• Ocean and Polar Research
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• v.38 no.4
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• pp.331-338
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• 2016

Many studies using tracers have been conducted to understand a physical process in a system. Rain-on-snow could accelerate snowmelt processes, which influences the hydrological process in both temperate and polar regions. Hydrological and ecological conditions will be affected by the amount and timing of discharge reaching the bottom of a snowpack. The discharge consists of the rain-on-snow, pore water penetrating into the snowpack and natural meltwater. In this study, after a rain-on-snow experiment, we conducted an isotopic hydrograph separation to distinguish rainwater and pore water from meltwater. Using the isotopic data of snow and meltwater from Lee et al. (2010), two components were separated based on the assumption that rainwater and pore water are new water and natural meltwater is old water. After the second rain-on-snow experiment, the maximum contributions of rainwater and pore water reached up to 69% of the discharge and then decreased. During the study period, the measured total discharge was 4153 L and 40% (based on hydrogen isotope) of rainwater and pore water was calculated in the discharge, which is not consistent with what Lee et al. (2016) calculated using chemical separation (63%). This inconsistency can be explained by how an end-member was defined in both approaches. The contributions of artificial rainonsnow and pore water to melwater discharge range between the two methods. This study will suggest a mixing calculation from isotopic compositions of the Southern Ocean.

• Ceramist
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• v.22 no.4
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• pp.357-367
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• 2019

Secondary Ion Mass Spectrometry(SIMS) is an analytical method that measures the distribution and concentration of elements or compounds by analyzing the mass of secondary ions released by irradiating ion beams with energy of hundreds eV to 20 keV on the sample surface. Unlike other similar analytical instruments, SIMS directly detect the elemental ions that constitute a sample, allowing you to accurately identify components and obtain concentration information in the depth direction. It is also a great feature for measuring isotopes and analyzing light elements, especially hydrogen. In particular, with the development of materials science, there is an increasing demand for trace concentration analysis and isotope measurements in the micro-regions of various materials. SIMS has a short history compared to other similar methods; nevertheless, SIMS is still advancing in hardware and is expected to contribute to the development of materials science through research and development of advanced analytical techniques.

• Bulletin of the Korean Chemical Society
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• v.28 no.11
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• pp.2009-2014
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• 2007

The aminolysis of diphenyl thiophosphinic chloride (2) with substituted anilines in acetonitrile at 55.0 oC is investigated kinetically. Kinetic results yield large Hammett ρX (ρnuc = ?3.97) and Bronsted βX (βnuc = 1.40) values. A concerted mechanism involving a partial frontside nucleophilic attack through a hydrogen-bonded, four-center type transition state is proposed on the basis of the primary normal kinetic isotope effects (kH/kD = 1.0-1.1) with deuterated aniline (XC6H4ND2) nucleophiles. The natural bond order charges on P and the degrees of distortion of 42 compounds: chlorophosphates [(R1O)(R2O)P(=O)Cl], chlorothiophosphates [(R1O)(R2O)P(=S)Cl], phosphonochloridates [(R1O)R2P(=O)Cl], phosphonochlorothioates [(R1O)R2P(=S)Cl], chlorophosphinates [R1R2P(=O)Cl], and chlorothiophosphinates [R1R2P(=S)Cl] are calculated at the B3LYP/ 6-311+G(d,p) level in the gas phase.

• Economic and Environmental Geology
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• v.34 no.1
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• pp.13-23
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• 2001

