• Journal of the Mineralogical Society of Korea
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• v.24 no.4
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• pp.313-320
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• 2011

Mica-type phyllosilicate particles in the shales of the Manhang formation at the Taeback area in the Kangwon Province were studied using electron probe microanalysis (EPMA) and transmission electron microscopy (TEM). The average chemical formula of the mica-type phyllosilicate mineral analysed by EPMA is $K_{1.35}(Fe_{0.18}Mg_{0.03}Al_{3.86})(Si_{6.55}Al_{1.45})O_{20}(OH)_4$. Low K contents compared to the ideal chemistry of muscovite indicate the presence of illite in the mica-type phyllosilicate particle. X-ray diffraction study showed that pyrophyllite commonly coexists with muscovite in the shales from the Manhang Formation. TEM observations showed both the interlayer and intralayer mixing of $9.3-{\AA}$ pyrophyllite and $10-{\AA}$ muscovite layers. The low K content of the mica-type phyllosilicates apparently come from the close mixing of pyrophyllite and muscovite.

• Journal of the Mineralogical Society of Korea
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• v.25 no.1
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• pp.1-8
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• 2012

The metamorphic environments occrrred in the Sadong and the Gobangsan formations were studied through the investigation of chloritoid and white mica in shales at Munkyung area. Two types of white mica occurs in the shale of Sadong formation; muscovite-dominant ($Mu_{76.1}Pa_{18.1}Ma_{5.8}$) and margarite-dominant ($Ma_{52.9}Mu_{31.6}Pa_{15.5}$). It is inferred that the muscovite-dominant white mica is generated by the diagenesis of Na-rich illite whereas the margarite-dominant white mica is generated by reactions between calcite and pyrophyllite separated from illite. In shales of the Gobangsan formation, chloritoids are observed with muscovite, pyrophyllite and chlorite. The chloritoids of the Gobangsan formation are considered to be originated from the reaction between pyrophyllite and chlorite. The Sadong and Gobangsan formations would have experienced the low-temperature metamorphism (anchizone) considering that white mica in general forms above the temperature of $200^{\circ}C$ and the assemblage of chloritoid-pyrophyllite-chlorite is stabilized below $280^{\circ}C$.

• Journal of the Mineralogical Society of Korea
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• v.26 no.1
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• pp.55-64
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• 2013

The generation of staurolite from the mixed-phase muscovite and the metamorphic environment of shales in the Baekunsa formation, Hongsan, Buyeo, were studied using electron probe micro analysis (EPMA). The average chemical composition of mica-type mineral is $(K_{1.11}Na_{0.26}Ca_{0.04})(Al_{3.93}Fe_{0.21}Mg_{0.07})(Si_{6.08}Al_{1.92})O_{20}(OH)_4$, and shows a characteristics of the so-called illite with a low content of interlayer cations and Fe, Mg in octahedral sites. The mica-type mineral shows a typical chemical composition of the mixed-phase among muscovite, pyrophyllite, and chlorite (mixed-phase muscovite, $Mu_{70.5}Py_{23.5}Ch_{6.0}$). The staurolite, in general, occurs with the mixed-phase muscovites, pyrophyllites, and aluminosilicates in the rock. We consider that staurolite can be formed by a reaction involving pyrophyllite such as pyrophyllite+chloritoid. The chloritoid is formed by a reaction between pyrophyllite and chlorite and is supposed to be used up in the process of staurolite formation. As a result, the mixed-phase muscovite, formed during the transition of illite to muscovite, plays an important role for the generation of the staurolite. Considering that the reaction occurs at the temperature higher than $300^{\circ}C$ and pyrophyllites transform into aluminosilicates at $350^{\circ}C$, the shale in the Baekunsa formation can be considered to have been experienced a metamorphic temperature between $300{\sim}350^{\circ}C$.

• Journal of the Mineralogical Society of Korea
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• v.25 no.3
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• pp.143-153
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• 2012

Mica-type minerals (illites) in the shales of the Jigunsan formation at Seokgaejae in Samchuk-City, Gangwon-do are studied using electron probe micro analysis (EPMA). The average chemical formula of the mica-type mineral obtained from the quantitative analysis is $(K_{1.17}Na_{0.04}Ca_{0.01})(Al_{2.80}Mg_{1.17}Fe_{0.78})(Si_{6.34}Al_{1.66})O_{20}(OH)_4$, which shows a chemical formula within the range of illite. These illites so called can be considered as mixed-phases among muscovite, pyrophyllite and chlorite due to the low contents of interlayer cations and high Mg, Fe. The formula of illite is separated into those three minerals and the method for the separation is newly formulated and proposed in this study. From the formula of illite, the content of muscovite is estimated from K (Na and Ca included), the content of chlorite by Mg+Fe, and the rest remains as pyrophyllite. The chemical formula of muscovite can be calculated by subtracting the compositions of pyrophyllite and chlorite from the analyzed composition of illite using an ideal formula for pyrophyllite and analyzed average formula for chlorite. The calculated formula of muscovite is supposed to be stoichiometric in principle. The result of the separation of analyzed illite is 61% muscovite, 27.3% chlorite and 11.7% pyrophyllite and the calculated formula of muscovite after separation is $(K,Na,Ca)_{2.00}Al_{3.69}(Si_{6.75}Al_{1.25})O_{20}(OH)_4$. The calculated formula of muscovite slightly low in Al content can be considered to be reasonable in general when the low content of Al in the rock and the uncertainties of chlorite compositions used in the calculation are counted. This supports that the method of separation proposed in this study is also applicable.

