• Title/Summary/Keyword: 마그마 기원의 열수

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The Origin and Evolution of the Mesozoic Ore-forming Fluids in South Korea: Their Genetic Implications (남한의 중생대 광화유체의 기원과 진화특성: 광상 성인과의 관계)

  • Choi, Seon-Gyu;Pak, Sang-Joon
    • Economic and Environmental Geology
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    • v.40 no.5
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    • pp.517-535
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    • 2007
  • Two distinctive Mesozoic hydrothermal systems occurred in South Korea: the Jurassic/Early Cretaceous(ca. $200{\sim}130$ Ma) deep-level ones during the Daebo orogeny and the Late Cretaceous/Tertiary(ca. $110{\sim}45$ Ma) shallow hydrothermal ones during the Bulgugsa event. The Mesozoic hydrothermal system and the metallic mineralization in the Korean Peninsula document a close spatial and temporal relationship with syn- to post-tectonic magmatism. The calculated ${\delta}^{18}O_{H2O}$ values of the ore-forming fluids from the Mesozoic metallic mineral deposits show limited range for the Jurassic ones but variable range for the Late Cretaceous ones. The orogenic mineral deposits were formed at relatively high temperatures and deep-crustal levels. The mineralizing fluids that were responsible for the formation of theses deposits are characterized by the reasonably homogeneous and similar ranges of ${\delta}^{18}O_{H2O}$ values. This implies that the ore-forming fluids were principally derived from spatially associated Jurassic granitoids and related pegmatite. On the contrary, the Late Cretaceous ferroalloy, base-metal and precious-metal deposits in the Taebaeksan, Okcheon and Gyeongsang basins occurred as vein, replacement, breccia-pipe, porphyry-style and skarn deposits. Diverse mineralization styles represent a spatial and temporal distinction between the proximal environment of subvolcanic activity and the distal to transitional condition derived from volcanic environments. The Cu(-Au) or Fe-Mo-W deposits are proximal to a magmatic source, whereas the polymetallic or the precious-metal deposits are more distal to transitional. On the basis of the overall ${\delta}^{18}O_{H2O}$ values of various ore deposits in these areas, it can be briefed that the ore fluids show very extensive oxygen isotope exchange with country rocks, though the ${\delta}D_{H2O}$ values are relatively homogeneous and similarly restricted.

Geologic, Fluid Inclusion, and Sulfur Isotopic Studies of Hydrothermal Deposit in the Tanggueng District, West Java, Indonesia (인도네시아 서부자바 땅긍(Tanggueng)지역 열수광상의 지질, 유체포유물 및 황동위원소 연구)

  • Jae-Ho Lee;In-Joon Kim
    • Economic and Environmental Geology
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    • v.36 no.5
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    • pp.321-328
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    • 2003
  • The epithermal gold and base metal deposit of the Tanggeung district of West Java consists of four major veins(Celak, Cigodobras, Cilangkap and Pasirbedil) with NS to N10$^{\circ}$∼20$^{\circ}$E and N75$^{\circ}$W strikes. The veins occur within fractures cutting the crystal and lithic tuff of Jampang Formation(Oligo-Miocene) in and around the Mt. Subang of the western Java, Indonesia. The ore mineralization is characterized by the occurrence of pyrite, sphalerite, galena, chalcopyrite, and small amounts of bornite and Fe-oxides. Hydrothermal alteration, associated with the mineralization, was dominantly silicified and enveloped by the phyllitic(sericitic), argillic and propylitic alteration containing the disseminated pyrite. Gangue minerals consist of interstratified smectite-illite, chlorite, sericite, and minor kaolinite. The presence of vapor-rich fluid inclusions in quartz veins suggests that boiling occurred locally throughout ore deposition. Fluid inclusion studies suggest that the ore fluid evolved from initial high temperatures(〓34$0^{\circ}C$) to later lower temperatures(〓19$0^{\circ}C$). Salinities range from 0.0 to 8.3 wt percent NaCl equiv. The relatively high increase in salinity(up to 8.3 wt percent NaCl equiv) might be explained by a local boiling and by a participation of magmatic fluids, supported by the sulfur isotope results. Evidence of fluid boiling suggests that the pressure decreased from 200 bars to 120 bars. This corresponds to the depths of approximately 750 to 1,200 m in a hydrothermal system that changed from lithostatic to hydrostatic conditions. Using homogenization temperatures and paragenetic constraints, the calculated $\delta$$^{34}$ S values of $H_2S$ in ore fluid are -0.2 to 1.8 permil close to the 0 permil isotopic value of magmatic sulfur.

