• Economic and Environmental Geology
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• v.38 no.6 s.175
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• pp.707-716
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• 2005

Organic geochemical analyses including Rock-Eval pyrolysis, elemental analysis and stable carbon isotope analysis were performed to evaluate the characteristics of organic matter in the ODP Leg 127 Site 794A sediments and to understand paleoceanographic changes. Based on the TOC contents, C/N ratio, HI vs. OI, $\delta^{13}C_{org}$ and C/S ratio, results imply that dark layers containing a large amount of terrigenous organic matter were deposited under the suboxic/anoxic conditions, whereas the light layers containing largely marine organic matter were deposited under the oxic conditions. These results indicate that increasing surface-productivity by the input of a large amount of terrigenous organic matter from adjacent continent led to the deposition of dark layers during the interglacial highstands, whereas marine primary production and dilution caused by Kosa from the China desert area led to the deposition of light layers with the decreased to terrigenous organic matter during the glacial lowstands.

• Economic and Environmental Geology
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• v.28 no.4
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• pp.337-350
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• 1995

The Hwacheon-ri mineralized area is located within the Cretaceous Gyeongsang Basin of the Korean peninsula. The mineralized area includes the Hwacheon, Daeweon, Kuryong and Cheongryong mines. Each of these mines occurs along copper-bearing hydrothermal quartz veins that crosscut late Cretaceous volcanic rocks, although some disseminated ores in host rocks also exist locally. Mineralization can be separated into three distinct stages (I, II, and III) which developed along preexisting fracture zones. Stage I is ore-bearing, whereas stages II and III are barren. The main phase of ore mineralization, stage I, can be classified into three substages (Ia, Ib and Ic) based on ore mineral assemblages and textures. Substage Ia is characterized by pyrite-arsenopyrite-molybdenite-pyrrhotite assemblage and is most common at the Hwacheon deposit. Substage Ib is represented by main precipitation of Cu, Zn, and Pb minerals. Substage Ic is characteristic of hematite occurrence and is shown only at the Kuryong and Cheongryong deposits. Some differences in the ore mineralization at each mine in the area suggest that the evolution of hydrothermal fluids in the area varied in space (both vertically and horizontally) with respect to igneous rocks relating the ore mineralization. Fluid inclusion data show that stage I ore mineralization mainly occurred at temperatures between ${\approx}350^{\circ}$ and ${\approx}200^{\circ}C$ from fluids with salinities between 9.2 and 0.5 wt.% eq. NaCl. In the waning period of substage Ia, the high temperature and salinity fluid gave way to progressively cooler, more dilute fluids of later substage Ib and Ic (down to $200^{\circ}C$, 0 wt.% NaCl). There is a systematic decrease in the calculated ${\delta}^{18}O_{H2O}$ values with paragenetic time in the Hwacheon-ri hydrothermal system from values of ${\approx}2.7$‰ for substage Ia, through ${\approx}-2.8$‰ for substage Ib, to ${\approx}-9.9$‰ for substage Ic. The ${\delta}D$ values of fluid inclusion water also decrease with decreasing temperature (except for the Daeweon deposit) from -62‰ (substage Ia) to -80‰ (substage Ic and stage III). These trends are interpreted to indicate the progressive cooler, more oxidizing unexchanged meteoric water inundation of an initial hydrothermal system which is composed of highly exchanged meteoric water. Equilibrium thermodynamic interpretation of the mineral assemblages with the variation in amounts of chalcopyrite through the paragenetic time, and the evolution of the Hwacheon-ri hydrothermal fluids indicate that the solubility of copper chloride complexes in the hydrothermal system was mainly controlled by the variation of temperature and $fo_2$ conditions.

