose extinction. Type I inclusions are liquid-rich and salinity is 0~7 wt% NaCl and the homogenization temperatures ($T_h$) $91{\sim}231^{\circ}C$ with eutectic temperatures ($T_e$) $-52{\sim}-20^{\circ}C$. Type II inclusions are vapor-rich (80~90 vol%). The salinity and $T_h$ ranges 3~6 wt% NaCl and $230{\sim}278^{\circ}C$, respectively with $T_e$ $-56{\sim}-23^{\circ}C$. Type III inclusions contain a daughter mineral other than NaCl. The salinity ranges 32~36 wt% NaCl and $T_h$ $210{\sim}271^{\circ}C$. The textural and fluid inclusion evidences suggest that the host Buncheon granite gneiss and Amethyst pegmatite experienced dynamic recrystallization and the studied fluid inclusions are metamorphic in origin. The metamorphic event possibly occurred at higher temperature than $271{\sim}278^{\circ}C$. The amethysts from Uljin Korea Amethyst can be distinguished from the synthetic amethyst on basis of the distinctive two and three-phases fluid inclusions. Furthermore, it is noticeable that Korea amethyst do not contain NaCl-bearing and $CO_2$-rich fluid inclusions unlike those compared to those from Eonyang and Samcheonpo deposits related to unmetamorphosed granitic rocks.

• Journal of the Mineralogical Society of Korea
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• v.26 no.4
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• pp.245-262
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• 2013

We analyzed 29 surface sediment samples in five submarine volcanoes (TA12, TA19, TA22, TA25, and TA26) located in the southern part of the Tonga arc for trace elements and rare earth elements to investigate characteristics of the hydrothermal alteration of surface sediments. Based on analytical results of trace element and rare earth element (REE), surface sediments of TA12, TA19, and TA22 submarine volcanoes, which are located in the northern part of the study area, were very little or not influenced by hydrothermal fluids. In contrast, some stations of TA25 and TA26 submarine volcanoes were strongly affected by hydrothermal fluids. However, these two submarine volcanoes showed different features in element concentration in the sediments. Some stations of TA25 submarine volcano showed enrichment of Ni, Cu, Sn, Zn, Pb, Cr, Cd, Sb, W, Ba, Ta, Rb, Sr, and As, however, those of TA26 submarine volcano showed enrichment of Sn, Zn, Pb, Cd, Sb, Ba, Rb, and Sr. Stations which enriched trace elements were observed, enriched REEs were also observed. Average upper continental crust (UCC)-normalized REE patterns of the surface sediments generally showed low light REE (LREE) abundances and increased heavy REE (HREE) abundances. Eu enrichment was identified at several stations of TA25 and TA26 submarine volcanoes. In addition, enrichment of Ce was found at some stations of TA26 submarine volcano and these enrichment patterns were similar with hydrothermal fluid of near stations. Furthermore, TA25 and TA26 submarine volcanoes showed different enrichment characteristics of trace elements and REE. Trace elements were concentrated at TA25 submarine volcano. TA26 submarine volcano, on the other hand, observed highly enrichment of REE especially, Eu and Ce. As a result of the investigation, the characteristics and concentrations of REEs and trace elements in the surface sediments of each submarine volcano can be applied to identify hydrothermal alteration of sediments during exploration for hydrothermal deposits.

• Journal of the Mineralogical Society of Korea
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• v.26 no.3
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• pp.161-174
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• 2013

