• Title/Summary/Keyword: Oxygen-hydrogen isotope

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Talc Mineralization in the Middle Ogcheon Metamorphic Belt (II) : Poongjeon Talc Deposit (중부옥천변성대의 활석광화작용에 관한 연구 (II) : 풍전활석광상을 중심으로)

  • Park, Hee-In;Lee, In Sung;Hur, Soon Do;Shin, Dong Bok
    • Economic and Environmental Geology
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    • v.30 no.6
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    • pp.543-551
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    • 1997
  • Poongjeon talc deposits is emplaced in dolomite and dolomitic limestone of the Cambro-Ordovician Samtaesan Formation. Ore in Poongjeon is low grade talc and the deposit has been known as the contact metasomatic or hydrothermal replacement type related to the intrusion of late Cretaceous granite in this area. X-ray diffraction, electron microprobe analysis, fluid inclusion and stable isotope analysis were utilized to examine the mineralogy of the ore and the origin of the ore fluid. The ore from Poongjeon mine mainly consists of talc and tremolite with minor amount of illite, vermiculite, smectite, and chlorite-vermiculite mixed layer. Occurrence of ore body indicates that the talc-tremolite ore was formed through the replacement by the $SiO_2$-rich hydrothermal fluid along the bedding and dike boundaries, or contact of amphibolite and basic dike with carbonate rocks. The temperature and pressure of the ore forming fluids at the time of the talc mineralization were estimated as $350^{\circ}C$ and 400 bar, respectively, based on the heating and freezing data of the fluid inclusions in quartz from talc-tremolite veins. During the talc-tremolite formation, fluids were divided into $CO_2$-enriched fluid and $CO_2$-poor fluid from $CO_2$ immiscibility (or effervescence). Oxygen isotope values (${\delta}^{18}O$) of the talc-tremolite fall within a range between 12.2 and 12.9‰. Hydrogen isotope values(${\delta}D$) of the ore range from -60 to -85‰ and $H_2O$ contents range from 2.0 to 3.4 wt.%. ${\delta}^{18}O$ and ${\delta}D$ values of talc ore indicate that the hydrothermal fluid involved in talc-tremolite formation was of igneous origin. Oxygen and hydrogen isotopic exchange between talc ore and the surface water was negligible after talc-tremolite ore formation.

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Nitrate Contamination of Confined Groundwaters: Application of Nitrogen, Oxygen, and Hydrogen Isotopes (피압대수층 지하수내 질소함유 원인연구: 질소, 산소, 수소동위원소 적용)

  • 추창오;이병대;조병욱;성익환;지세정
    • The Journal of Engineering Geology
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    • v.12 no.3
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    • pp.285-294
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    • 2002
  • The origin of nitrate in confined groundwater was studied using oxygen ($\delta$180), hydrogen ($\delta$D), and nitrogen ($\delta$15N) stable isotopes, along with chemical data of NO3-N. We analyzed groundwaters from more than sixty manufactories producing natural mineral waters around the country During the period of 1998-2001, an average value of nitrate was fair]y low (0.95 mg/$\ell$), however, groundwaters from six sites showed more than 2 mg/$\ell$ of nitrate. The stable isotope data of the groundwaters are -8.3~-11 $\textperthousand$ $\delta$8O, -60~-75 $\textperthousand$ $\delta$D, which lies in an average range of the groundwaters. The nitrogen isotope data with -11.8~-5.1$\textperthousand$ $\delta$15N suggest that manure, organic nitrate, and fertilizers can not be the origin of nitrate in the goundwaters.

A Study on the Recharge Characteristics of Groundwater in the Jeju Samdasoo Watershed Using Stable Water Isotope Data (안정동위원소를 이용한 제주삼다수 유역의 지하수 함양 특성 연구)

  • Shin, Youngsung;Kim, Taehyeong;Moon, Suhyung;Yun, Seong-Taek;Moon, Dukchul;Han, Heejoo;Kang, Kyounggu
    • Journal of Soil and Groundwater Environment
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    • v.26 no.3
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    • pp.25-36
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    • 2021
  • This study evaluated monthly, seasonal and altitudinal changes of oxygen and hydrogen isotope compositions of wet precipitation samples (n = 238) that were collected for last four years from 7 altitudes (from 265 to 1,500 m above sea level) in the Jeju Samdasoo watershed at the southeastern part of Jeju island, in order to examine the recharge characteristics of groundwater that is pumped out for the production of the Samdasoo drinking mineral water. Precipitation samples showed a clear seasonal change of O-H isotopic composition as follow, due to the different air masses and relative humidity: 𝛿D = 7.3𝛿18O + 11.3 (R2 = 0.76) in the wet season (June to September), while 𝛿D = 7.9𝛿18O + 9.5 (R2 = 0.91) in the dry season (October to May). In contrast, the stable isotope compositions of groundwater were nearly constant throughout the year and did not show a distinct monthly or seasonal change, implying the well-mixing of infiltrated water during and after its recharge. An altitudinal effect of the oxygen isotope compositions of precipitation was also remarkable with the decrease of -0.19‰ (R2 = 0.91) with the elevation increase by 100 m. Based on the observed altitudinal change, the minimum altitude of groundwater recharge was estimated as 1,200 m above the sea level in the Jeju Samdasoo watershed.