Mesothermal Gold Mineralization in the Boseong-Jangheung area, Chollanamdo-province (전라남도 보성-장흥지역의 중열수 금광화작용)

  • 허철호;윤성택;소칠섭
    • Economic and Environmental Geology
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    • v.35 no.5
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    • pp.379-393
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    • 2002
  • Within the Boseong-Jangheung area of Korea, five hydrothermal gold (-silver) quartz vein deposits occur. They have the characteristic features as follows: the relatively gold-rich nature of e1ectrurns; the absence of Ag-Sb( -As) sulfosalt mineral; the massive and simple mineralogy of veins. They suggest that gold mineralization in this area is correlated with late Jurassic to Early Cretaceous, mesothermal-type gold deposits in Korea. Fluid inclusion data show that fluid inclusions in stage I quartz of the mine area homogenize over a wide temperature range of 200$^{\circ}$ to 460$^{\circ}$C with salinities of 0.0 to 13.8 equiv. wt. % NaCI. The homogenization temperature of fluid inclusions in stage II calcite of the mine area ranges from 150$^{\circ}$ to 254$^{\circ}$C with salinities of 1.2 to 7.9 equiv. wt. % NaCI. This indicates a cooling of the hydrothermal fluid with time towards the waning of hydrothermal activity. Evidence of fluid boiling including CO2 effervescence indicates that pressures during entrapment of auriferous fluids in this area range up to 770 bars. Calculated sulfur isotope composition of auriferous fluids in this mine area (${\delta}^34S$_{{\Sigma}S}$$\textperthousand$) indicates an igneous source of sulfur in auriferous hydrothermal fluids. Within the Sobaegsan Massif, two representative mesothermal-type gold mine areas (Youngdong and Boseong-Jangheung areas) occur. The ${\delta}^34S values of sulfide minerals from Youngdong area range from -6.6 to 2.3$\textperthousand$ (average=-1.4$\textperthousand$, N=66), and those from BoseongJangheung area range from -0.7 to 3.6$\textperthousand$ (average=1.6$\textperthousand$, N=39). These i)34S values of both areas are comparatively lower than those of most Korean metallic ore deposits (3 to 7TEX>$\textperthousand$). And, within the Sobaegsan Massif, the ${\delta}^34S values of Youngdong area are lower than those of Boseong-Jangheung area. It is inferred that the difference of ${\delta}^34S values within the Sobaegsan Massif can be caused by either of the following mechanisms: (1) the presence of at least two distinct reservoirs (both igneous, with ${\delta}^34S values of < -6 $\textperthousand$ and 2$\pm$2 %0) for Jurassic mesothermal-type gold deposits in both areas; (2) different degrees of the mixing (assimilation) of 32S-enriched sulfur (possibly sulfur in Precambrian pelitic basement rocks) during the generation and/or subsequent ascent of magma; and/or (3) different degrees of the oxidation of an H2S-rich, magmatically derived sulfur source ${\delta}^34S = 2$\pm$2$\textperthousand$) during the ascent to mineralization sites. According to the observed differences in ore mineralogy (especially, iron-bearing ore minerals) and fluid inclusions of quartz from the mesothermal-type deposits in both areas, we conclude that pyrrhotite-rich, mesothermal-type deposits in the Youngdong area formed from higher temperatures and more reducing fluids than did pyrite(-arsenopyrite)-rich mesothermal-type deposits in the Boseong-Jangheung area. Therefore, we prefer the third mechanism than others because the ${\delta}^34S values of the Precambrian gneisses and Paleozoic sedimentary rocks occurring in both areas were not known to the present. In future, in order to elucidate the provenance of ore sulfur more systematically, we need to determine ${\delta}^34S values of the Precambrian metamorphic rocks and Paleozoic sedimentary rocks consisting the basement of the Korean Peninsula including the Sobaegsan Massif.