The geology of the weondong deposit area consists mainly of Cambro-Ordovician and Carboniferous-Triassic formations, and intruded quartz porphyry and dyke. The skarn mineralized zone in the weondong deposit is the most prospective region for the useful W-mineral deposits. To determine the skarn-mineralization age, U-Pb SHRIMP and K-Ar age dating methods were employed. The U-Pb zircon ages of quartz porphyry intrusion (WD-A) and feldspar porphyry dyke (WD-B) are 79.37 Ma and 50.64 Ma. The K-Ar ages of coarse-grained crystalline phlogopite (WD-1), massive phlogopite (WDR-1), phlogopite coexisted with skarn minerals (WD-M), and vein type illite (WD-2) were determined as $49.1{\pm}1.1$ Ma, $49.2{\pm}1.2$ Ma, $49.9{\pm}3.6$ Ma, and $48.3{\pm}1.1$ Ma, respectively. And the ages of the high uranium zircon of hydrothermally altered quartz porphyry (WD-C) range from 59.7 to 38.7 Ma, which dependson zircon's textures affected by hydrothermal fluids. It is regarded as the effect of some hydrothermal events, which may precipitate and overgrow the high-U zircons, and happen the zircon's metamictization and dissolution-reprecipitation reactions. Based on the K-Ar age datings for the skarn minerals and field evidences, we suggest that the timing of W-skarn mineralization in weondong deposit may be about 50 Ma. However, for the accurate timing of skarn mineralization in this area, the additional researches about the sequence of superposition at the skarn minerals and geological relationship between skarn deposits and dyke should be needed in the future.

• Journal of the Mineralogical Society of Korea
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• v.26 no.4
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• pp.229-244
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• 2013

Arsenic contamination may be brought about by a variety of natural and anthropogenic causes. Among diverse naturally-occurring chemical speciations of arsenic, trivalent (As(III), arsenite) and pentavalent (As(V), arsenate) forms have been reported to be the most predominant ones. It has been well known that the behavior of arsenic is chiefly affected by aluminum, iron, and manganese oxides. For this reason, this study was initiated to evaluate the applicability of manganese slag (Mn-slag) containing high level of Mn, Si, and Ca as an efficient sorbent of arsenic. The main properties of Mn-slag as a sorbent were investigated and the sorption of each arsenic species onto Mn-slag was characterized from the aspects of equilibrium as well as kinetics. The specific surface area and point of zero salt effect (PZSE) of Mn-slag were measured to be $4.04m^2/g$ and 7.73, respectively. The results of equilibrium experiments conducted at pH 4, 7 and 10 suggest that the sorbed amount of As(V) was relatively higher than that of As(III), indicating the higher affinity of As(V) onto Mn-slag. As a result of combined effect of pH-dependent chemical speciations of arsenic as well as charge characteristics of Mn-slag surface, the sorption maxima were observed at pH 4 for As(V) and pH 7 for As(III). The sorption of both arsenic species reached equilibrium within 3 h and fitting of the experimental results to various kinetic models shows that the pseudo-second-order and parabolic models are most appropriate to simulate the system of this study.

• Economic and Environmental Geology
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• v.50 no.4
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• pp.303-311
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• 2017

The laboratory scale experiment was performed to evaluate the sealing capacity of the capping rock such as tuff and mudstone, measuring the intial supercritical $CO_2$ ($scCO_2$) injection pressure and the $scCO_2$-water-rock reaction for 90 days. The drilling cores sampled from 800 m in depth around the Janggi basin, Korea were used for the experiment. The mineralogical changes of mudstone and tuff were measured to evaluate the geochemical stability during the $scCO_2$-water-rock reaction at $CO_2$ storage condition (100 bar and $50^{\circ}C$). The rock core was fixed in the high pressurized stainless steel cell and was saturated with distilled water at 100 bar of pore water pressure. The effluent of the cell was connected to the large tank filled with 3 L of water and 2 L of $scCO_2$ at 100 bar, simulating the subsurface injection condition. The $scCO_2$ injection pressure, which was higher than 100 bar, was controlled at the influent port of the cell until the $scCO_2$ begin to penetrate into the rock and the initial injection pressure (> 100 bar) of $scCO_2$ into the rock was measured for each rock. The mineralogical compositions of mudstones after 90 days reaction were similar to those before the reaction, suggesting that the mudstone in the Janggi basin has remained relatively stable for the $scCO_2$ involved geochemical reaction. The initial $scCO_2$ injection pressure (${\Delta}P$) of a tuff in the Janggi basin was 15 bar and the continuous $scCO_2$ injection into the tuff core occurred at higher than 20 bar of injection pressure. For the mudstone in the Janggi basin, the initial $scCO_2$ injection pressure was higher than 150 bar (10 times higher than that of the tuff). From the results, the mudstone in Janggi basin was more suitable than the tuff to shield the $scCO_2$ leakage from the reservoir rock at subsurface.