Kinetic Isotope Effects Involving Deuterated Benzylamine Nucleophiles

  • Lee, Ik-Choon;Koh, Han-Joong;Sohn, Dong-Sook;Lee, Byung-Choon
    • Bulletin of the Korean Chemical Society
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    • v.12 no.1
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    • pp.101-103
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    • 1991
  • The kinetic isotope effects (KIE) are determined for the reactions of benzyl benzenesulfonates (BBS), ethyl benzenesulfonates (EBS) and phenacyl benzensulfonates (PAB) with deuterated benzylamine nucleophiles. The inverse secondary ${\alpha}$-deuterium KIE observed were somewhat smaller than those for the corresponding reactions with aniline nucleophiles. The primary $KIE_s$ obtained with PAB were slightly greater than those for the corresponding reactions with anilines, which suggested that the inverse secondary KIE is decreased due to a relatively earlier transition state for bond-making with little change in the hydrogen bonding strength to the carbonyl oxygen.

Oxygen and Hydrogen Isotopic Compositions of the Hwacheon Granite (화천화강암의 산소와 수소 동위원소 조성)

  • Park Young-Rok;Ko Bokyun
    • The Journal of the Petrological Society of Korea
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    • v.13 no.4
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    • pp.214-223
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    • 2004
  • Oxygen and hydrogen isotopic compositions of the Jurassic peraluminous Hwacheon granite were measured, and compared with those of other Jurassic peraluminous Daebo granite in Korea. $\delta$$\^$18/O values for quartz and feldspar of the Hwacheon granite range from 8.2 to 10.6 and 5.8 to 9.0$\textperthousand$, respectively. Whole rock $\delta$$\^$18/O values for banded biotite gneiss country rocks surrounding the Hwacheon granites range from 8.1 to 9.4$\textperthousand$. Whole rock and biotite $\delta$D Values for Hwacheon granite range from -84 to -113 and -107 to -113$\textperthousand$, respectively. Whole rock $\delta$D values for banded biotite gneiss country rocks range from -76 to -100$\textperthousand$. Both $\delta$$\^$18/O and $\delta$D values of the Hwacheon granite are characterized by low values compared to the 'normal' values for the fresh peraluminous granitic rocks. Low $\delta$$\^$18/O values of the Hwacheon granite resulted from fluid-rock interaction for a long period. Isotopic modelling result renders that a relatively low-$\delta$$\^$18/O fluid below -1$\textperthousand$ was involved in subsolidus isotopic exchange under a relatively high fluid/rock ratio (<-6). The fluid of meteoric origin has experienced a modification of oxygen isotopic composition as a result of fluid-rock interaction with the Hwacheon granite and surrounding metapelitic country rocks.

Seasonal Variation of Surface Water Quality in a Catchment Contaminated by $NO_3-N$ (질산성 질소로 오염된 소유역 하천 수질의 계절 변화)

  • Kim Youn-Tae;Woo Nam-Chil;Lee Kwang-Sik;Song Yun-Goo
    • Journal of Soil and Groundwater Environment
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    • v.10 no.2
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    • pp.20-27
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    • 2005
  • The seasonal variation of water quality was studied in the Hwabongcheon. It runs though a small catchment where shallow groundwater was contaminated with $NO_3-N$ by intensive livestock facilities. A direct inflow of animal waste and incoming of contaminated groundwater affected its water quality. In the dry season, an important factor of water quality in the Hwabongcheon was direct inflow of animal waste. In the wet season, concentrations of $NO_3-N$ in the Hwabongcheon were elevated in spite of being diluted by precipitation. It could be explained by the effect of increased incoming of contaminated groundwater and showed by oxygen and hydrogen isotope values. $NO_3-N$ concentration in the Cheongmicheon was lower than that in the Hwabongcheon, so it increased next a junction. This effect was intense in wet season because $NO_3-N$ concentration in the Hwabongcheon was high.