• Proceedings of the Petrological Society of Korea Conference
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• 2009.05a
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• pp.15-17
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• 2009

• The Journal of the Petrological Society of Korea
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• v.7 no.2
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• pp.132-145
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• 1998

The coal-bearing siliciclastic rocks of the Lower Permian Jangseong Formation, Samcheog coalfield, represent a megacyclothem which shows cyclic repetitions of sandstone, shale, coaly shale, and coals. Petrographic, geochemical, and SEM studies for sandstone samples, and XRD analysis for clay minerals were carried out to understand diagenesis in the sandstones of the Jangseong Formation. The Jangseong sandstones are composed of 60% quartz (mainly monocrystalline quartz) and 36% clay matrix and cement with minor amounts of feldspar, lithic fragments and accessory minerals (less than 4%). Jangseong sandstones are classified mostly as quartzwackes and partly as lithic graywackes according to the scheme of Dott(1964). The textural relationships between authigenic minerals and cements in thin sections and SEM photomicrographs suggest the paragenetic sequence as follows; (1) mechanical compaction, (2) cementation by quartz overgrowth, (3) formation of authigenic clay minerals (illite, kaolinite), (4) dissolution of framework grains and development of secondary porosity, and (5) later-stage pore-filling by pyrophyllite. We propose that these diagenetic processes might be due to organic-inorganic interaction between the dominant framework grains and the formation water. The Al, Si ions and organic acid, derived from dewatering of interbedded organic-rich shale and coals, were transported into the Jangseong sandstones. This caused changes in the chemistry of the formation water of the sandstones, and resulted in overgrowth of quartz and precipitation of authigenic clay minerals of kaolinite and illite. The secondary pores, produced during dissolution of clay and framework grains by organic acid and $CO_2$ gas, were conduit for silica-rich solution into the Jangseong sandstones and the influx of silica-rich solution produced the late-stage pyrophyllite after the expanse of kaolinite. The origin of the solution that formed pyrophyllite is not likely to be the organic-rich formation water based on the observation of fracture-filling pyrophyllite in the Jangseong sandstones, but the process of pyrophyllite pore-filling was indirectly related to organic-inorganic interaction.

• 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.27 no.4
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• pp.271-281
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• 2014

The physicochemical properties of clay minerals have been investigated at the atomistic to nano scale. The microscopic studies are often challenging to perform by using experimental approaches alone. In particular, hydroxyl groups of octahedral sheets in 2:1 clay minerals have been hypothesized to impact the sorption process of metal cations; however, X-ray based techniques alone, a common tool for mineral structure examination, cannot properly test the hypothesis. The current study has examined whether computational mineralogy techniques can be applied to examine the hydroxyl structures of clay minerals. Based on quantum-mechanics and molecular-mechanics computational methods, geometry optimizations were carried out for representative dioctahedral and trioctahedral phyllosilicate minerals. Both methods well reproduced the experimental lattice parameters; however, for structural distortion occurring in the tetrahedral or octahedral sheets, molecular mechanics showed significant deviations from experimental data. The orientation angle of the hydroxyl with respect to (001) basal plane is determined by the balance of repulsion between the hydroxyl proton and Si cations of tetrahedral sites; the quantum-mechanics method predicted $25-26^{\circ}$ for the angle, whereas the angle predicted by the molecular-mechanics method was much higher by $10^{\circ}$ (i.e., $35^{\circ}$). These results demonstrate that computational mineralogy techniques are a reliable tool for clay mineral studies and can be used to further elucidate the roles of hydroxyls in metal sorption process.

• Journal of the Mineralogical Society of Korea
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• v.29 no.4
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• pp.209-220
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• 2016

Clay minerals are a major player to determine geochemical cycles of trace metals and carbon in the critical zone which covers the atmosphere down to groundwater aquifers. Molecular dynamics (MD) simulations can examine the Earth materials at an atomic level and, therefore, provide detailed fundamental-level insights related to physicochemical properties of clay minerals. In the current study, we have applied classical MD simulations with clayFF force field to dioctahedral clay minerals (i.e., gibbsite, kaolinite, and pyrophyllite) to analyze and compare structural parameters (lattice parameter, atomic pair distance) with experiments. We further calculated vibrational power spectra for the hydroxyls of the minerals by using the MD simulations results. The MD simulations predicted lattice parameters and interatomic distances respectively deviated less than 0.1~3.7% and 5% from the experimental results. The stretching vibrational wavenumber of the hydroxyl groups were calculated $200-300cm^{-1}$ higher than experiment. However, the trends in the frequencies among different surface hydroxyl groups of each mineral was consistent with experimental results. The angle formed by the surface hydroxyl group with the (001) plane and hydrogen bond distances of the surface hydroxyls were consistent with experimental result trends. The inner hydroxyls, however, showed results somewhat deviated from reported data in the literature. These results indicate that molecular dynamics simulations with clayFF can be a useful method in elucidating the roles of surface hydroxyl groups in the adsorption of metal ions to clay minerals.