• Economic and Environmental Geology
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• v.31 no.3
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• pp.201-213
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• 1998

From the Jungwon and Munkyeong areas which are among the famous producers of the carbonate-type groundwaters in Korea, various kinds of natural waters (deep groundwater, shallow groundwater and surface water) were collected between 1996 and 1997 and were studied for hydrogeochemical and environmental isotope (${\delta}^{34}S_{so4}$, ${\delta}^{18}O$, ${\delta}D$)systematics. Two types of deep groundwaters (carbonate type and alkali type) occur together in the two areas, and each shows distinct hydrogeochemical and environmental isotope characteristics. The carbonate type waters show the hydrochemical feature of the 'calcium(-sodium)-bicarbonate(-sulfate) type', whereas the alkali type water of the 'sodium-bicarbonate type'. The former type waters are characterized by lower pH, higher Eh, and higher amounts of dissolved ions (especialJy, $Ca^{2+}$, $Na^{+}$, $Mg^{2+}$, $HCO_3{^-}$ and $SO_4{^{2-}}$). Two types of deep groundwaters are all saturated or supersaturated with respect to calcite. Two types of deep groundwaters were both derived from pre-thermonuclear (about more than 40 years old) meteoric waters (with lighter 0 and H isotope data than younger waters, i.e., shallow cold groundwaters and surface waters) which evolved through prolonged water-rock interaction. Based on the geologic setting, water chemistry, and environmental isotope data, however, each of these two different types of deep groundwaters represents distinct hydrologic and hydrogeochemical evolution at depths. The carbonate type groundwaters were formed through mixing with acidic waters that were derived from dissolution of pyrites in hydrothermal vein ores (for the Jungwon area water) or in anthracite coal beds (for the Munkyeong area water). If the deeply percolating meteoric waters did not meet pyrites during the circulation, only the alkali type groundwaters would form. This hydrologic and hydrogeochemical model may be successfully applied to the other carbonate type groundwaters in Korea.

• Economic and Environmental Geology
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• v.27 no.3
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• pp.219-229
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• 1994

The Sangra Pb-Zn deposit is located in the Gampo area. Most Cretaceous sedimentary rocks and Paleogene felsic intrusives in the study area have experienced intense propylitization. Such propylitization and Pb-Zn mineralization in ore veins are involved with the fluid having very low oxygen isotopic composition.Sulfurisotopic equilibrium temperature during the main Pb-Zn mineralization (late stage I) is calculated as $T=275^{\circ}{\sim}295^{\circ}C$. Oxygen and sulfur fugacity in late stage I fluid is estimated as $logfO_2=-34.4{\sim}-29.1$ and $logfS_2=-12.0{\sim}-8.2$ bars. It is inferred that the sulfur isotopic composition oflate stage I fluid was very high such as ${\delta}^{34}S_{{\Sigma}S}=+22.4{\sim}+22.5$‰ and the origin of sulfur was ocean water sulfate. Oxygen and hydrogen isotopic composition of water in ore-forming fluid was gradually increased and more abundantly affected by ocean water from early to late mineralization stage as follows; (late stage I) ${\delta}^{18}O_{H2O}=-7.2{\sim}-1.1$‰, ${\delta}D_{H2O}=-87{\sim}-84$‰, (stage II) ${\delta}^{18}O_{H2O}=-2.4{\sim}-0.8$‰, ${\delta}D_{H2O}=-39{\sim}-21$‰ (stage III) ${\delta}^{18}O_{H2O}=+0.7{\sim}+12.6$‰, ${\delta}D_{H_2O}=-49{\sim}-42$‰. The pH in ore-forming fluid was about 4.7 during late stage I and is thought to have been gradually decreased from late stage I to stage II mineralization.

• 한국해양학회지
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• v.29 no.3
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• pp.258-268
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• 1994

Nitrogenous new production and regenerated production were measured in the southern part of the Yellow Sea (Hwanghae) using a stable isotope /SUP 15/N nitrate and ammonia between April 25∼30, 1993. Nitrogen production varied between 155 and 688 mg N m/SUP -2/ d/SUP -1/, which belongs to meso to eutrophic area values. This is equivalent to 881∼3909 mg C m/SUP -2/ d/SUP -1/, assuming the Redfield ratio for C:N of 5.7:1 (by weight). the f0ratio which is the fraction of new production from primary production, varied between 0.12 and 0.26, indicating that 74 to 88% of primary production was supported by the regeneration of nutrients within the euphoric zone. This low f0ratio is the characteristics of the oligo- to mesotrophic area. Contrary to the expected, the ambient nutrient concentration was not an important factor for controlling productivity in this area during the study period. The difference in productivity among stations was mainly due to the variations in phytoplankton biomass in different water masses.