Geochemistry of Geothermal Waters in Korea: Environmental Isotope and Hydrochemical Characteristics I. Bugok Area (한반도 지열수의 지화학적 연구: 환경동위원소 및 수문화학적 특성 I. 부곡 지역)

  • Yun, Seong-Taek;Koh, Yong-Kwon;Kim, Chun-Soo;So, Chil-Sup
    • Economic and Environmental Geology
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    • v.31 no.3
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    • pp.185-199
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    • 1998
  • Hydrogeochemical and environmental isotope studies were undertaken for various kinds of water samples collected in 1995-1996 from the Bugok geothermal area. Physicochemical data indicate the occurrence of three distinct groups of natural water: Group I ($Na-S0_4$ type water with high temperatures up to $77^{\circ}C$, occurring from the central part of the geothermal area), Group II (warm $Na-HCO_{3}-SO_{4}$ type water, occurring from peripheral sites), Group III ($Ca-HCO_3$ type water, occurring as surface waters and/or shallow cold groundwaters). The Group I waters are further divided into two SUbtypes: Subgroup Ia and Subgroup lb. The general order of increasing degrees of hydrogeochemical evolution (due to the degrees of water-rock interaction) is: Group III$\rightarrow$Group II$\rightarrow$Group I. The Group II and III waters show smaller degrees of interaction with rocks (largely calcite and Na-plagioclase), whereas the Group I waters record the stronger interaction with plagioclase, K-feldspar, mica, chlorite and pyrite. The concentration and sulfur isotope composition of dissolved sulfate appear as a key parameter to understand the origin and evolution of geothermal waters. The sulfate was derived not only from oxidation of sedimentary pyrites in surrounding rocks (especially for the Subgroup Ib waters) but also from magmatic hydrothermal pyrites occurring in restricted fracture channels which extend down to a deep geothermal reservoir (typically for the Subgroup Ia waters). It is shown that the applicability of alkaliion geothermometer calculations for these waters is hampered by several processes (especially the mixing with Mg-rich near-surface waters) that modify the chemical composition. However, the multi-component mineral/water equilibria calculation and available fluid inclusion data indicate that geothermal waters of the Bugok area reach temperatures around $125^{\circ}C$ at deep geothermal reservoir (possibly a cooling pluton). Environmental isotope data (oxygen-18, deuterium and tritium) indicate the origin of all groups of waters from diverse meteoric waters. The Subgroup Ia waters are typically lower in O-H isotope values and tritium content, indicating their derivation from distinct meteoric waters. Combined with tritium isotope data, the Subgroup Ia waters likely represent the older (at least 45 years old) meteoric waters circuated down to the deep geothermal reservoir and record the lesser degrees of mixing with near-surface waters. We propose a model for the genesis and evolution of sulfate-rich geothermal waters.