Bentonite layers are intercalated within the basal conglomerates in the Tertiary sedimentary basins of Kampo, Janggi and Pohang, southeastern Korea. Eighteen samples of the bentonites went through X-ray diffraction, scanning electron microscopy, heavy mineral analyses, chemical analyses and oxygen, hydrogen stable isotope analyses to define the mineralogical characters of the bentonites. Heavy minerals such as zircons, apatites, amphiboles and biotites separated from bentonites show clean and euhedral surfaces, which are the characteristic features of volcanic origin. But biotites from the Chunbook Conglomerate are found as altered and heavily broken flakes which implies longer transportation of these bentonites. $TiO_{2}/Al_{2}O_{3} ratios of <2 $\mu$m particle fractions (the Chunbook Conglomerate 0.031; Janggi 0.029; Kampo 0.025) suggest that those are originated from volcanic tuffs. That is, the higher the value is, the more mafic in chemical compositions of the original tuffs. Authigenic montmorillonite and zeolite minerals were observed by SEM, which indicates diagenesis origin of bentonites. But the samples from the Chunbook Conglomerate showed only chaotically packed clay flakes in the matrix of sands or conglomerates, which implies detrital influence, not authigenic origin. The structural formulae of montmorillonite from these basins reflects their environment of formation. Fe (Ⅵ) can show the redox condition of its past environment and much lower $Fe^{2+}(Ⅵ)/Fe^{3+}(Ⅵ)$ ratios in montmorillonite of the Chunbook Conglomerate imply the greater oxidizing influence. Calculated burial depths from oxygen stable isotope data of the samples from the Chunbook Conglomerate generally fall to the range of 929~963 m whereas the real burial depth of this area is only 530~580 m. This could be explained as the bentonites of the Chunbook conglomerate had not been formed in situ. Discriminant analyses with the data from chemical analyses and structural formulae of montmorillonites show that bentonites from three different basins could definitely be distinguished with each other. This result arises from the different chemical compositions of original volcanic ashes and the difference of sedimentary environments.

• The Sea:JOURNAL OF THE KOREAN SOCIETY OF OCEANOGRAPHY
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• v.9 no.2
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• pp.64-72
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• 2004

We measured the vertical profiles of $O_2$, H$_2$S, and pH in sediment pore water beneath marine cage fish farms using a microsensor with a 25 ${\mu}{\textrm}{m}$ sensor tip size. The sediments are characterized by high organic material load. The oxygen consumption, hydrogen sulfide oxidation, and sulfate reduction rates in the microzonations (derived from the vertical distribution of chemical species concentration) were estimated by adapting a simple one-dimensional diffusion-reaction model. The oxygen penetration depth was 0.75 mm. The oxic microzonations were divided into upper and lower layers. Due to hydrogen sulfide oxidation within the oxic zone, the oxygen consumption rate was higher in the lower layer. The total oxygen consumption rate integrated with reaction zone depth was estimated to be 0.092 $\mu$mol $O_2$cm$^{-2}$ hr$^{-1}$ . The total hydrogen sulfide oxidation rate occurring within 0.7 mm thickness was estimated to be 0.030 $\mu$mo1 H$_2$S cm$^{-2}$ hr$^{-1}$ , and its turnover time in the oxic sediment layer was estimated to be about 2 minutes. This suggests that hydrogen sulfide was oxidized by both chemical and microbial processes in this zone. The molar consumption ratio, calculated to be 0.84, indicates that either other electron accepters exit on hydrogen sulfide oxidation, or elemental sulfur precipitation occurs near the $O_2$- H$_2$S interface. Total sulfate reduction flux was estimated to be 0.029 $\mu$mol cm$^{-2}$ hr$^{-1}$ , which accounted for more than 60% of total $O_2$ consumption flux. This result implied that the degradation of organic matter in the anoxic layer was larger than in the oxic layer.

• Economic and Environmental Geology
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• v.35 no.4
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• pp.299-316
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• 2002

The Samkwang gold-silver deposits consist of gold-silver-bearing hydrothermal massive quartz veins which filled the fractures along fault shear (NE, NW) zones within Precambrian banded or granitic gneiss of Gyeonggi massif. Ore mineralization of this deposits occurred within a single stage of quartz vein which was formed by multiple episodes of fracturing and healing. Based on vein mineralogy and paragenesis, massive quartz veins are divided into two main paragenetic stages which are separated by a major faulting event. Main ore mineralization occurred at stage I. Wall-rock alteration from this deposits occur as mainly sericitization, chloritization, silicification and minor amounts of pyritization, carbonitization, propylitization and argillitization. Ore minerals are composed mainly of arsenopyrite (29.21-32.24 As atomic %), pyrite, sphalerite (6.45-13.82 FeS mole %), chalcopyrite, galena with minor amounts of pyrrhotite, marcasite, electmm (39.98-66.82 Au atomic %) and argentite. Systematic studies of fluid inclusions in early quartz veins and microcracks indicate two contrasting physical-chemical conditions: 1). temperature (215-345$^{\circ}$C) and pressure (1296-2022 bar) event with $H_{2}O-CO_{2}-CH_{4}-NaCl$fluids (0.8-6.3 wt. %) related to the early sulfide deposition, 2). temperature (203-441$^{\circ}$C) and pressure (320 bar) event with $H2_{O}$-NaCI $\pm$ $CO_{2}$ fluids (5.7-8.8 wt. %) related to the late sulfide and electrum assemblage. The H20-NaCI $\pm$ $CO_{2}$ fluids represent fluids evolved through fluid unmixing of an $H_{2}O-CO_{2}-CH_{4}-NaCl$fluids due to decreases in fluid pressure and influenced of deepcirculated meteoric waters possibly related to uplift and unloading of the mineralizing suites. Calculated sulfur isotope compositions (${\delta}^{34}S_{fluid}$) of hydrothermal fluids (1.8-4.9$\textperthousand$) indicate that ore sulfur was derived from an igneous source. Measured and calculated oxygen and hydrogen isotope compositions (${\delta}^{18}O_{I120}$, ${\delta}D$) of ore fluids (-5.9~10.9$\textperthousand$, -102~-87$\textperthousand$) indicate that mesothermal auriferous fluids at Samkwang gold-silver deposits were likely mixtures of $H_{2}O$-rich, isotopically less evolved meteoric water and magmatic fluids.

