• Economic and Environmental Geology
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• v.28 no.4
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• pp.351-367
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• 1995

The elemental geochemistry and oxygen isotopes of illite/smectite (I/S) have been studied in relationship to the mineralogical trend in the Reindeer D-27 well, Beaufort-Mackenzie Basin. The increase in concentrations of $K_2O$, Rb and rare earth elements (REE), the decrease in concentrations of tetrahedral elements such as Mg, Ti, Sc, Zn and Zr, and the increase in concentrations of tetrahedral elements such as Be and V can be related to I/S compositions that vary systematically with depth. Layer formulae of S- and I-layers are estimated as $[Al_{1.57}Fe_{.19}Mg_{.31}Ti_{.07}][Si_{3.84}Al_{.16}]O_{10}(OH)_2$ and $[Al_{1.84}Mg_{.16}][Si_{3.33}Al_{.67}]O_{10}(OH)_2$, respectively. The mobilization of REE appears to occur during illitization. The increase in concentrations of REE, especially La and Ce, with depth is probably linked to incorporation of ions with high valency (e.g. $V^{5+}$) in tetrahedral sites. The excess valency due to V is partly counter-balanced by ions with low valency (e.g. $Be^{2+}$) and, in turn, the local valency deficiency caused by $Be^{2+}$ could be compensated by high-charge interlayer cations such as REE (＋3). ${\delta}^{18}O$ values of I/S range from 2.91 to 15.72‰ (SMOW), and increase with depth, contrasting to trends observed in the Gulf Coast and elsewhere. The increase in ${\delta}^{18}O$ of I/S results from the rapid increase in ${\delta}^{18}O$ of pore water that overcomes the decrease in temperature-dependent fractionation values with increasing burial depth (${\delta}^{18}O_{pore\;water}>-d{\Delta}/_{I/S-water};\;d{\delta}^{18}O_{I/S}>0$). Calculated ${\delta}^{18}O$ values of pore water in equilibrium with I/S suggest that the original water was probably meteoric water. The stratification of pore water is postulated from the presence of an isotopically light interval, about 450m thick. The depth range of the isotopically light zone overlaps, but does not coincide with the interval of lowered I-content and $K_2O$ concentrations, suggesting that oxygens may have been exchanged independently of mineralogical and geochemical reactions.

• Economic and Environmental Geology
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• v.53 no.1
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• pp.23-32
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• 2020

Geological CO₂ sequestration is a global warming response technology to limit atmospheric emissions by injecting CO₂ captured on a large scale into deep geological formations. The presented results concern mineralogical and hydrogeological investigations (FE-SEM, XRD, XRF, and MICP) of mudstone samples from drilling cores of the Pohang basin, which is the research area for the first demonstration-scale CO₂ storage project in Korea. They aim to identify the mineral properties of the mudstone constituting the caprock and to quantitatively evaluate the hydrogeologic sealing capacity that directly affects the stability and reliability of geological CO₂ storage. Mineralogical analysis showed that the mudstone samples are mainly composed of quartz, K-feldspar, plagioclase and a small amount of pyrite, calcite, clay minerals, etc. Mercury intrusion capillary pressure analysis also showed that the samples generally had uniform particle configurations and pore distribution and there was no distinct correlation between the estimated porosity and air permeability. The allowable CO₂ column heights based on the estimated pore-entry pressures and breakthrough pressures were found to be significantly higher than the thickness of the targeting CO₂ injection layer. These results showed that the mudstone layers in the Yeongil group, Pohang basin, Korea have sufficient sealing capacity to suppress the leakage of CO₂ injected during the demonstration-scale CO₂ storage project. It should be noticed, however, that the applicability of results and analyses in this study is limited by the lack of available samples. For rigorous assessment of the sealing efficiency for geological CO₂ storage operations, significant efforts on collection and multi-aspect evaluation for core samples over entire caprock formations should be accompanied.

