• 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.22 no.2
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• pp.115-127
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• 2009

Mineral quantification was performed on sediments of the Ulleung basin by X-ray powder diffraction and the computer software based on Rietveld quantification method. The sediments are dominated by amorphous opal-A with quartz, feldspars, micas, clays, calcite, and pyrite. The opal-A shows iterative variation in abundance with increasing burial depth. In addition, the relative abundance of opal-A is coincident with abundance of organic carbon contents, indicating that the Ulleung sediment consists mostly of amorphous silica derived from organism in the pelagic environment. Upward increase in the abundance of opal-A is markedly shown in the cores located in the slope region. On the other hand, there is a distinct tendency that the abundance of calcite is inversely proportional to that of opal-A. This indicates that the abundance of opal-A increases during the rise of sea level. Also, the fall of sea level lowers the abundance of opal-A.

• Journal of the Mineralogical Society of Korea
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• v.24 no.3
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• pp.151-164
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• 2011

Mineralogical and petrological characteristics were investigated on matrix of dense gray, vesiculate gray, brown and black pumice in Ulleung Island by using XRD, FT-IR, XRF, SEM and thermal analysis. According to the analysis, most of pumice matrix are amorphous and include very small amount of sanidine and anorthoclase. Since the adsorption moistures, which commonly observed as O-H peak in FT-IR spectrum, are not identified in thermal analysis, it seems reasonable to conclude that content of the adsorption moisture has very low level. Although pumice has a large specific surface area, with long time elapsed after eruption, pumice matrix shows very low degree of hydration alteration due to the low level of water content. In SEM images, most surfaces of pumice show morphological characteristics such as various shapes of vesicle with wrinkled and thin walls resulted from ductile coalescence. Dense gray pumice formed in the initial stage includes small vesicles less than $15{\mu}m$ in size with subangular to angular shapes, free of ovoid vesicle. These characteristics are interpreted to have related to the hydrous environment derived from phreato-plinian eruption. Submicron particles observed as amorphous alumina silicate assemblages in vesicle surface are considered as particles sticked to the matrix surface through rapidly cooling process during ascent of alkali phonolitic magma. It indicates that these particles coexisted partly with crystallized alkali feldspar.

• Journal of the Mineralogical Society of Korea
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• v.27 no.1
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• pp.1-15
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• 2014

Probing the electronic structures of crystalline Mg-silicates at high pressure is essential for understanding the various macroscopic properties of mantle materials in Earth's interior. Quantum chemical calculations based on the density functional theory are used to explore the atomic configuration and electronic structures of Earth materials at high pressure. Here, we calculate the partial density of states (PDOS) and O K-edge energy-loss near-edge structure (ELNES) spectra for $MgSiO_3$ perovskite at 25 GPa and 120 GPa using the WIEN2k program based on the full-potential linearized projected augmented wave (FP-LPAW) method. The calculated PDOS and O K-edge ELNES spectra for $MgSiO_3$ Pv show significant pressure-induced changes in their characteristic spectral features and relative peak intensity. These changes in spectral features of $MgSiO_3$ Pv indicate that the pressure-induced changes in local atomic configuration around O atoms such as Si-O, O-O, and Mg-O length can induce the significant changes on the local electronic structures around O atoms. The result also indicates that the significant changes in O K-edge features can results from the topological densification at constant Si coordination number. This study can provide a unique opportunity to understand the atomistic origins of pressure-induced changes in local electronic structures of crystalline and amorphous $MgSiO_3$ at high pressure more systematically.

• Economic and Environmental Geology
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• v.47 no.4
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• pp.421-430
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• 2014

In this study, a series of autoclave experiments were conducted in order to investigate the geochemical and mineralogical effects of carbon dioxide on deep subsurface environments. High pressure and temperature conditions of $50^{\circ}C$ and 100 bar, which are representative environments for geological $CO_2$ sequestration, were created in stainless-steel autoclaves for simulating the interactions in the $scCO_2$-groundwater-mineral reaction system. Zeolite, a widespread mineral in Pohang Basin where many researches have been focused as a candidate for geological $CO_2$ sequestration, and groundwater sampled from an 800 m depth aquifer were applied in the experiments. Geochemical and mineralogical alterations after 30 days of $scCO_2$-groundwater-zeolite sample reactions were quantitatively examined by XRD, XRF, and ICP-OES investigations. The results suggested that dissolution of zeolite sample was enhanced under the acidic condition induced by dissolution of $scCO_2$. As the cation concentrations released from zeolite sample increase, $H^+$ in groundwater was consumed and pH increases up to 10.35 after 10 days of reaction. While cation concentrations showed increasing trends in groundwater due to dissolution of the zeolite sample, Si concentrations decreased due to precipitation of amorphous silicate, and Ca concentrations decreased due to cation exchange and re-precipitation of calcite. Through the reaction experiments, it was observed that introduction of $CO_2$ could make alterations in dissolution characteristics of minerals, chemical compositions and properties of groundwater, and mineral compositions of aquifer materials. Results also showed that geochemical reactions such as cation exchange or dissolution/precipitation of minerals could play an important role to affect physical and chemical characteristics of geologic formations and groundwater.