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Stable Isotope and Fluid Inclusion Studies of the Daebong Gold-silver Deposit, Republic of Korea (대봉 금-은광상에 대한 유체포유물 및 안정동위원소 연구)

  • 유봉철;이현구;김상중
    • Economic and Environmental Geology
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    • v.36 no.6
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    • pp.391-405
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    • 2003
  • The Daebong gold-silver deposit consists of mesothermal massive quartz veins thar are filling the fractures along fault shear (NE, NW) Bones within banded or granitic gneiss of Precambrian Gyeonggi massif. Based on vein mineralogy, ore textures and paragenesis, ore mineralization of this deposits is composed of massive white quartz vein(stage I) which was formed in the same stage by multiple episodes of fracturing and healing, and transparent quartz vein(stage II) which is separated by a major faulting event. Stage I is divided into the 3 substages. Ore minerals of each substages are as follows: 1) early stage I=magnetite, pyrrhotite, arsenopyrite, pyrite, sphalerite, chalcopyrite, 2) middle stage I=pyrrhotite, arsenopyrite, pyrite, marcasite, sphalerite, chalcopyrite, galena, electrum and 3) late stage I=pyrite, sphalerite, chalcopyrite, galena, electrum, argentite, respectively. Ore minerals of the stage II are composed of pyrite, sphalerite, chalcopyrite, galena and electrum. Systematic studies (petrography and microthermometry) of fluid inclusions in stage I and II quartz veins show fluids from contrasting physical-chemical conditions: 1) $H_2O-CO_2-CH_4-NaCl{\pm}N-2$ fluid(early stage I=homogenization temperature: 203∼3$88^{\circ}C$, pressure: 1082∼2092 bar, salinity: 0.6∼13.4 wt.%, middle stage I=homogenization temperature: 215∼28$0^{\circ}C$, salinity: 0.2∼2.8 wt.%) related to the stage I sulfide deposition, 2) $H_2O-NaCl{\pm}CO_2$ fluid (late stage I=homogenization temperature: 205∼2$88^{\circ}C$, pressure: 670 bar, salinity: 4.5∼6.7 wt.%, stage II=homogenization temperature: 201-3$58^{\circ}C$, salinity: 0.4-4.2 wt.%) related to the late stage I and II sulfide deposition. $H_2O-CO_2-CH_4-NaCl{\pm}N_2$ fluid of early stage I is evolved to $H_2O-NaCl{\pm}CO_2$ fluid represented by the $CO_2$ unmixing due to decrease in fluid pressure and is diluted and cooled by the mixing of deep circulated meteoric waters ($H_2O$-NaCl fluid) possibly related to uplift and unloading of the mineralizing suites. $H_2O-NaCl{\pm}CO_2$ fluid of stage II was hotter than that of late stage I and occurred partly unmixing, mainly dilution and cooling for sulfide deposition. Calculated sulfur isotope compositions ({\gamma}^{34}S_{H2S}$) of hydrothermal fluids (3.5∼7.9%o) indicate that ore sulfur was derived from mainly an igneous source and partly sulfur of host rock. Measured and calculated oxygen and hydrogen isotope compositions ({\gamma}^{18}O_{H_2O}$, {\gamma}$D) of ore fluids (stage I: 1.1∼9.0$\textperthousand$, -92∼-86{\textperthansand}$, stage II: 0.3{\textperthansand}$, -93{\textperthansand}$) and ribbon-banded structure (graphitic lamination) indicate that mesothermal auriferous fluids of Daebong deposit were two different origin and their evolution. 1) Fluids of this deposit were likely mixtures of $H_2O$-rich, isotopically less evolved meteoric water and magmatic fluids and 2) were likely mixtures of $H_2O$-rich. isotopically heavier $\delta$D meteoric water and magmaticmetamorphic fluids.

Alteration Zoning, Mineral Assemblage and Geochemistry of the Hydrothermal Clay Deposits Related to Cretaceous Felsic Magmatism in the Haenam Area, Southwest Korea (한국 서남부, 해남지역에서 백악기 산성마그마티즘에 관련된 열수점토광상의 누대분배, 광물조합의 지구화학적 연구)