• Journal of the Mineralogical Society of Korea
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• v.15 no.2
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• pp.95-103
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• 2002

The object of this study was to interpret the ralationship between expandability (% $S_{XRD}$), MacEwan crystallite thickness ( $N_{CSD}$), and mean fundamental particle thickness ( $N_{F}$ ) in illite-semctite mixed layer (I-S), quantitatively. This interpretation was extracted from comparison of two structural models (MacEwan crystallite model and fundamental particle model) of I-S mixed layers. In I-S structure, % $S_{XRD}$, $N_{CSD}$, and $N_{F}$ are not independent parameters but are related to each others by particular geometric relations. % $S_{XRD}$ is dependent on $N_{CSD}$ by short-stack effect, whereas, % $S_{XRD}$ and $N_{F}$ have relation to smectite interlayer number (Ns)=( $N_{F-}$1)/(100%/% $S_{XRD-}$ $N_{F}$ . Therefore, % $S_{XRD}$ and $N_{F}$ should satisfy a specific physical condition, 1< $N_{F}$ <100%/% $S_{XRD}$, because $N_{s}$ is positive. Based on this condition, this study suggested % $S_{XRD}$ vs $N_{F}$ diagram which can be used to interpret % $S_{XRD}$, $N_{F}$ , $N_{S}$ , and ordering, quantitatively. The diagram was examined by XRD data for I-S samples from Ceumseongsan volcanic complex, Korea. I-S samples showed that $N_{F}$ departs from the physical upper-limit ( $N_{F}$ =100%/% $S_{XRD}$) with decrease in % $S_{XRD}$. This phenomenon may happen due to decrease of stacking-capability of fundamental particles with their thickening.g.s with their thickening.g.

• Journal of the Mineralogical Society of Korea
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• v.15 no.2
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• pp.104-113
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• 2002

The sorption of Cd$^{2+}$ on calcite was studied in aqueous solutions of several electrolytes. The Cd$^{2+}$ concentration, 10$^{-8}$ M, was kept well below saturation with respect to CdCO$_3$(s). Sorption behavior of Cd$^{2+}$ in different ionic strengths of NaClO$_4$solutions shows that sorption is independent of ionic strength. This result suggests that Cd$^{2+}$ sorption on calcite surface is of a specific nature, and adsorption is controlled by an inner-sphere type of surface complex. Two stages in the sorption behavior could be identified: an initial rapid uptake, followed by slower uptake reaching a maximum steady state by 145 hrs. No evidence was observed for surface precipitation, although it can not be entirely ruled out. Desorption of Cd$^{2+}$ from the calcite surface after resuspension into Cd-free solution is initially very rapid, but depends partly on the previous sorption history. Desorption behavior of Cd$^{2+}$ show that an initial rapid desorption followed either by slow uptake reaching a maximum, as in the adsorption experiments, or slowing desorption to reach a steady state minimum. This irreversible behavior of Cd$^{2+}$ sorption and desorption may act as one of the controls for regulating the mobility of dissolved Cd$^{2+}$ natural aqueous systems. Calculated adsorption partition coefficients suggest that overall sorption and desorption process in the concentration range are controlled by d single mechanism.ingle mechanism.

• Journal of the Mineralogical Society of Korea
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• v.15 no.2
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• pp.122-131
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• 2002

Muscovite, chlorite and biotite in metapelites of the Ogcheon Hetamorphic Belt are studied using electron probe microanalysis (EPMA), backscattered electron images (BEI) of scanning electron microscopy (SEM) and lattice fringe images of transmission electron microscopy (TEM). These minerals are observed to be intergrown under a polarized light microscope and are apparently interlayered below EPMA resolution; EPMA data often indicate mixtures of phyllosilicates such as muscovite/chlorite (M/C), biotite/chlorite (B/C), muscovite/pyrophyllite/chlorite (M/P/C). biotite/pyrophyllite/chlorite (B/P/C) or biotite/muscovite/chlorite (B/M/C). BEI observations show that the three minerals (muscovite, chlorite and biotite) are mixed at various scales in a grain through the garnet zone, and the interlayering of the three minerals are observed from TEM lattice fringe images and selected area electron diffraction patterns. The result of TEM observations reveals that 7-$\AA$ layers (serpentine, precursor of chlorite) are interlayered within 10-$\AA$ layers (muscovite) at 100~200 $\AA$ scale as well as M/C in the chlorite zone. The 7-$\AA$ layers become smaller in size and less frequent in the biotite tone, and 10-$\AA$ layers are interlayered with chlorite (14 $\AA$) at an individual layer scale. The 7-$\AA$ layers are no longer observed in the garnet zone, and 10-$\AA$ layers (biotite) are interlayered with chlorite (B/C) at 50~100 $\AA$ scale. Relatively large scale (1000~2000 $\AA$) of intergrowth is also frequently observed from the garnet zone samples. However, rocks from all three metamorphic zones show interlayering of a few units of 7-, 10- and 14-$\AA$ layers with each other at TEM observations. The result of this study implies that metamorphic minerals such as muscovite, chlorite and biotite form through disequilibrum mineral reactions resulting in inhomogenious phases.