• Economic and Environmental Geology
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• v.39 no.6 s.181
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• pp.653-662
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• 2006

Quartz veins from the Jukwangri area of Hwawon-myeon are epithermal quartz veins that are filling the NW or NE-trending faults within Precambrian metasedimentary rocks. Based on their prolongation and ore grades, No. 1 quartz vein can be traced for about 200 m and varies 0.1 to 3 m in thickness. Mineralization of No. 1 quartz vein can be divided into hypogene and supergene stages. Hypogene stage is associated with hydrothermal alteration minerals(phyllic and argillic zones) such as illite, sericite and sulfides such as pyrite, arsenopyrite, sphalerite. chalcopyrite, galena, argentian tetrahedrite. Supergene stage is composed of Fe-Mn oxide, Zn-Fe oxide and Pb oxide. Fluid inclusion data indicate that homogenization temperature and salinity of hypogene stage range from 187 to $306^{\circ}C$ and ken 0.0 to 6.2 wt.% eq. NaCl, respectively. They suggest that ore forming fluids were progressively cooled and diluted from mixing with meteoric water. Oxygen($-4.1{\sim}4.1%o$) and hydrogen($-107{\sim}-88%o$) isotope com-positions indicated that hydrothermal fluids were derived from meteoric and evolved by progressive mixing with meteoric water during mineralization.

• Economic and Environmental Geology
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• v.32 no.5
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• pp.469-483
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• 1999

Two different types of deep groundwaters occur together in the Jungwon area: $CO_2$-rich water and alkali water. Each water shows distrinct hydrogeochemical and environmental isotopic characteristics. The $CO_2$-rich waters are characterized by lower pH(6.0~6.4), higher Eh (25~85mV) and higher TDS content (up to 3,300 mg/l), whereas the alkali type waters have higher pH (9.1~9.5), lower Eh (-136~-128mV) and lower TDS content (168~254 mg/l). The CO2-rich waters ($Pco_2$=up to 1atm) were probably evolved by the local supply of deep $CO_2$ during the deep circulation, resulting in enhanced dissolution of surrounding rocks to yield high concentrations of $Ca^{2+}, Na^+, Mg^{2+}, K^+\; and \;HCO_3\;^-$ under low pH conditions. On the other hand, the alkali type waters ($Pco_2$=about 10-4.6 atm) were evolved through lesser degrees of simple wate/rock (granite) interaction under the limited suppy of $CO_2$. The alkali waters are relatively enriched in F- (up to 14mg/l), whereas the F- concentration of$CO_2$-rich water is lower (2.2~4.8 mg/l) due to the buffering by precipitation of fluorite. The oxygen-hydrogen isotopes and tritium data indicate that compared to shaltion ($\delta$18O=-9.5~-7.8$\textperthousand$),two different types fo deep groudwaters (<1.0TU)were both derived from pre-thermonuclear (more than 40 years old) meteoric waters with lighter O-H isotopic composition ($\delta$18O=-9.5~-7.8$\textperthousand$) and have evolved through prolonged water/rock interaction. The $CO_2$-rich waters also show some degrees of isotopic re-equilibration with $CO_2$ gas. The $\delta^{34}S$ values of dissolved sulfates (+24.2~+27.6$\textperthousand$) in the $CO_2$-rich waters suggest the reduction of sulfate by organic activity at depths. The carbon isotope data show that dissolved carbon in the $CO_2$-rich waters were possibly derived either from dissolution of calcite or from deep $CO_2$ gas. However, strontium isotope data indicate Ca in the $CO_2$-rich waters were derived mainly from plagioclase in granite, not from hydrothermal calcites.