• The Korean Journal of Petroleum Geology
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• v.3 no.1 s.4
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• pp.28-39
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• 1995

The objective of this study is to investigate the origin of the dolomite in the Pungchon Formation of the Choseon Supergroup near Taebaeg City, Kangwondo, Korea. The Pungchon Formation is composed of limestone, dolomitic limestone, and dolomite with thin beds of flat pebble conglomerate (FPC) and mudrock. Texturally, the dolomite in the Pungchon Formation can be divided into four types; 1) coarse-sized, xenotopic dolomite in massive dolomite, 2) medium-siEed, idiotopic dolomite in flat pebble conglomerate, 3) xenotopic dolomite replacing ooids, algalnodules, and echinoderms, and 4) the dolomite in mottled fabric. The dolomite in mottled fabric can be subdivided into three types; a) coarse-sized, xenotopic saddle dolomite cement, b) medium-sized, idiotopic, cloudy-centered, clear-rimmed (CCCR) dolomite, and c) coarse-sized, idiotopic dolomite. The carbon isotopic composition of the Pungchon dolomite is in the range of $-2.8-1.4\%_{\circ}(PBD)$, suggesting that the carbon isotopic composition was buffered by the preexisting marine carbonates. Lighter oxygen isotopic values ($\delta^{18}O-15.7-8.7\%_{\circ}, PBD$) indicate that the Pungchon dolomite may have formed under high temperature in a burial diagenetic environment. The higher initial $^{87}Sr/^{86}Sr$ ratio of the Pungchon dolomite (0.7010-0.7161) than that of the coeval Cambrian seawater (0.7088-0.7092) indicates that dolomitizing fluids had been modified from the isotopic exchange with continental crust. Low Sr and Na contents(<200 ppm) of dolomite agree well with previously reported data for burial dolomite. Hifh Fe and Mn contents of the dolomite support the idea that the Pungchon dolomite may have formed in a deep burial diagenetic environment.

• The Sea:JOURNAL OF THE KOREAN SOCIETY OF OCEANOGRAPHY
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• v.18 no.1
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• pp.40-46
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• 2013

The isotope ratios of $^{13}C/^{12}C$ and $^{18}O/^{16}O$ for a sample in a mass spectrometer are measured relative to those of a pure $CO_2$ reference gas (i.e., laboratory working standard). Thus, the calibration of a laboratory working standard gas to the international isotope scales (Pee Dee Belemnite (PDB) for ${\delta}^{13}C$ and Vienna Standard Mean Ocean Water (V-SMOW) for ${\delta}^{18}O$) is essential for comparisons between data sets obtained by other groups on other mass spectrometers. However, one often finds difficulties in getting well-calibrated standard gases, because of their production time and high price. Additional difficulty is that fractionation processes can occur inside the gas cylinder most likely due to pressure drop in long-term use. Therefore, studies on laboratory production of pure $CO_2$ isotope standard gas from stable solid calcium carbonate standard materials, have been performed. For this study, we propose a method to extract pure $CO_2$ gas without isotope fractionation from a solid calcium carbonate material. The method is similar to that suggested by Coplen et al., (1983), but is better optimized particularly to make a large amount of pure $CO_2$ gas from calcium carbonate material. The $CaCO_3$ releases $CO_2$ in reaction with 100% pure phosphoric acid at $25^{\circ}C$ in a custom designed, evacuated reaction vessel. Here we introduce optimal procedure, reaction conditions, and samples/reactants size for calcium carbonate-phosphoric acid reaction and also provide the details for extracting, purifying and collecting $CO_2$ gas out of the reaction vessel. The measurements for ${\delta}^{18}O$ and ${\delta}^{13}C$ of $CO_2$ were performed at Seoul National University using a stable isotope ratio mass spectrometer (VG Isotech, SIRA Series II) operated in dual-inlet mode. The entire analysis precisions for ${\delta}^{18}O$ and ${\delta}^{13}C$ were evaluated based on the standard deviations of multiple measurements on 15 separate samples of purified $CO_2$. The pure $CO_2$ samples were taken from 100-mg aliquots of a solid calcium carbonate (Solenhofen-ori $CaCO_3$) during 8-day experimental period. The multiple measurements yielded the $1{\sigma}$ precisions of ${\pm}0.01$‰ for ${\delta}^{13}C$ and ${\pm}0.05$‰ for ${\delta}^{18}O$, comparable to the internal instrumental precisions of SIRA. Therefore, we conclude the method proposed in this study can serve as a way to produce an accurate secondary and/or laboratory $CO_2$ standard gas. We hope this study helps resolve difficulties in placing a laboratory working standard onto the international isotope scales and does make accurate comparisons with other data sets from other groups.

