• Journal of the Mineralogical Society of Korea
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• v.30 no.2
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• pp.59-70
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• 2017

$SiO_2$ is one of the most abundant constituents of the Earth's crust and mantle. Probing its electronic structures at high pressures is essential to understand their elastic and thermodynamic properties in the Earth's interior. The in situ high-pressure x-ray Raman scattering (XRS) experiment has been effective in providing detailed bonding transitions of the low-z materials under extreme compression. However, the relationship between the local atomic structures and XRS features at high pressure has not been fully established. The ab initio calculations have been used to overcome such experimental difficulties. Here we report the partial density of states (PDOS) of O atoms and the O K-edge XRS spectra of ${\alpha}-quartz$, ${\alpha}-cristobalite$, and $CaCl_2$-type $SiO_2$ phases calculated using ab initio calculations based on the full-potential linearized augmented plane wave (FP-LAPW) method. The unoccupied O PDOSs of the $CaCl_2$-type $SiO_2$ calculated with and without applying the core-hole effects present significantly distinctive features. The unoccupied O p states of the ${\alpha}-quartz$, ${\alpha}-cristobalite$ and $CaCl_2$-type $SiO_2$ calculated with considering the core-hole effect present similar features to their calculated O K-edge XRS spectra. This confirms that characteristic features in the O K-edge XRS stem from the electronic transition from 1s to unoccupied 2p states. The current results indicate that the core-hole effects should be taken in to consideration to calculate the precise O K-edge XRS features of the $SiO_2$ polymorphs at high pressure. Furthermore, we also calculated O K-edge XRS spectrum for $CaCl_2$-type $SiO_2$ at ~63 GPa. As the experimental spectra for these high pressure phases are not currently available, the current results for the $CaCl_2$-type $SiO_2$ provide useful prospect to predict in situ high-pressure XRS spectra.

• Korean Journal of Fisheries and Aquatic Sciences
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• v.18 no.5
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• pp.455-463
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• 1985

Thermal-denaturation of myofibrillar protein of dorsal skeletal muscle from file fish was investigated by measuring denaturation constant($K_D$) and thermodynamic parameters at various temperatures. The protective effects of sucrose, sorbitol and amino acids when added individually or combined were also discussed. The denaturation rate as reflected in inactivation of myofibrillar protein Ca-ATPase was followed the first order reaction. The $K_D$ values at $25^{\circ}C,\;30^{\circ}C,\;and\;35^{\circ}C$ were $19.52{\times}10^{-5},\;112.25{\times}10^{-5},\;and\;247.20{\times}10^{-5}$, respectively. The activation energy of the reaction at $30^{\circ}C$ was 43 kcal/mole. The protective effects of sucrose, sorbitol, glycine, alanine and Na-glutamate were increased with the concentration but the effects of sorbitol and Na-glutamate decreased beyond 1.0 mole. Basic amino acids such as arginine and lysine did not revealed any protective effect on the thermal denaturation. In case of mixed addition, the effects of Na-glutamate to glycine, sorbitol to glycine, and sorbitol to sucrose or sorbitol to Na-glutamate were enhanced 1.2 to 7.0 times as much as that of control (ratio of mixing; 1:1, range of concentration; 0.5 to 1.25 mole). Under the frozen condition at $-20^{\circ}C$, two mixtures such as Na-glutamate to glycine and sorbitol to sucrose apparently revealed the protective effects.

• Journal of the Korean Geographical Society
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• v.28 no.1
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• pp.1-15
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• 1993