• Journal of Soil and Groundwater Environment
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• v.17 no.5
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• pp.10-19
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• 2012

The aim of this study was to examine chemical and isotopic compositions of groundwater and lake water near an area contaminated by petroleum and to evaluate influence of petroleum on them during the period from March to August 2011. In dry season, $Ca^{2+}$ and $SO{_4}^{2-}$ were dominant in the groundwater and lake water and $Ca^{2+}$ and $HCO{_3}^-$ were significant in wet season. ${\delta}^{18}O$ and ${\delta}D$ of the groundwater and lake water were plotted near LMWL (${\delta}D=8.06{\delta}^{18}O+12.5$). ${\delta}^{18}O$ and ${\delta}D$ of the lake water did not show seasonal variation. However, ${\delta}^{18}O$ and ${\delta}D$ of the groundwater were enriched in wet season compared with those in dry season because of influence of small ponds around wells where evaporation losses were slightly experienced. Redox condition of most lake water was oxidation environment in contact with the atmosphere during the study period. However, redox condition of groundwater was transitional environment in dry season and oxidation environment in wet season because of influence of contaminant such as petroleum. In some groundwater, the concentrations of $NO{_3}^-$ in some groundwater were less than 1 mg/L because of denitrification. Also, $NO{_3}^-$ showed positive correlation with $SO{_4}^{2-}$ and weak negative correlation with $HCO{_3}^-$, because of influence of denitrification.

• Analytical Science and Technology
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• v.15 no.5
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• pp.417-426
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• 2002

Inductively Coupled Plasma Dynamic Reaction Cell Quadrupole Mass Spectrometry (ICP-DRC-QMS) was characterized for the detection of the six naturally occurring calcium isotopes. The effect of the operating conditions of the DRC system was studied to get the best signal-to-noise ratio. This experiment shows that the potentially interfering ions such as $Ar^+$, ${CO_2}^+$, ${NO_2}^+$, $CNO^+$ at the calcium masses m/z 40, 42, 43, 44 and 48 were removed by flowing $NH_3$ gas at the rate of 0.7 mL/min $NH_3$ as reactive cell gas in the DRC with a RPq value (rejection parameter) of 0.6. The limits of detection for $^{40}Ca$, $^{42}Ca$, $^{43}Ca$, $^{44}Ca$, and $^{48}Ca$ were 1, 29, 169, 34, and 15 pg/mL, respectively. This method was applied to the determination of calcium in synthetic food digest samples (CCQM-P13) provided by LGC for international comparison. The isotope dilution method was used for the determination of calcium in the samples. The uncertainty evaluation was performed according to the ISO/GUM and EURACHEM guidelines. The determined mean concentration and its expanded uncertainty of calcium was ($66.4{\pm}1.2$) mg/kg. In order to assess our method, two reference samples, Riverine Water reference sample (NRCC SLRS-3) and Trace Elements in Water reference sample (NIST SRM 1643d), were analyzed.

• Economic and Environmental Geology
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• v.26 no.4
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• pp.433-444
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• 1993

Electrum (32~73 atom. % Ag)-sulfide mineralization of the Bodeok mine in the Boseong area was deposited in two stages of mineralogically simple, massive quartz veins that fill the fractures along fault shear zones in Precambrian gneiss. Radiometric dating indicates that mineralization is Late Jurassic age ($155.9{\pm}2.3$ Ma). Fluid inclusion data show that ore mineralization was formed from $H_2O-CO_2$ fluids with variable $CO_2$ contents ($X_{CO_2}=0.0$ to 0.7) and low salinities (0.0 to 7.4 wt. % eq. NaCl) at temperatures between $200^{\circ}$ and $370^{\circ}C$. Evidence of fluid unmixing ($CO_2$ effervescence) indicates pressures up to 1 kbar. Gold-silver deposition occurred later than base-metal sulfide deposition, at temperatures near $250^{\circ}C$ and was probably a result of cooling and decreasing sulfur activity caused by sulfide precipitation and/or $H_2S$ loss (through fluid unmixing). Calculated sulfur isotope compositions of ore fluids (${\delta}^{34}S_{{\Sigma}S}=1.7$ to 3.3‰) indicate an igneous source of sulfur in hydrothermal fluids. Measured and calculated O and H isotope compositions of ore fluids (${\delta}^{18}O_{water}=4.8$ to 7.2‰, ${\delta}D_{water}=-73$ to -76‰) indicate that mesothermal auriferous fluids at Bodeok were likely mixtures of $H_2O-rich$, isotopically evolved meteoric waters and magmatic $H_2O-CO_2$ fluids.