  • Kim, In Joon
    • Economic and Environmental Geology
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    • v.25 no.4
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    • pp.397-416
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    • 1992
  • In the present study, three clay deposits, named the Seongsan, Ogmaesan and Haenam deposits, were investigated. The altered zones are recognized in the hydrothermally altered rocks of the clay deposits from the center of the alteration to the margin: Kaolin, Kaolin-Quartz, Quartz, Sericite and Chlorite zones in the Seongsan deposits; Quartz zone, Alunite zone, Kaolin zone, Sericite zone and Chlorite zone in the Ogmaesan deposits; Quartz zone, Pyrophyllite zone, Sericite zone and Chlorite zone in the Haenam deposits. These zones can be grouped into two types of alteration: Acidic alteration such as Pyrophyllite zone, Alunite zone, Quartz zone, Kaolin zone, Kaolin-Quartz zone and a part of Sericite zone; Propylitic alteration such as Chlorite zone and a part of Sericite zone. All clay deposits belong to high-sulfidation (acid-sulfate) system. The rocks of the acidic alterations are composed of pyrophyllite, alunite, kaolin minerals, sericite, quartz and pyrite. On the basis of bulk chemical compositions, it was found that some components such as $SiO_2$, $TiO_2$, $Fe_2O_3$, FeO, MgO, CaO, $K_2O$ and $Na_2O$ were mobilized considerably from the original rocks. The mobility of these major elements is related to, and controls, mineral assemblages in each altered zone. Polytypes of sericite are determined as $2M_1$ and 1M by X-ray diffraction method. The amount of $2M_1$ is nearly equal to that of 1M in the Seongsan deposits whereas $2M_1$ is less and higher than that of 1M in the Ogmaesan and the Haenam deposits. These facts indicate that formation temperature of sericite is relatively high in the Haenam deposits, moderate in the Seongsan deposits, and low in the Ogmaesan deposits. The ratios of Na/(K+Na) for alunite in the Ogmaesan deposits determined by electron microprobe analyzer (EPMA) are higher than those in the Seongsan deposits. Thus, the alunite of the Ogmaesan deposits must have been formed from the solutions with relatively high aqueous Na/(K+Na) ratios and low pH at a high temperature rather than that of the Seongsan deposits. From all data, it is clarified that alunite is hypogene in origin, and has been formed by oxidation of hydrogen sulfide in the steam-heated environment, and that alunite has been produced by the spectacular solfataric alteration observed at the surface of some present-day hydrothermal systems.

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Stable isotope, Fluid Inclusion and Mineralogical Studies of the Samkwang Gold-Silver Deposits, Republic of Korea (삼광 금-은광상의 산출광물, 유체포유물 및 안정동위원소 연구)

  • 유봉철;이현구;최선규
    • 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.

Contrasting Styles of Gold and Silver Mineralization in the Central and Southeastern Korea (한국 중부와 동남부지역 금·은광화작용의 성인적 특성)