This research aims to investigate some respects of chemical weathering processes, espcially the amount of solute leaching, formation of clay minerals, and the chemical weathering rate of granite rocks under present climatic conditions. For this purpose, I investigated geochemical mass balance in a small catchment and the mineralogical composition of weathered bedrocks including clay mineral assemblages at four res-pective sites along one slope. The geochemical mass blance for major elements of rock forming minerals was calculated from precipitation and streamwater data which are measured every week for one year. The study area is a climatically and litholo-gically homogeneous small catchment($3.62Km^2$)in Anyang-shi, Kyounggi-do, Korea. The be-drock of this area id Anyang Granite which is composed of coarse-giained, pink-colored miner-als. Main rock forming minerals are quartz, K-Feldspar, albite, and muscovite. One of the chracteristics of this granite rock is that its amount of Ca and Mg is much lower than other granite rock. The leaching pattern in the weathering profiles is in close reltion to the geochemical mass balance. Therefore the removal or accumulation of dissolved materials shows weathering patterns of granite in the Korean peninsula. Oversupplied ions into the drainage basin were $H^+$, $K^+$, Fe, and Mn, whereas $Na^2+$, $Mg^2+$, $Ca^2+$, Si, Al and $HCO-3^{-}$ were removed from the basin by the stream. The consumption of hydrogen ion in the catchment implies the hydrolysis of minerals. The surplus of $K^+$ reflects that vegetation is in the aggravation stage, and the nutrient cycle of the forest in study area did not reach a stable state. And it can be also presumed that the accumulation of $K^+$ in the top soil is related to the surplus of $K^+$. Oversupplied Fe and Mn were presumed to accumulate in soil by forming metallic oxide and hydroxide. In the opposite, the removal of $Na^+$, Si, Al resulted from the chemical weathering of albite and biotite, and the amount of removal of $Na^+$, Si, Al reflected the weathering rate of the bedrock. But $Ca^2+$ and $Mg^2+$ in stream water were contaminated by the scattered calcareous structures over the surface. Kaolinite is a stable clay mineral under the present environment by the thermodynamical analysis of the hydrogeochemical data and Tardy's Re value. But this result was quite different from the real assemblage of clay miner-als in soil and weathered bedrock. This differ-ence can be explained by the microenvironment in the weathering profile and the seasonal variation of climatic factors. There are different clay forming environments in the stydy area and these differences originate from the seasonal variation of climate, especially the flushing rate in the weathering profile. As it can be known from the results of the analysis of thermodynamic stability and characteristics of geochemical mas balance, the climate during winter and fall, when it is characterized by the low flushing rate and high solute influx, shows the environmental characteristics to from 2:1 clay minerals, such as illite, smectite, vermiculite and mixed layer clay minerals which are formed by neoformation or transformation from the primary or secondary minerals. During the summer and spring periods, kaoli-nite is a stable forming mineral. However it should consider that the other clay minerals can transformed into kaolinite or other clay minerals, because these periods have a high flushing rte and temperature. Materials which are directly regulated by chemical weathering in the weathered bedrock are $Na^+$, Si, and Al. The leaching of Al is, however, highly restricted and used to form a clay mineral, and that of Si falls under the same category. $Na^+$ is not taked up by growing veget ation, and fixed in the weathering profile by forming secondary minerals. Therefore the budget of $Na^+$ is a good indicator for the chemical weathering rate in the study area. The amount of chemical weathering of granite rocks was about 31.31g/$m^2+$/year based on $Na^+$ estimation.

• The Korean Journal of Pesticide Science
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• v.2 no.1
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• pp.46-52
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• 1998

The hydrolysis rate of insecticidal buprofezin(IUPAC : tert-butylimino-3-isopropyl-5-phenylperhydro-1,3,5-thiadiazin-4-one) in the range of pH 2.0 and 12.0 have been examined in 15%(v/v) aqueous dioxane at $45^{\circ}C$. The hydrolysis mechanism of buprofezin is proposed from the pH-effect, solvent effect(${\ell}{\gg}m$), thermodynamic parameter(${\Delta}H^{\neq}$=11.12 $Kcal{\cdot}mol^{-1}$ &, ${\Delta}S^{\neq}=5.0e.u.$), rate equation and hydrolysis product, l-isopropyl-3-phenyl urea. General acid catalyzed hydrolysis and specific acid catalyzed($k_{H3O+}$) hydrolysis through $A-S_{E}2$ and A-2(or $A_{AC}2$) reaction mechanism with orbital-control reaction proceed below pH 8.0 and above pH 9.0, the nucleophilic addition-elimination, $Ad_{N}-E$ mechanism via tetrahedral($sp^{3}$) intermediate is initiation by general base catalyzed($k_{H2O}$) reaction. Buprofezin was more stable in alkaline ($k=10^{-8}sec.^{-1}$) than acid solutions from the sigmoid pH-rate profile. And the half-life($t=\frac{1}{2}$) of hydrolysis reaction in neutral aqueous solution(pH 7.0) at $45^{\circ}C$ was about 3 months.