• Economic and Environmental Geology
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• v.49 no.2
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• pp.77-88
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• 2016

Chrysotile is a 1:1 sheet silicate mineral belonging to serpentine group. It has been highlighted studies because of uses, shapes and structural characteristics of the fibrous chrysotile. However, it was designated as Class 1 carcinogen, so high attentions were being placed on detoxification studies of chrysotile. The objectives of this study were to investigate changes of mineralogical characteristics of chrysotile and to suggest detoxification mechanism of chrysotile by thermal decomposition. Samples for this study were obtained from LAB Chrysotile mine in Canada. The samples were heated in air in the range of 600 to $1,300^{\circ}C$. Changes of mineralogical characteristics such as crystal structure, shape, and chemical composition of the chrysotile fibers were examined by TG-DTA, XRD, FT-IR, TEM-EDS and SEM-EDS analyses. As a result of thermal decomposition, the fibrous chrysotile having hollow tube structure was dehydroxylated at $600-650^{\circ}C$ and transformed to disordered chrysotile by removal of OH at the octahedral sheet (MgOH) (Dehydroxylation 1). Upon increasing temperature, it was transformed to forsterite ($Mg_2SiO_4$) at $820^{\circ}C$ by rearrangement of Mg, Si and O (Dehydroxylation 2). In addition, crystal structure of forsterite had begun to transform at $800^{\circ}C$, and gradually grown 3-dimensionally to enstatite ($MgSiO_3$) by recrystallization after the heating above $1,100^{\circ}C$. And then finally transformed to spherical minerals. This study showed chrysotile structure was collapsed about $600-700^{\circ}C$ by dehydroxylation. And then the fibrous chrysotile was transformed to forsterite and enstatite, as non-hazardous minerals. Therefore, this study indicates heat treatment can be used to detoxification of chrysotile.

• Journal of the Mineralogical Society of Korea
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• v.20 no.1 s.51
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• pp.47-60
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• 2007

While sedimentological researches on Western coastal tidal flats of Korea have been much pelformed previously, mineralogical and biogeochemical studies are beginning to be studied. The objectives of this study were to investigate mineralogical characteritics of the inter-tidal flat sediments and to explore phase transformation of iron(oxyhydr)oxides and biomineralization by metal-reducing bacteria enriched from the inter-tidal flat sediments from Muan, Jeollanam-do, Korea. Inter-tidal flat sediment samples were collected in Chungkye-myun and Haeje-myun, Muan-gun, Jeollanam-do. Particle size analyses were performed using the pipette method and sedimentation method. The separates including sand, silt and clay fractions were examined by scanning electron microscopy (SEM) with energy dispersive X-ray (EDX) analysis, transmission electron microscopy (TEM), and X-ray diffiaction (XRD). After enriching the metal-.educing bacteria from the into,-tidal flat sediments, the bacteria were used to study phase transformation of the synthesized iron (oxyhydr)oxides and iron biomineralization using lactate or glucose as the electron donors and Fe(III)-containing iron oxides as the electron accepters. Mineralogical studies showed that the sediments of tidal flats in Chung]rye-myun and Haeje-myun consist of quartz, plagioclase, microcline, biotite, kaolinite and illite. Biogeochemical researches showed that the metal-reducing bacteria enriched from the inter-tidal flat sediments reduced reddish brown akaganeite and mineralized nanometer-sized black magnetite. The bacteria also reduced the reddish brown ferrihydrite into black amorphous phases and reduced the yellowish goethite into greenish with formation of nm-sized phases. These results indicate that microbial Fe(III) reduction may play one of important roles in iron and carbon biogeochemistry as well as iron biomineralization in subsurface environments.