• Economic and Environmental Geology
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• v.29 no.4
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• pp.411-419
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• 1996

The Janggun magnetite deposits occur as the lens-shaped magnesian skarn, magnetite and base-metal sulfide orebodies developed in the Cambrian Janggun Limestone Formation. The K-Ar age of alteration sericite indicates that the mineralization took place during late Cretaceous age (107 to 70 Ma). The ore deposition is divided into two stages as a early skarn and late hydrothermal stage. Mineralogy of skara stage (107 Ma) consists of iron oxide, base-metal sulfides, Mg-Fe carbonates and some Mg- and Ca-skarn minerals, and those of the hydrothermal stage (70 Ma) is deposited base-metal sulfides, some Sb- and Sn-sulfosalts, and native bismuth. Based on mineral assemblages, chemical compositions and thermodynamic considerations, the formation temperature, $-logfs_2$, $-logfo_2$ and pH of ore fluids progressively decreased and/or increased with time from skarn stage (433 to $345^{\circ}C$, 8.8 to 9.9 atm, 29.4 to 31.6 atm, and 6.1 to 7.2) to hydrothermal stage (245 to $315^{\circ}C$, 11.2 to 12.3 atm, 33.6 to 35.4 atm, and 7.3 to 7.8). The ${\delta}^{34}S$ values of sulfides have a wide range between 3.2 to 11.6‰. The calculated ${\delta}^{34}S_{H_2S}$ values of ore fluids are relatively homo-geneous as 2.9 to 5.4‰ (skam stage) and 8.7 to 13.5‰ (hydrothermal stage), which are a deep-seated igneous source of sulfur indicates progressive increasing due to the mixing of oxidized sedimentary sulfur with increasing paragenetic time. The ${\delta}^{13}C$ values of carbonates in ores range from -4.6 to -2.5‰. Oxygen and hydrogen isotope data revealed that the ${\delta}^{38}O_{H_2O}$ and ${\delta}D$ values of ore fluids decreased gradually with time from 14.7 to 1.8‰ and -85 to -73‰ (skarn stage), and from 11.1 to -0.2‰ and -87 to -80‰ (hydrothermal stage), respectively. This indicates that magmatic water was dominant during the early skarn mineralization but was progressively replaced by meteoric water during the later hydrothermal replacement.

• Economic and Environmental Geology
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• v.25 no.3
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• pp.233-243
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• 1992

Ore mineralization of the Hwanghak copper deposit in the Ogsan area occurred in three stages of quartz (stage I and II) and calcite (stage III) veining along fissures in Early Cretaceous sedimentary rocks. Ore minerals are pyrite, pyrrhotite, chalcopyrite (dominant), sphalerite, hematite, galena, and Ag-, Pb-, and Bi-sulfosalts. These were deposited during the first stage at temperatures between $370^{\circ}C$ and < $200^{\circ}C$ from fluids with salinities between 0.5 and 7.6 equiv. wt. % NaCl. There is evidence of boiling and this suggests pressures of less than 180 bars during the first stage. Equilibrium thermodynamic interpretation accompanying with mineral paragenesis and fluid inclusion data indicates that copper precipitation in the hydrothermal system occurred due to cooling and changing in chemical conditions ($fs_2$, $fo_2$, pH). Gradual temperature decrease from $350^{\circ}$ to $250^{\circ}C$ of ore fluids by boiling and mixing with less-evolved meteoric waters mainly led to copper deposition through destabilization of copper chloride complexes. Sulfur isotope values of sulfide minerals decrease systematically with paragenetic time from calculated ${\delta}^{34}S_{H_2S}$ values of 8.2 to 4.7‰. These values, together with the observed change from sulfide-only to sulfide-hematite assemblages and fluid inclusion data, suggest progressively more oxidizing conditions, with a corresponding increase of the $sulfate/H_2S$ ratio of hydrothermal fluids. Measured and calculated hydrogen and oxygen isotope valutls of ore-forming fluids suggest meteoric water dominance, approaching unexchanged meteoric water values.