• The Journal of Engineering Geology
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• v.19 no.4
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• pp.529-541
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• 2009

Hydrochemical, stable isotopic ($\delta^{18}O$ and dD) and noble gas isotopic analyses of seven hot spring water samples, eleven groundwater samples and six surface water samples collected from the Icheon and Pocheon area were carried out to find out hydrochemical characteristics, and to interpret the source of noble gases and the geochemical evolution of the hot spring waters. The hot spring waters show low temperature type ranging from 21.5 to $31.4^{\circ}C$ and the pH value between 6.69 and 9.21. Electrical conductivity of hot spring waters has the range from 310 to $735\;{\mu}S/cm$. Whereas the hot spring water in the Icheon area shows the geochemical characteristics of neutral pH, the $Ca-HCO_3$(or $Ca(Na)-HCO_3$) chemical type and a high uranium content, the hot spring water in the Pocheon area shows the characteristics of alkaline pH, the $Na-HCO_3$ chemical type and a high fluorine content. These characteristics indicate that the hot spring water in the Icheon area is under the early stage in the geochemical evolution, and that the hot spring water in the Pocheon area has been geochemically evolved. The $\delta^{18}O$ and ${\delta}D$ values of hot spring waters show the range of $-10.1{\sim}-8.69%o$ and from $-72.2{\sim}-60.8%o$, respectively, and these values supply the information of the recharge area of hot spring waters. The $^3He/^4He$ ratios of the hot spring waters range from $0.09\;{\times}\;10^{-6}$ to $0.65\;{\times}\;10^{-6}$ which are plotted above the mixing line between air and crustal components. Whereas the helium gas in the Icheon hot spring water was mainly provided from the atmospheric source mixing with the mantle(or magma) origin, the origin of helium gas in the Pocheon hot spring water shows a dominant crustal source. $^{40}Ar/^{36}Ar$ ratios of hot spring water are in the range of an atmosphere source.

• The Journal of Engineering Geology
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• v.15 no.4 s.42
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• pp.391-405
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• 2005

Chemical and isotopic analysis for stream water, shallow groundwater, intermediate groundwater and deep groundwater was carried out to grasp hydrogeochemical characteristics of groundwater in the Heunghae area, Pohang city. Water type of stream water and shallow groundwaters is typified as Ca-Cl type, intermediate groundwater is $Na-HCO_3$, and deep groundwater is prominent in Wa-Cl type. $HCO_3^-\;and\;SiO_2$ in shallow groundwater are originated from weathering of silicate minerals, whereas those of deep groundwaters are resulted from weathering of carbonate minerals. Ca and Mg ions in both shallow and deep groundwaters are resulted from weathering of calcite and dolomite. $SO_4^{2-}$ in shallow groundwater is originated mainly from pyrite oxidation. As well depth increases, pH and TDS increase, but Eh and DO decrease. Alkali metal contents(K, Na, Li) increases as well depth increases, but alkali earth metal(Mg, Ca) and hi concentrations increase as well depth decreases. Anions, halogen elements(F, Cl, Br), and $HCO_3$ contents increase as well depth increases. The average stable isotope value of the groundwater of each depth is as follows; deep groundwater: ${\delta}^{18}O=-10.1\%o,\;{\delta}D=-65.8\%_{\circ}$, intermediate groundwater: ${\delta}^{18}O=-8.9\%_{\circ},\;{\delta}D=-59.6\%_{\circ}$, shallow groungwater : ${\delta}^{18}O=-8.0\%_{\circ},\;{\delta}D=-53.6\%_{\circ}$, surface water : ${\delta}^{18}O=-7.9\%_{\circ},\;{\delta}D=-53.3\%_{\circ}$ respectively.