• Applied Biological Chemistry
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• v.47 no.3
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• pp.344-350
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• 2004

This study was conducted to develop and assess the applicability of mixed-bed ion exchange resin capsules for water quality monitoring in small agricultural watershed. Recoveries of resin capsules for inorganic N and P ranged from 96 to 102%. The net activation energies and pseudo-thermodynamic parameters, such as ${\Delta}G^{o\ddag},\;{\Delta}H^{o\ddag},\;and\;{\Delta}S^{o\ddag}$ for ion adsorption by resin capsules, exhibited relatively low values, indicating the process might be governed by chemical reactions such as diffusion. However, those values increased with temperature coinciding with the theory. The reaction reached pseudo-equilibrium within 24 hours for $NH_4-N\;and\;NO_3-N$, and only 8 hours for $PO_4-P$, respectively. The selectivity of resin capsules were in the order of $NO_3\;^-\;>\;NH_4\;^+\;>\;PO_4\;^{3-}$, coinciding with that of encapsulated Amberlite IRN-150 resin. At the initial state of equilibrium, the resin adsorption quantity was linearly proportional to the mass of ions in the streams, but the rate of movement leveled off, following Langmuir-type sorption isotherm. The overall results demonstrated that the resin capsule system was suitable for water quality monitoring in small agricultural watershed, judging from the reaction mechanism(s) of the resin capsule and the significance of model in field calibration.

• Korean Journal of Agricultural and Forest Meteorology
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• v.9 no.1
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• pp.1-16
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• 2007

The use of information on natural resources is indispensable to most agricultural activities to avoid disasters, to improve input efficiency, and to increase lam income. Most information is prepared and managed at a spatial scale called the "Hydrologic Unit" (HU), which means watershed or small river basin, because virtually every environmental problem can be handled best within a single HU. South Korea consists of 840 such watersheds and, while other watershed-specific information is routinely managed by government organizations, there are none responsible for agricultural weather and climate. A joint research team of Kyung Hee University and the Agriculture, forestry and Fisheries Information Service has begun a 4-year project funded by the Ministry of Agriculture and forestry to establish a watershed-specific agricultural weather information service based on "high definition" digital climate maps (HD-DCMs) utilizing the state of the art geospatial climatological technology. For example, a daily minimum temperature model simulating the thermodynamic nature of cold air with the aid of raster GIS and microwave temperature profiling will quantify effects of cold air drainage on local temperature. By using these techniques and 30-year (1971-2000) synoptic observations, gridded climate data including temperature, solar irradiance, and precipitation will be prepared for each watershed at a 30m spacing. Together with the climatological normals, there will be 3-hourly near-real time meterological mapping using the Korea Meteorological Administration's digital forecasting products which are prepared at a 5 km by 5 km resolution. Resulting HD-DCM database and operational technology will be transferred to local governments, and they will be responsible for routine operations and applications in their region. This paper describes the project in detail and demonstrates some of the interim results.

• Economic and Environmental Geology
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• v.50 no.1
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• pp.35-44
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• 2017

The Hadong-Sancheong Proterozoic anorthosite complex occurs in the southwestern region of the Ryongnam massif. The geology of the area mainly consists of metamorphic rocks of the Jirisan metamorphic complex as basement rocks, charnockite, and the Hadong-Sancheong anorthosite, which are intruded by the Mesozoic igneous rocks. Hadong-Sancheong anorthosite complex is divided into the Sancheong anorthosite and the Hadong anorthosite which occur at north-southern and south area of the Jurassic syenite, respectively. The Hadong Fe-Ti-bearing dike-like ore bodies developed intermittently in the Hadong anorthosite with north-south direction and extend about 14 km. The Hadong Fe-Ti-bearing ore bodies consist mainly of magnetite and ilmenite with rutile, titanite, and minor amounts of sulfides(pyrrhotite, pyrite, chalcopyrite and sphalerite). The Hadong Fe-Ti-bearing ore bodies show a paragenetic sequence of magnetite-ilmenite ${\rightarrow}$ magnetite-ilmenite-pyrrhotite ${\rightarrow}$ ilmenite-pyrrhotite-rutile-titanite(and/or pyrite) ${\rightarrow}$ sulfides. Equilibrium thermodynamic interpretation of the mineral paragenesis and assemblages indicate that early Fe-Ti-bearing ore mineralization in the ore bodies occurs at about $700^{\circ}C$ which corresponds to oxygen fugacity of about $10^{-11.8}{\sim}10^{-17.2}$ atm with the decrease tendency of sulfur fugacity to about $10^0$ atm as equilibrium of $Fe_3O_4-FeS$. The change of ore mineral assemblages from Fe-Ti-bearing minerals to sulfides in late ore mineralization of the ore bodies indicates that oxygen fugacity would have slightly decreased to ${\geq}10^{-20.2}$ atm and increased sulfur fugacity to ${\geq}10^0$ atm.