• Bulletin of the Korean Chemical Society
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• v.24 no.1
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• pp.91-94
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• 2003

Kinetic studies of the reaction of O-methyl-S-phenylthiocarbonates with benzylamines in methanol at 45.0 ℃ have been carried out. The reaction proceeds by a stepwise mechanism in which the rate-determining step is the breakdown of the zwitterionic tetrahedral intermediate, $T^{\pm}$, with a hydrogen-bonded four-center type transition state (TS). These mechanistic conclusions are drawn based on (ⅰ) the large magnitude of ${\rho}_X\;and\;{\rho}_Z$, (ⅱ) the normal kinetic isotope effects $(k_H/k_D\;>\;1.0)$ involving deuterated benzylamine nucleophiles, (ⅲ) the positive sign of ${\rho}_{XZ}$ and the larger magnitude of ${\rho}_{XZ}$ than that for normal $S_N2$ processes, and lastly (ⅳ) adherence to the reactivity-selectivity principle (RSP) in all cases.

• Bulletin of the Korean Chemical Society
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• v.4 no.3
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• pp.120-123
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• 1983

The reaction of hexacyanoferrate (Ⅲ) with nitrotoluenes in aqueous acetic acid containing perchloric acid(1.0 M) at $50^{\circ}C$ gave the corresponding aldehyde as the major product. The order with respect to each of the reactants ― substrate, oxidant and acid ― was found to be unity. The Hammett plot yielded a ${\sigma}^+$ value of -1.30, and the kinetic isotope effect gave a $k_H/k_D$ value of 6.2. The pathway for the conversion of the nitrotoluenes to the products has been mechanistically visualized as proceeding through the benzylic radical intermediate, formed in the rate determining step of the reaction.

• Journal of the Korean Magnetic Resonance Society
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• v.25 no.1
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• pp.1-7
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• 2021

Employing of 13C stable-isotopes in NMR metabolomics can give unique splitting patterns and coupling constants information originated from 13C-13C coupling interaction that provide an important structural information regarding the cellular metabolic process. But it has been known that an undesirable signal distortion in 2D heteronuclear correlation study, due to 13C-13C interaction, hampers an analysis of the coupling information. Recently, we proposed J-scaled distortion-free heteronuclear single-quantum coherence (HSQC) sequence which provides a distortion-free 13C-13C coupling information with a selective resolution enhancement of JCC splitting. In this paper, we dicuss theoretical aspect and practical feature of J-scaled HSQC pulse sequence. The conceptual explanation of orgin of the signal distortion by 13C-13C coupling interaction and design of J-scaled HSQC through exemplified results are provided in brief.

• Bulletin of the Korean Chemical Society
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• v.35 no.8
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• pp.2263-2270
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• 2014

Solvolysis rate constants of 2-phenylethyl-(2-$PhCH_2CH_2OCOCl$, 1) and 2,2-diphenylethyl chloroformate (2,2-$Ph_2CHCH_2OCOCl$, 2), together with the previously studied solvolyses of ${\alpha}$- and ${\beta}$-substituted chloroformate ester derivatives, are reported in pure and binary solvents at $40.0^{\circ}C$. The linear free energy relationship (LFER) and sensitivities (l and m) to changes in solvent nucleophilicity ($N_T$) and solvent ionizing power ($Y_{Cl}$) of the solvolytic reactions are analyzed using the Grunwald-Winstein equation. The kinetic solvent isotope effects (KSIEs) in methanol and activation parameter values in various solvents are investigated for 1 and 2. These results support well the bimolecular pathway with same aspects. Furthermore, the small negative values of the entropies of activation of solvolysis of 1 and 2 in the highly ionizing aqueous fluoroalcohols are consistent with the ionization character of the rate-determining step, and the KSIE values of 1.78 and 2.10 in methanol-d indicate that one molecule of solvent acts as a nucleophile and the other acts as a general-base catalyst. It is found that the ${\beta}$-substituents in alkyl chloroformate are not the important factor to decide the solvolysis reaction pathway.