• Journal of the Korean Society of Groundwater Environment
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• v.5 no.4
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• pp.177-191
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• 1998

For various kinds of waters including surface water, shallow groundwater (＜70 m deep) and deep groundwater (500∼810 m deep) from the Pungki area, an integrated study based on hydrochemical, multivariate statistical, thermodynamic, environmental isotopic (tritium, oxygen-hydrogen, carbon and sulfur), and mass-balance approaches was attempted to elucidate the hydrogeochemical and hydrologic characteristics of the groundwater system in the gneiss area. Shallow groundwaters are typified as the 'Ca-HCO$_3$'type with higher concentrations of Ca, Mg, SO$_4$and NO$_3$, whereas deep groundwaters are the 'Na-HCO$_3$'type with elevated concentrations of Na, Ba, Li, H$_2$S, F and Cl and are supersaturated with respect to calcite. The waters in the area are largely classified into two groups: 1) surface waters and most of shallow groundwaters, and 2) deep groundwaters and one sample of shallow groundwater. Seasonal compositional variations are recognized for the former. Multivariate statistical analysis indicates that three factors may explain about 86% of the compositional variations observed in deep groundwaters. These are: 1) plagioclase dissolution and calcite precipitation, 2) sulfate reduction, and 3) acid hydrolysis of hydroxyl-bearing minerals(mainly mica). By combining with results of thermodynamic calculation, four appropriate models of water/ rock interaction, each showing the dissolution of plagioclase, kaolinite and micas and the precipitation of calcite, illite, laumontite, chlorite and smectite, are proposed by mass balance modelling in order to explain the water quality of deep groundwaters. Oxygen-hydrogen isotope data indicate that deep groundwaters were originated from a local meteoric water recharged from distant, topograpically high mountainous region and underwent larger degrees of water/rock interaction during the regional deep circulation, whereas the shallow groundwaters were recharged from nearby, topograpically low region. Tritium data show that the recharge time was the pre-thermonuclear age for deep groundwaters (＜0.2 TU) but the post-thermonuclear age for shallow groundwaters (5.66∼7.79 TU). The $\delta$$\^$34/S values of dissolved sulfate indicate that high amounts of dissolved H$_2$S (up to 3.9 mg/1), a characteristic of deep groundwaters in this area, might be derived from the reduction of sulfate. The $\delta$$\^$13/C values of dissolved carbonates are controlled by not only the dissolution of carbonate minerals by dissolved soil CO$_2$(for shallow groundwaters) but also the reprecipitation of calcite (for deep groundwaters). An integrated model of the origin, flow and chemical evolution for the groundwaters in this area is proposed in this study.

• The Journal of the Petrological Society of Korea
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• v.18 no.2
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• pp.79-91
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• 2009

Jurassic hornblende gabbo intrusives are distributed in Otanri, Chuncheon, and in Guwoonri, Hwacheon located in the northern part of Gyeonggi Massif. The intrusives composed mainly of amphiboles and plagioclase can be divided into two distinct rocks depending on the shape of amphiboles: (i) subspherical amphibole gabbro which has subspherical amphibole phenocryst as a major mafic phase(Sag); (ii) prismatic amphibole gabbro which has prismatic amphiboles as a principal mafic mineral(Pag). Subspherical amphiboles in Sag have higher Cr content and higher Mg($Mg+Fe^{2+}$) ratio relative to the prismatic amphiboles in Pag. This is indicative of conversion of pyroxene into amphibole with pyroxene pseudomorph. Oxygen isotopic results of plagioclase and amphibole separated from the hornblende gabbro suggest that theses minerals have experienced oxygen isotopic exchange with relatively heavy-$^{18}O$fluid for a long period, and magmatic fluid has been involved in the formation of subspherical amphiboles. Amphiboles in hornblende gabbro are composed of distinct species of pargasite, magnesiohornblende, actinolite, which formed at different stages.