• Economic and Environmental Geology
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• v.36 no.4
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• pp.285-293
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• 2003

Tailings of Dukum mine in the vadose and saturated zone were investigated to reveal the mobility of metal elements and the condition of mineralogical solubility according to redox environments throughout the geochemical analysis, thermodynamic modelling, and mineralogical study for solid-samples and water samples(vadose zone; distilled water: tailings=5 : 1 reacted, saturated zone; pore-water extracted). In the vadose zone, sulfide oxidation has generated low-pH(2.72∼6.91) condition and high concentration levels of S $O_4$$^{2-}$(561∼1430mg/L) and other metals(Zn : 0.12∼l57 mg/L, Pb : 0.06∼0.83 mg/L, Cd : 0.06∼l.35 mg/L). Jarosite$(KFe_3(SO_4)_2(OH)_6)$ and gypsum$(CaSO_4{\cdot}2H_2O$) were identified on XRD patterns and thermodynamics modelling. In the saturated zone, concentration of metal ions decreased because pH values were neutral(7.25∼8.10). But Fe and Mn susceptible to redox potential increased by low-pe values(7.40∼3.40) as the depth increased. Rhodochrosite$(MnCO_3)$ identified by XRD and thermodynamics modelling suggested that $Mn^{4+}$ or $Mn^{3+}$ was reduced to $Mn^{2+}$. Along pH conditions, concentrations of dissolved metal ions has been most abundant in vadose zone throughout borehole samples. It was observed that pH had more effect on metal solubilities than redox potential. How-ever, the release of co-precipitated heavy metals following the dissolution of Fe-Mn oxyhydroxides could be the mechanism by which reduced condition affected heavy metal solubility considering the decrease of pe as depth increased in tile saturated zone.

• Journal of the Mineralogical Society of Korea
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• v.21 no.4
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• pp.341-347
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• 2008

The feasibility of commercializing the hydrothermal synthesis of Na-A type zeolite from siliceous mudstone has been conducted using a 50-liter bench-scale autoclave and the application of the zeolite as an environmental remediation agent. Siliceous mudstone, which is widely distributed around the Pohang area, was adopted as a precursor. The siliceous mudstone is favorable for the synthesis of zeolite because it contains 70.7% $SiO_2$ and 10.0% $Al_2O_3$, which are major ingredient of zeolite formation. The synthesis of zeolite was carried out under the following conditions that had been obtained from the previous laboratory-scale tests: 10hr reaction time, $80^{\circ}C$ reaction temperature, $Na_2O/SiO_2$ ratio = 0.6, $SiO_2/Al_2O_3$ ratio = 2.0 and $H_2O/Na_2O$ ratio= 98.6. The crystallinity and morphology of the zeolite formed were similar to those obtained from the laboratory-scale tests. The recovery and cation exchange ion capacity were 95% and 215 cmol/kg, respectively, which are slightly higher than those obtained in laboratory scale tests. To examine the feasibility of the zeolite as an environmental remediation agent, experiments for heavy metal adsorption to zeolite were conducted. Its removal efficiencies of heavy metals in simulated waste solutions decreased in the following sequences: Pb > Cd > Cu = Zn > Mn. In a solution of 1500 mg/L total impurity metals, the removal efficiencies for these impurity metals were near completion (> 99%) except for Mn whose efficiency was 98%. Therefore, the synthetic Na-A type zeolite was proven to be a strong absorbent effective for removing heavy metals.