• Journal of the Korean Society for Marine Environment & Energy
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• v.13 no.3
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• pp.187-197
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• 2010

Carbon dioxide Capture and Storage(CCS) is regarded as one of the most promising options to response climate change. CCS is a three-stage process consisting of the capture of carbon dioxide($CO_2$), the transport of $CO_2$ to a storage location, and the long term isolation of $CO_2$ from the atmosphere for the purpose of carbon emission mitigation. Up to now, process design for this $CO_2$ marine geological storage has been carried out mainly on pure $CO_2$. Unfortunately the $CO_2$ mixture captured from the power plants and steel making plants contains many impurities such as $N_2$, $O_2$, Ar, $H_2O$, $SO_2$, $H_2S$. A small amount of impurities can change the thermodynamic properties and then significantly affect the compression, purification, transport and injection processes. In order to design a reliable $CO_2$ marine geological storage system, it is necessary to analyze the impact of these impurities on the whole CCS process at initial design stage. The purpose of the present paper is to compare and analyse the relevant physical property models including BWRS, PR, PRBM, RKS and SRK equations of state, and NRTL-RK model which are crucial numerical process simulation tools. To evaluate the predictive accuracy of the equation of the state for $CO_2-SO_2$ mixture, we compared numerical calculation results with reference experimental data. In addition, optimum binary parameter to consider the interaction of $CO_2$ and $SO_2$ molecules was suggested based on the mean absolute percent error. In conclusion, we suggest the most reliable physical property model with optimized binary parameter in designing the $CO_2-SO_2$ mixture marine geological storage process.

• 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.

• Economic and Environmental Geology
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• v.50 no.6
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• pp.435-443
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• 2017

The Hanae deposit is located within the Cretaceous Gyeongsang Basin. The Cu-bearing hydrothermal quartz vein formed by narrow open-space filling along fracture in the sedimentary rocks as Jindong Formation. The Hanae Cu-bearing hydrothermal deposit shows a paragenetic sequence of pyrrhotite-pyrite $\rightarrow$ pyrite-chalcopyrite-sphalerite(${\pm}$Bi-bearing tellurides) $\rightarrow$ Ag-bearing telluride mineralization $\rightarrow$ secondary mineralization. Fluid inclusion data indicate that the Hanae Cu-bearing hydrothermal mineralization occurred from dominantly aqueous fluids at temperatures of $400^{\circ}C-200^{\circ}C$. Equilibrium thermodynamic interpretation of the mineral paragenesis and assemblages combined with fluid inclusion data indicate that early main Cu-bearing ore mineralization in the vein starts at about $350^{\circ}C$ which corresponds to sulfur fugacity from about $10^{-9.2}$ to $10^{-8.7}bar$ with oxygen fugacity of about $10^{-32.1}$ to $10^{-29.8}bar$. Late main Cu-bearing ore mineralization in the vein occurs at about $250^{\circ}C$ which corresponds to sulfur fugacity from about $10^{-13.5}$ to $10^{-11.7}bar$ with oxygen fugacity of about $10^{-38.4}$ to $10^{-35.2}bar$. The late Ag-bearing telluride mineralization in the Hanae hydrothermal system occurs at about $200^{\circ}C$ which corresponds to minium Tellirium fugacity value of about $10^{-18}bar$ with sulfur fugacity of about $10^{-14.0}$ to $10^{-10.9}bar$.