Oxygen and Hydrogen Isotope Studies of the Hydrothermal Clay Deposits and Surrounded Rocks in the Haenam Area, Southwestern Part of the Korean Peninsula (한국 서남부, 해남지역의 열수 점토광상과 주변암에 대한 산소 및 수소동위원소 연구)

  • Kim, In Joon;Kusakabe, Minoru
    • Economic and Environmental Geology
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    • v.26 no.1
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    • pp.11-20
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    • 1993
  • In the present study, three representative hydrothermal clay deposits, named the Seongsan, Ogmaesan and Haenam deposits, were selected for oxygen and hydrogen isotope studies. Oxygen and hydrogen isotopic compositions of quartz, sericite, alunite and kaolin minerals from Seongsan, Ogmaesan, Haenam deposits and surrounded rocks of clay deposits have been measured. The ${\delta}^{18}O$ values of quartz, kaolin, sericite and alunite in the Seongsan mine are +8.4 to +11.1‰, +3.6 to 5.4‰, +4.8 to +5.8‰ and + 3.0 to +6.6‰, respectively. In the Ogmaesan mine, the ${\delta}^{18}O$ values of quartz, kaolin, sericite and alunite are +8.0 to +13.6‰, +2.8 to +6.7‰, +4.8 to +8.4‰ and +0.9 to +2.4‰, respectively. The ${\delta}^{18}O$ values of the Haenam mine range from +7.9 to +10.1‰ for quartz and from +4.5 to +6.5‰ for sericite. The ${\delta}^{18}O$ values of the whole-rocks range from + 3.0 to + 7.8‰ for the granitic rocks. The ${\delta}^{18}O$ values of the whole-rocks range from + 3.2 to + 10.7‰ for the volcanic rocks. The 8D values of kaolin, sericite and alunite in the Seongsan mine are -78 to -86‰, -71 to -90‰ and -43 to -77‰, respectively. In the Ogmaesan mine, the ${\delta}D$ values of kaolin, sericite and alunite are -73 to -80‰, -74 to -88‰ and -57 to -98‰, respectively. The ${\delta}D$ values of the Haenam mine range from -76 to -85‰ for sericite. The ${\delta}D$ values of the whole-rocks range from -77 to -105‰ for the granitic rocks. The ${\delta}D$ values of the wholerocks range from -76 to -100‰ for the volcanic rocks. The main result obtained oxygen and hydrogen isotope data can lead to the following interpretations on the origin of hydrothermal fluids in the clay deposits: Through the oxygen isotopic study, the formation temperature of the clay deposits was estimated from the coexisting minerals such as quartz-kaolin minerals and -sericite. Formation temperature of the acidic alteration zone is 165 to $280^{\circ}C$ in the Seongsan deposits, 175 to $250^{\circ}C$ in the Ogmaesan deposits and 250 to $350^{\circ}C$ in the Haenam deposits. Three clay deposits has been formed by magmatic water mixed with meteoric water. Furthermore, from this isotopic data, it is clarified that kaolin minerals and alunite are hypogene in origin, and has been formed by oxidation of hydrogen sulfide in the steam-heated environment, and that alunite has been produced in the spectacular solfataric alteration observed at the surface of some present-day hydrothermal systems. Oxidation of the $H_2S$ is thought to be generated when the vapor phase generated by boiling of the deep-seated water under the water table.

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Oxygen and Hydrogen Isotope Studies of Fluid-Rock Interaction of the Radons-Sancheong Anorthositic Rocks (하동-산청 회장암질암의 유체-암석 상호반응에 대한 산소와 수소 동위원소 연구)

  • Park Young-Rok;Ko Bokyun;Lee Kwang-Sik
    • The Journal of the Petrological Society of Korea
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    • v.13 no.4
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    • pp.224-237
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    • 2004
  • The anorthositic rocks of the study area are divided into the northern Sancheong and southern Hadong anorthositic rocks depending on the different distribution patterns and lithologies. In order to evaluate the characteristics of the hydrothermal systems developed in the study area, oxygen and hydrogen isotopic compositions of the anorthositic rocks were measured. Oxygen isotopic values of the plagioclase exhibit an interesting spatial distribution. Plagioclase collected from the Sancheong anorthositic rocks in the northern part tends to have a relatively restricted range of $\delta$$^{18/0}$ values between 7.3 and 8.8$\textperthousand$, which are heavier than 'normal' $\delta$$^{18/O}$ value (6-6.5$\textperthousand$) typical for plagioclase of the fresh mantle-derived anorthosite, whereas plagioclase from the southern part is characterized by a wide range of $\delta$$^{18/O}$ values between -4.4 and 8.2$\textperthousand$ and much lighter values than 'normal' value for plagioclase of the fresh mantle-derived anorthosite. Plagioclase from the middle part has $\delta$$^{18/O}$ values heavier than the plagioclase from the southern part, but lighter than that from the northern part. The spatial distribution of $\delta$$^{18/O}$ values suggests that the decoupled hydrothermal flow systems might have been developed in the study area. Meteoric water dominated in the hydrothermal flow systems developed in the southern area, whereas magmatic fluid dominated in the northern area. The relationship between water content and hydrogen isotopic composition of anorthosites shows a positive correlation. The positive correlation indicates that fluids exsolved from magma during magmatic differentiation caused deuteric alteration of anorthositic rocks involving replacement of pyroxenes to amphiboles. After the deuteric alteration, hydrothermal system developed by meteoric water dominated the southern area, and erased record of the hydrothermal system developed by magmatic fluid at earlier stage. However, the development of meteoric hydrothermal system has been limited in the southern area only, and could not affect the Sancheong anorthositic rocks in the northern area. The abundant occurrences of secondary alteration minerals such as sericite, calcite, and chlorite in the southern Hadong anorthosite relative to the northern Sancheong anorthositc seem to be related to the overlapping of two distinct hydrothermal systems in the southern area.

