• Journal of the Mineralogical Society of Korea
• /
• v.30 no.4
• /
• pp.161-172
• /
• 2017

Clay minerals play a major role in the geochemical cycles of metals in the Critical Zone, the Earth surface-layer ranging from the groundwater bottom to the tree tops. Atomistic scale research of the very fine particles can help understand the fundamental mechanisms of the important geochemical processes and possibly apply to development of hybrid nanomaterials. Molecular dynamics (MD) simulations can provide atomistic level insights into the crystal structures of clay minerals and the chemical reactivity. Classical MD simulations use a force field which is a parameter set of interatomic pair potentials. The ClayFF force field has been widely used in the MD simulations of dioctahedral clay minerals as the force field was developed mainly based on dioctahedral phyllosilicates. The ClayFF is often used also for trioctahedral mineral simulations, but disagreement exits in selection of the interatomic potential parameters, particularly for Mg atom-types of the octahedral sheet. In this study, MD simulations were performed for trioctahedral clay minerals such as brucite, lizardite, and talc, to test how the two different Mg atom types (i.e., 'mgo' or 'mgh') affect the simulation results. The structural parameters such as lattice parameters and interatomic distances were relatively insensitive to the choice of the parameter, but the vibrational power spectra of hydroxyls were more sensitive to the choice of the parameter particularly for lizardite.

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

• Journal of the Mineralogical Society of Korea
• /
• v.27 no.4
• /
• pp.271-281
• /
• 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.

• 한국해양학회지
• /
• v.26 no.4
• /
• pp.313-323
• /
• 1991

Fine-grained sediments of the Han River and adjacent Kyonggi Bay have been studied using the powder x-ray diffractometer in order to study the distributional characteristics of clay minerals in the bottom and suspended sediments. The result of the XRD analyse shows that the major clay minerals in the lower Han River are composed of illite (57.1%), kaolinite (22.9%), and chlorite (19.6%) and that those of the Han River Estuary are composed of illite (67.2%), chlorite (16.5%), kaolinite 915.5%), and smectite (1.3%). The variation of mineral content shows distinct distributional characteristics depending on sedimentary environments. The illite content increases gradually approaching the Kyonggi Bay and kaolinite content decreases toward the sea within the range between 11% and 23%. The trend of chlorite is similar to that of kaolinite, the amount of which ranges between 14% and 19%. Smectite content is lower than 3%. Analysis of illite using peak-intensity ratio (001/002) indicates that two types of illites occur in the study area. Dioctahedral-type illite occurs as an indicator of the marine sediments. The illites distributed between the Kyonggi Bay and the Han River are mixtures of dioctahedral- and trioctahedral-types. This study indicates that the distribution of illite, kaolimite, and chlorite has been influenced mainly by the supply from the Han River and redistributed by estuarine circulation, such as tidal circulation and seasonal variation of river discharge. However, smectite is apparently supplied from other sources such as Yellow Sea or China. This study suggests that estuarine mixing system and seasonal variations of river discharge are the major factors controlling the distribution pattern of clay minerals in the study area.

• Journal of Korean Society of Forest Science
• /
• v.86 no.2
• /
• pp.186-199
• /
• 1997