• Journal of the Mineralogical Society of Korea
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• v.21 no.4
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• pp.425-434
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• 2008

Arsenic contamination in soil and groundwater has recently been one of the most serious environmental concerns. This arsenic contamination can be originated from natural or anthropogenic sources. It has been well known that arsenic behavior in geo-environmental is controlled by various oxides or hydroxides, such as those of iron, manganese, and aluminum, and clay minerals. Among those, particularly, iron (oxy)hydroxides are the most effective scavengers for arsenic. For this reason, this study characterized arsenic adsorption of magnetite which is a kind of iron oxide in nature. The physicochemcial features of the magnetite were investigated to evaluate adsorption of arsenite [As(III)] and arsenate [As(V)] onto magnetite. In addition to experiments on adsorption equilibria, kinetic experiments were also conducted. The point of zero charge (PZC) and specific surface area of the laboratory-synthesized magnetite used as an arsenic adsorbent were measured 6.56 and $16.6\;g/m^2$, which values seem to be relatively smaller than those of the other iron (oxy)hydroxides. From the results of equilibria experiments, arsenite was much more adsorbed onto magnetite than arsenate, indicating the affinity of arsenite on magnetite is larger than arsenate. Arsenite and arsenate showed adsorption maxima at pHs 7 and 2, respectively. In particular, adsorption of arsenate decreased with increase in pH as a result of electrical repulsion caused by anionic arsenate and negatively-charged surface of magnetite. These results indicate that the surface charge of magnetite and the chemical speciation of arsenic should be considered as the most crucial factors in controlling arsenic. The results of kinetic experiments show that arsenate was adsorbed more quickly than arsenite and adsorption of arsenic was investigated to be mostly completed within the duration of 4 hours, regardless of chemical speciation of arsenic. When the results of kinetic experiments were fitted to a variety of kinetic models proposed so far, power function and elovich model were evaluated to be the most suitable ones which can simulate adsorption kinetics of two kinds of arsenic species onto magnetite.

• Journal of the Mineralogical Society of Korea
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• v.26 no.2
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• pp.101-110
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• 2013

Due to the large specific surface area and great reactivity toward environmental contaminants, nanocrystalline mackinawite (FeS) has been widely applied for the remediation of contaminated groundwater and soil. Furthermore, nanocrystalline FeS is rather thermodynamically stable against anoxic corrosion, and its reactivity can be regenerated continuously by the activity of sulfate-reducing bacteria. However, nanocrystalline mackinawite is prone to either spread out along the groundwater flow or cause pore clogging in aquifers by particle aggregation. Accordingly, this mineral should be modified for the application of permeable reactive barriers (PRBs). In this study, coating methods were investigated by which mackinawite nanoparticles were deposited on the surface of alumina or activated alumina. The amount of FeS coating was found to significantly vary with pH, with the highest amount occurring at pH ~6.9 for both minerals. At this pH, the surfaces of mackinawite and alumina (or activated alumina) were oppositely charged, with the resultant electrostatic attraction making the coating highly effective. At this pH, the coating amounts by alumina and activated alumina were 0.038 and 0.114 $mmol{\cdot}FeS/g$, respectively. Under anoxic conditions, arsenite sorption experiments were conducted with uncoated alumina, uncoated activated alumina, and both minerals coated with FeS at the optimal pH for comparison of their reactivity. Uncoated activated alumina showed the higher arsenite removal compared to uncoated alumina. Notably, the arsenite sorption capacity of activated alumina was little changed by the coating with FeS. This might be attributed to the abundance of highly reactive hydroxyl functional groups (${\equiv}$AlOH) on the surface of activated alumina, making the arsenite sorption by the coated FeS unnoticeable. In contrast, the arsenite sorption capacity of alumina was found to increase substantially by the FeS coating. This was due to the consumption of the surface hydroxyl functional groups on the alumina surface and the subsequent occurrence of As(III) sorption by the coated FeS. Alumina, on the surface area basis, has about 8 times higher FeS coating amount and higher As(III) sorption capacity than silica. This study indicates that alumina is a better candidate than silica for the coating of nanocrystalline mackinawite.