• Journal of the Mineralogical Society of Korea
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• v.19 no.4 s.50
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• pp.265-275
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• 2006

It is in its infancy to use bacteria as a novel biotechnology for leaching precious and heavy metals from raw materials. The objective of this study was to investigate biogeochemical processes of iron leaching from magnetite reduction by iron-reducing bacteria isolated from intertidal flat sediments, southwestern part of Korea. Microbial leaching experiments were performed using commercial magnetite, Aldrich magnetite, in well-defined mediums with and without bacteria. Water soluble Fe production was determined by ICP analysis of bioleached samples in comparison to uninoculated controls, and the resulting precipitated solids were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The extent of iron leaching from magnetite in the aerobic conditions (Fe = 107 ppm) was higher than that in the anaerobic environments (Fe = 94 ppm). In the anaerobic conditions, Fe(III) in commercial magnetite was also reduced to Fe(II), but no secondary mineral phases were observed. Amorphous iron oxides formed in the medium under aerobic conditions where there was sufficient supply of oxygen from the atmosphere. SEM observation suggests that the reduction process involves dissolution-precipitation mechanisms as opposed to solid state conversion of magnetite to amorphous iron oxides. The ability of bacteria to leach soluble iron and precipitate amorphous iron oxides from crystalline magnetite could have significant implications for biogeochemical processes in sediments where Fe(III) in magnetite plays an important role in the largest pool of electron acceptor as well as the tool as a novel biotechnology for leaching precious and heavy metals from raw materials.

• Journal of the Mineralogical Society of Korea
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• v.19 no.4 s.50
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• pp.277-289
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• 2006

This study was carried out to find a new material having high removal efficiency for the harmful red tide. C. polykrikoides grow very fast and accumulate into dense and visible patches near the surface of the seawater ('Water bloom'). Some mineral medicines and Hwangto (reddish soil consist of clay minerals and Fe-oxides) were used in this study to remove C. polykrikoides. The pre-determined sprinkling ratio of mineral vs. seawater which contains approximately 5,000 cells/mL of C. polykrikoides was 10 g/L. In order to quantify the removal efficiency, the density of living cells was measured by counting with the Intervals of 0, 10, 30, and 60 minutes after sprinkling. Five Hwangtos feom different localities were examined in this study. It is found that a material with a high concentration of Fe and Al was the most effective to remove C. polykrikoides. After the sprinkling of the Hwangto showing the best removal efficiency in the test, 99% of total algaes were found to be eliminated within 60 minutes. Jeokeokji showed the highest removal efficiency among clay mineral medicines(92% removal efficiency after 60 minutes), and the rests in decreasing order are as follows: Gamto (91%) > Baekseokji (89%) > Hydromica (81%). In addition, Fe-oxide mineral medicine similarly looking as fine-grained earthy Daejaseok showed 100% removal efficiencyafter 30 minutes, and Wooyoeryang, 95% after 60 minutes. It is noted that even little addition (1 g/L) of Daejaseok, 10% of Hwangto concentration into seawater showed the removal efficiency of 100% after 60 minutes. From the results, it could be concluded that the fine-grained earthy Daejaseok was the most effective natural mineral medicine to remove the C. polykrikoides from seawater. Under the microscope the removal mechanism was found to be activated in the following order: adsorption, swelling of chain colony, chain colony crisis and algaecide.