• Journal of the Korean Society of Groundwater Environment
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• v.6 no.4
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• pp.171-179
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• 1999

The $CO_2$-rich waters in the Chojeong area are characterized by low pH (5.0~5.8), high $CO_2$pressure (about 1 atm) and high amounts of total dissolved iou (up to 989 mg/L) and chemically belong to Ca-HC $O_3$type. The oxygen. deuterium and tritium isotope data indicate that the mixing process occurred between $CO_2$-rich water and surface water and/or shallow groundwaters and also suggest that the $CO_2$-rich water has been derived from meteoric waters. According to $\delta$$^{13}$ C values (-8.6~-5.3$\textperthousand$). the $CO_2$ in the water is attributed from deep seated $CO_2$gas. The high dissolved carbon (-14.4~-6.8$\textperthousand$. $\delta$$^{13}$ C) in groundwater of the granitic terrain might be affected by $CO_2$-rich water, whereas the dissolved carbon (-17.9~-15.2$\textperthousand$. $\delta$$^{13}$ C) in groundwater of the metamorphic terrain is likely controlled by soil $CO_2$ and from the reaction with calcite in phyllite. Sulfur isotope data (＋3.5~＋11.3$\textperthousand$,$\delta$$^{34}$ $S_{SO4}$) also support the mixing process between $CO_2$-rich water and shallow groundwater. Strontium isotopic ratio ($^{87}$ Sr/$^{86}$ Sr) indicates that the $CO_2$-rich water (0.7138~0.7156) is not related to vein calcite (0.7184) of Buak mine or calcite (0.7281~0.7346) in phyllite. By nitrogen isotope ($\delta$$^{15}$ $N_{NO3}$) the sources of nitrogen (up to 55.0 mg/L, N $O_3$) in the $CO_2$-rich water are identified as fertilizer and animal manure. It also indicates the possibility of denitrification during the circulation of nitrogen in the Chojeong area. The possible evolution model of the $CO_2$-rich water based on the hydrochemical and environmental isotopic data was proposed in this study. The $CO_2$-rich waters from the Chojeong area were primarily derived from the reaction with granite by supply of deep seated $CO_2$. and then the $CO_2$-rich water was mixed and diluted with the local groundwater.ter.

• Economic and Environmental Geology
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• v.42 no.6
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• pp.527-539
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• 2009

The Kumho River flows through volcanic and sedimentary rocks at upstream and downstream regions and also through industrial district including dyeing complex before it meets the Nakdong River, and as a result, many factors can influence the geochemistry of river water. The concentrations of dissolved ions generally increased as it flows downstream. The concentrations of cations are in the order of Ca>Na>Mg>K, and those of anions are $HCO_3$>$SO_4$>Cl>$NO_3$. These results show that the weathering of sandstone and shale containing carbonate including calcite caused the enrichment of Ca and $HCO_3$. At first 4 sampling sites, Si contents are relatively high mainly due to the weathering of silicate minerals of volcanic rocks. However, Na and $SO_4$ contents are higher at downstream sites due to the industrial and municipal sewage. Piper diagram also shows that the geochemical patterns changed from Ca-$HCO_3$ to Ca-Cl/Ca-$SO_4$ and Na-Cl/Na-$SO_4$ type. When comparing the samples collected in May and July, the concentrations of dissolved ions in July are generally lower than those in May, which indicates that dilution by precipitation played an important role. In July the relative concentration of Ca increased, indicating that Ca in soils probably from fertilizer were mixed into the river water by precipitation. The river waters are mainly from precipitation. The dissolved ions are mainly from weathering of carbonate minerals and pollutants from municipal sewage and discharged water from industrial complex. The composition of oxygen and deutrium isotope in July showed higher values, which is contrary to the amount effect, maybe due to Youngchon Dam. The nitrogen isotope showed lower values in July than those in May, which can be interpreted to indicate mixing of nitrate from soils and fertilizer in the cultivated land by the heavy rain. The isotope composition of nitrate increased downstream, indicating that the influence of sewage and animal manure also increased downstream.