  • Choi, Seon-Gyu;Choi, Sang-Hoon
    • Economic and Environmental Geology
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    • v.28 no.6
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    • pp.587-597
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    • 1995
  • Two distinct precious-metal mineralizations actively occur at central and southeastern Korea which display consistent relationships among geologic, geochemical and genetic environments. A large number of preciousmetal vein deposits in the central Korea occur in or near Mesozoic granite batholiths elongated in a NE-SW direction. Whereas, gold and/or silver deposits in the southeastern Korea occur within Cretaceous volcanic and sedimentary rocks. However, most of the precious-metal deposits in the southeastern Korea show characteristics of the silver-rich deposits than the gold-rich deposits in the central Korea. Two epochs of main igneous activities are recognized: a) Jurassic Daebo igneous activity between 121 and 183 Ma, and b) Cretaceous Bulgugsa igneous activity between 60 and 110 Ma. Precious-metal mineralization took place between 158 and 71 Ma, coinciding with portions of the two magmatic activities. Contrasts in the style of mineralization, together with radiometric age data and differences in geologic settings reflect the genetically variable natures of hydrothermal activities from middle Jurassic to late Cretaceous time. The compilation and re-evaluation of these data suggest that the genetic types of hydrothermal precious-metal vein deposits in the central and southeastern Korea varied with time. The Jurassic and early Cretaceous mineralizations are characterized by the Au-dominant type, but tend to change to the Au-Ag and/or Ag-dominant types at late Cretaceous. The Jurassic Au-dominant deposits commonly show several characteristics; prominent associations with pegmatites, simple massive vein morphologies, high fmeness values in ore-concentrating parts, and a distinctively simple ore mineralogy such as Fe-rich sphalerite, galena, chalcopyrite, Au-rich electrum, pyrrhotite and/or pyrite. The Cretaceous precious-metal deposits are generally characterized by some- features such as complex vein morphologies, low to medium fmeness values in the ore concentrates, and abundance of ore minerals including Ag sulfosalts, Ag sulfides, Ag tellurides and native silver. Mineralogical and fluid inclusion studies indicate that the Jurassic Au-dominant deposits in the central area were formed at the high temperature (about $300^{\circ}$ to $500^{\circ}C$) and pressure (about 4 to 5 kbars), whereas mineralizations of the Cretaceous Au-Ag and Ag-dominant deposits were occurred at the low temperature (about $200^{\circ}$ to $350^{\circ}C$) and pressure (<0.5 kbars) from the ore fluids containing more amounts of less-evolved meteoric waters.

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Mineralogy and Genetic Environments of the Seongdo Pb-Zn deposit, Goesan (괴산 성도 연-아연 광상의 산출광물과 생성환경)

  • Ahn, Seongyeol;Shin, Dongbok
    • Economic and Environmental Geology
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    • v.50 no.5
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    • pp.325-340
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    • 2017
  • The Seongdo Pb-Zn deposit, located in the northwestern part of the Ogcheon Metamorphic Belt, consists of skarn ore replacing limestone within the Hwajeonri Formation of Ogcheon Group and hydrothermal vein ore filling the fracture of host rock. Skarn minerals comprise mostly hedenbergitic pyroxene, garnet displaying oscillatory zonal texture composed of grossular and andradite, and a small amount of wollastonite, tremolite, and epidote, indicating reducing condition of formation. Ore minerals of skarn ore include sphalerite and galena with a small amount of pyrite, pyrrhotite, and chalcopyrite. In hydrothermal vein ore, arsenopyrite, sphalerite, chalcopyrite, and pyrite occur with a small amount of galena, native Bi, and stannite. Chemical compositions of sphalerite vary from 17.4 mole% FeS in average for dark grey sphalerite, 3.6 mole% for reddish brown sphalerite in skarn ore, and to 10.3 mole% FeS in hydrothermal vein ore. In comparison with representative metallic deposits in South Korea on the FeS-MnS-CdS diagram, skarn and hydrothermal vein ore plot close to the field of Pb-Zn deposits and Au-Ag deposits, respectively. Arsenic contents of arsenopyrite in hydrothermal vein ore decrease from 31.93~33.00 at.% in early stage to 29.58~30.21 at.% in middle stage, and their corresponding mineralizing temperature and sulfur fugacity are $441{\sim}490^{\circ}C$, $10^{-6}{\sim}10^{-4.5}atm$. and $330{\sim}364^{\circ}C$, <$10^{-8}atm$. respectively. Phase equilibrium temperatures calculated from Fe and Zn contents for coexisting sphalerite and stannite in hydrothermal vein are $236{\sim}254^{\circ}C$. Sulfur isotope compositions are 5.4~7.2‰ for skarn ore and 5.4~8.4‰ for hydrothermal vein ore, being similar or slightly higher to magmatic sulfur, suggesting that ore sulfur was mostly of magmatic origin with partial derivation from host rocks. However, much higher sulfur isotope equilibrium temperatures of $549^{\circ}C$$487^{\circ}C$, respectively for skarn ore and hydrothermal ore, than those estimated from phase equilibria imply that isotopic equilibrium has not been fully established.