The soils derived from granite gneiss occupy almost one third of the land area in Korea. The soils under forest vegetation, formed on granite gneiss, in Sun chon-shi, Chollanam-do in southern part of Korea, were studied to evaluate the weathering and the transformation of primary minerals into secondary minerals, clay minerals. The studied soils contained large amounts of ferromagnesian minerals, weathered biotites and were well weathered, strongly acid and low in organic matters and in ration exchange capacity. The clay contents in the Bt horizon were almost two times higher than those in the C horizon. The O horizon had a thin layer which consisted of a little decomposed plant components with a granic fabric and high porosity, and showed the micromorphological characteristics of moder humus. The related distribution pattern of the E horizon were enaulic and large amounts of silts and small amounts of sand grains were another characteristics of the E horizon. The most striking micromorphological features were multilaminated clay coating and infillings in the voids in the Bt and C horizons, and generally limpid ferriargillans ejected from the biotites and imparted red color to the soils in the Bt horizon. High clay contents in the Bt horizon was not only due to clay translocation, but also due to intensive in situ mineral weathering in this horizon. The most significant pedogenic process, revealed by the petrographic microscope and SEM, was the formation of iron oxides from biotites, the formation of tubular halloysites and the weathering models of biotites; wedge weathering and layer weathering. The thick coating on the weathering biotites showed the characteristics of the weathering process and the synthetic hematites were revealed in clays by TEM. Total chemical analysis of clays revealed extensive loss of Ca, and Na and the concentration of Fe and Al. Mineralogical studies of clays by XRD showed that micas were almost completely weathered to kaolinite, vermiculite-kaolinite intergrade, hematite, gibbsite, while halloysites from other primary minerals. Some dioctahedral mica appeared to be resistant in the soils. Parent rock of the soils contained a considerable amounts of biotites and this forest soils showed especially a dominant characteristics of biotite weathering.

• Journal of the Mineralogical Society of Korea
• /
• v.4 no.1
• /
• pp.11-21
• /
• 1991

XRD patterns of biedellite-nontronite and saponite-iron saponite series were investigated using one-dimensional pattern simulation method. Ethylene-glycolate smectites show stronger 002 and 003 reflections than hydrated specimens do. The intensities of the 002 and 003 reflections change systematically as a function of Fe enrichment in both types of smectites. The intensity ratio of 002/003 increases with increasing. Fe in both dioctahedral to the higher scattering factor of Fe than those of Al and Mg, and the scattering power of various smectites can be compared quantitatively by calculating the scattering factors of octahedral cations. Interlayer cations cause less effect on XRD profile than octahedral cations as Fe do. Although 001 reflections provide informations about the overall scattering power of the octahedral sheet, some ferrous dioctahedtal smectite cannot be distinguished unambiguously from trioctahedral smectites on the basis of XRD profile. Simulation showed that heterogeneous smectites exhibit 001 intensity distribution that is almost identical to that of homogeneous smectites having the average composition of heterogeneous ones. The broadening of 001 reflections may not be useful in evaluating the degree of heterogeneity of smectite unless other factors affecting the broadening are well known.

• Journal of the Mineralogical Society of Korea
• /
• v.15 no.2
• /
• pp.85-94
• /
• 2002

XRF, XRD, EPMA have been used to investigate microstructures and mineralogical changes caused by the faulting and fluids associated with faulting in the Quaternary fault gouge zones at the Sangchon, Ipsil and Wangsan faults located at the southeastern part of the Korean Peninsula. The chemical compositions of faulted rocks and protoliths analyzed by XRF show that the fault gouges are relatively enriched in TiO$_2$, P$_2$O$_{5}$, MgO, and Fe$_2$O$_3$) compared with protoliths, indicating that the fluids associated with faulting were highly activated. XRD results show that the fault gouges predominantly consist of quartz, feldspar, calcite and clay minerals. Clay minerals formed in the gouge zones are mainly composed of smectite characterized by a dioctahedral sheet. Based on EPMA analyses various kinds of sulfide, carbonate, phosphate minerals were identified in the gouge zones and protoliths. Xenotime of grey fault gouge of the Sangchon fault and sulfide minerals of contact andesitic rock of Ipsil fault and contact grey andesitic rock of Wangsan fault were probably formed by inflow of hydrothermal solution associated with faulting prior to the Quaternary. Carbonate minerals of contact andesitic rock and gouge zone of the Ipsil fault were formed by inflow of fluid associated with faulting prior to the Quaternary. They are heavily fractured and have reaction rim on their edge, indicating that faultings and inflow of fluids were highly activated after carbonate minerals were formed. Calcites of Wangsan fault seemed to be formed in syntectonic or posttectonic Quaternary faulting.g.