• Journal of the Mineralogical Society of Korea
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• v.28 no.3
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• pp.245-253
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• 2015

The performance of $TiO_2$ photo-catalytic oxidation process is significantly dependent on the amount of hydroxyl radicals produced during the process, and it is an essential prerequisite to quantify its production. However, precise and accurate methods for quantification of hydroxyl radicals have not been developed so far. For this reason, this study was initiated to compare existing methods for analysis of hydroxyl radicals produced by $TiO_2$ photo-catalytic oxidation and to propose a new method to overcome the limitation of established methods. To simulate $TiO_2$ photo-catalytic oxidation process, Degussa P25 which has been widely used as a standard $TiO_2$ photo-catalyst was used with the dose of 0.05 g/L. The light source of process was UVC mercury low-pressure lamp (11 W, $2,975mW/cm^2$). The results indicate that both potassium iodide (KI)/UV-vis spectrometer and terephthalic acid (TPA)/fluorescence spectrometer methods could be applied to qualitatively measure hydroxyl radicals via detection of triiodide ion ($I_3{^-}$) and 2-hydroxyterephthalic acid which are produced by reactions of iodine ion ($I^-$) and TPA with hydroxyl radicals, respectively. However, it was possible to quantitatively measure hydroxyl radicals using TPA method coupled with high-performance liquid chromatograph (HPLC). The analytical results using TPA/HPLC method show that hydroxyl radical of 0.013 M was produced after 8 hours operation of photo-catalytic oxidation under specific experimental conditions of this study. The proposed method is expected to contribute to precise the evaluation of the performance of photo-catalytic oxidation process.

• Journal of the Mineralogical Society of Korea
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• v.25 no.4
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• pp.271-282
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• 2012

We explore the effect of removal of organic ligand on the atomic configurations around oxygen in hydroxyl groups in amorphous silica gel (synthesized through hydrolysis of $SiCl_4$ in diethyl-ether) using high resolution $^{17}O$ solid state NMR spectroscopy. $^1H$ and $^{29}Si$ MAS NMR spectra for amorphous silica gel showed diverse hydrogen environments including water, hydroxyl groups (e.g., hydrogen bonded silanol, isolated silanol), and organic ligands (e.g., alkyl chain) that may interact with surface hydroxyls in the amorphous silica gel, for instance, forming silica-organic ligand complex (e.g., Si-$O{\cdots}R$). These physically and chemically adsorbed organic ligands were partly removed by ultrasonic cleaning under ethanol and distilled water for 1 hour. Whereas $^{17}O$ MAS NMR spectra with short pulse length ($0.175{\mu}s$) at 9.4 T and 14.1 T for as-synthesized amorphous silica gel showed the unresolved peak for Si-O-Si and Si-OH structures, the $^{17}O$ MAS NMR spectra with long pulse length ($2{\mu}s$) showed the additional peak at ~0 ppm. The peak at ~0 ppm may be due to Si-OH structure with very fast relaxation rate as coupled to liquid water molecules or organic ligands on the surface of amorphous silica gel. The observation of the peak at ~0 ppm in $^{17}O$ MAS NMR spectra for amorphous silica gel became more significant as the organic ligands were removed. These results indicate that the organic ligands on the surface of amorphous silica gel interact with oxygen atoms in Si-OH and provide the information about atomic structure of silanol and siloxane in amorphous silica gel. The current results could enhance the understanding of dehydration mechanism of diverse silicates, which is known as atomic scale origins of intermediate depth (approximately, 70~300 km) earthquakes in subduction zone.

• Journal of the Mineralogical Society of Korea
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• v.25 no.4
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• pp.197-210
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• 2012

Hematite has been known to be the most stable form of various iron (oxyhydr)oxides in the surface environments. In this study, its properties as an adsorbent were examined and also adsorption of arsenic onto hematite was characterized as well. The specific surface area of hematite synthesized in our laboratory appeared to be $31.8g\;m^2/g$ and its point of zero salt effect, (PZSE) determined by potentiometric titration was observed 8.5. These features of hematite may contribute to high capacity of arsenic adsorption. From several adsorption experiments undertaken at the identical solution concentrations over pH 2~12, the adsorption of As(III) (arsenite) was greater than that of As(V) (arsenate). As of pH-dependent adsorption patterns, in addition, arsenite adsorption gradually increased until pH 9.2 and then sharply decreased with pH, whereas adsorption of arsenate was greatest at pH 2.0 and steadily decreased with the increasing pH from 2 to 12. The characteristics of these pH-dependent adsorption patterns might be caused by combined effects of the variation in the chemical speciation of arsenic and the surface charge of hematite. The experimental results on adsorption kinetics show that adsorption of both arsenic species onto hematite approached equilibrium within 20 h. Additionally, the pseudo-second-order model was evaluated to be the best fit for the adsorption kinetics of arsenic onto hematite, regardless of arsenic species, and the rate constant of As(V) adsorption was investigated to be larger than that of As(III).