Gold-Silver Mineralization of the Mujeong Mine, Korea (무정광산의 금-은 광화작용)

  • 김상중
    • Economic and Environmental Geology
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    • v.32 no.3
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    • pp.237-245
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    • 1999
  • The Mujeong au-Ag hydrothermal vein type deposits occur within the Teriary igneous rocks of the Janggi basin. Ore minerals consist of pyrite, pyrrhotite, sphalertite, chalcopyrite, galena, cosalite, lillianite, argentite and electrum, and associated with epidotization, sericitization and pyritization. Fluid inclusion studies reveal that ore fluids were low saline with a simple NaCl-$H_{2}O$ system. Fluid inclusion data indicate that homogenization temperatures and salinities of fluid are 150 to $340^{\circ}C$ and 1.0 to 6.5wt.% NaCl equivalent, respectively. Sulfur isotope compositions of sulfied minerals ( ${\delta}^{34}S$=6.2 to 9.6$\textperthousand$) indicate that the ${\delta}^{34}S_{H2S}$ value of ore fluids was about 10.4$\textperthousand$. This ${\delta}^{34}S_{H2S}$ value is likely consistent with and hydrothermal sulfur, whereas the fluids were highly influenced by mixing with meteoric water. Measured and calculated oxygen and hydrogen isotope values (${\delta}^{18}O_{H2O}$=-2.7 to 3.4 $\textperthousand$, ${\delta}D_{H2O}$ = -83.6 to -52.7 $\textperthousand$) of ore forming fluids suggest mixing with hydrothermal and meteoric water. Equilibrium thermodynamic interpretation by mineral assemblages and chemistry indicates that sulfur fugacities (-log $fs_2$) ore forming fluids range from 9.0 to 12.6 atm stage II.

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Nucleophilic Substitution Reactions of N-Methyl α-Bromoacetanilides with Benzylamines in Dimethyl Sulfoxide

  • Adhikary, Keshab Kumar;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • v.32 no.3
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    • pp.857-862
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    • 2011
  • Kinetic studies of the reactions of N-methyl-Y-${\alpha}$-bromoacetanilides with substituted X-benzylamines have been carried out in dimethyl sulfoxide at $25.0^{\circ}C$. The Hammett plots for substituent X variations in the nucleophiles (log $k_N$ vs ${\sigma}_X$) are slightly biphasic concave upwards/downwards, while the Bronsted plots (log $k_N$ vs $pK_a$) are biphasic concave downwards with breakpoints at X = H. The Hammett plots for substituent Y variations in the substrates (log $k_N$ vs ${\sigma}_Y$) are biphasic concave upwards/downwards with breakpoints at Y = H. The cross-interaction constant $\rho_{XY}$ values are all negative: $\rho_{XY}$ = -0.32 for X = Y = electron-donating; -0.22 for X = electron-withdrawing and Y = electron-donating; -1.80 for X = electron-donating and Y = electronwithdrawing; -1.43 for X = Y = electron-withdrawing substituents. Deuterated kinetic isotope effects are primary normal ($k_H/k_D$ > 1) for Y = electron-donating, while secondary inverse ($k_H/k_D$ < 1) for Y = electronwithdrawing substituent. The proposed mechanisms of the benzylaminolyses of N-methyl-Y-${\alpha}$-bromoacetanilides are a concerted mechanism with a five membered ring TS involving hydrogen bonding between hydrogen (deuterium) atom in N-H(D) and oxygen atom in C = O for Y = electron-donating, while a concerted mechanism with an enolate-like TS in which the nucleophile attacks the ${\alpha}$-carbon for Y = electronwithdrawing substituents.