Choi, Sang Hoon;So, Chil Sup;Kweon, Soon Hag;Choi, Kwang Jun
Economic and Environmental Geology
/
v.27
no.2
/
pp.147-160
/
1994
Copper-bearing hydrothermal vein mineralization of the Samsan area was deposited in two stages (I and II) of quartz-calcite-sulfide veins which fill fissures in Cretaceous volcanic and sedimentary rocks of the Gyeongsang basin. The major ore minerals, chalcopyrite and sphalerite, together with pyrite, galena, hematite, and minor sulfosalts, occur with epidote and chlorite as gangue minerals in stage I quartz veins. Chlorite geothermometry, fluid inclusion and stable isotope data indicate that copper ore was deposited mainly at temperatures between $330^{\circ}C$ and $280^{\circ}C$ from fluids with salinities between 12 and 3 equiv. wt % NaCl. Evidence of fluid boiling indicates a range of pressures from ${\leq}100$ to 200 bars bars. Within ore stage I there was an apparent decrease in ${\delta}^{34}S$ values of $H_{2}S$ with paragenetic time, from 8.0 to 2.3 per mil. This pattern was likely achieved through progressive increases in activity of oxygen accompanying boiling and mixing. In the early part of the first stage, the high temperature, high salinity fluids gave way to progressively cooler and more dilute fluids of the late parts in the first stage and of the second stage. There is a systematic decrease in calculated ${\delta}^{18}O_{water}$ values with decreasing temperature in the Samsan hydrothermal system, from values of -86 per mil for early portion of stage I through -5.9 per mil for late portion of stage I to -6.3 per mil for stage II. The ${\delta}D$ values of fluid inclusion waters also decrease with paragenetic time from -76 per mil to -86 per mil. These trends combined with mineral paragenesis and fluid inclusion data are interpreted to indicate progressive cooler, more oxidizing meteoric water inundation of an early exchanged meteoric hydrothermal system.
Lead and zinc mineralization of the Kwangsin mine was formed in quartz and carbonate veins that filled fault-related fractures in the limestone-rich Samtaesan Formation of the Chosun Supergroup and the phyllite-rich Suchangni Formation of unknown age. A K-Ar date of alteration sericite indicates that the Pb-Zn mineralization took place during Late Cretaceous (83.5 Ma), genetically in relation to the cooling of the nearby Muamsa Granite (83~87 Ma). Mineral paragenesis can be divided into three stages (I, II, III): (I) the deposition of barren massive white quartz, (II) the main Pb-Zn mineralization with deposition of white crystalline quartz and/or carbonates (rhodochrosite and dolomite), and (III) the deposition of post-ore barren calcite. Mineralogic and fluid inclusion data indicate that lead-zinc minerals in middle stage II (IIb) were deposited at temperatures between $182^{\circ}$ and $276^{\circ}C$ from fluids with salinities of 2.7 to 5.4 wt. % equiv. NaCl and with log $fs_2$ values of -15.5 to -11.8 atm. The relationship between homogenization temperature and salinity data indicates that lead-zinc deposition was a result of fluid boiling and later meteoric water mixing. Ore mineralization occurred at depths of about 600 to 700 m. Sulfur isotope compositions of sulfide minerals (${\delta}^{34}S_{CDT}=9.0{\sim}14.5$ ‰) indicate a relatively high ${\delta}^{34}S_{{\Sigma}S}$ value of ore fluids (up to 14 ‰), likely indicating an igneous source of sulfur largely mixed with an isotopically heavier sulfur source (possibly sulfates in surrounding sedimentary rocks). There is a remarkable decrease of calculated ${\delta}^{18}O$ value of water in hydrothermal fluids with increasing paragenetic time: stage I, 14.6~10.1 ‰; stage IIa, 5.8~2.2 ‰; stage IIb, 0.8~2.0 ‰; stage IIc, -6.1~-6.8 ‰, This indicates a progressive increase of meteoric water influx in the hydrothermal system at Kwangsin. Measured and calculated hydrogen and oxygen isotope values indicate that the Kwangsin hydrothermal fluids was formed from a circulating (due to intrusion of the Muamsa Granite) meteoric waters which evolved through interaction mainly with the Samtaesan Formation (${\delta}^{18}O=20.1$ to 24.9 ‰) under low water/rock ratios.
Baekun gold-silver deposit is an epithermal quartz vein that is filling the fault zone within Triassic or Jurassic foliated granodiorite. Mineralization is associated with fault-breccia zones and can be divided into two stages. Stage I which can be subdivided early and late depositional stages is main ore mineralization and stage II is barren. Early stage I is associated with wallrock alteration and the formation of sulfides such as arsenopyrite, pyrite, pyrrhotite, sphalerite, marcasite, chalcopyrite, stannite, galena. Late stage I is characterized by Au-Ag mineralization such as electrum, Ag-bearing tetrahedrite, stephanite, boulangerite, pyrargrite, argentite, schirmerite, native silver, Ag-Te-Sn-S system, Ag-Cu-S system, pyrite, chalcopyrite and galena. Fluid inclusion data indicate that homogenization temperatures and salinity of stage I range from $171.6^{\circ}C\;to\;360.8^{\circ}C\;and\;from\;0.5\;to\;10.2\;wt.\%\;eq.$ NaCl, respectively. It suggest that ore forming fluids were cooled and diluted with the mixing of meteoric water. Also, Temperature (early stage I: $236\~>380^{\circ}C,\;$ late stage $I: <197\~272^{\circ}C$) and sulfur fugacity (early stage $I:\;10^{-7.8}$ a atm., late stage I: $10^{-14.2}\~10^{-l6}atm$.) deduced mineral assemblages from stage 1 decrease with paragenetic sequence. Sulfur ($2.4\~6.1\%_{\circ}$(early stage $I=3.4\~5.3\%_{\circ},\;late\;stage\;I=2.4\~6.1\%_{\circ}$)), oxygen ($4.5\~8.8\%_{\circ}$(quartz: early stage $I=6.3\~8.8\%_{\circ}$, late stage $I=4.5\~5.6\%_{\circ}$)), hydrogen ($-96\~-70\%_{\circ}$ (quartz: early stage $I=-96\~-70\%_{\circ},\;late\;stage\;f=-78\~-74\%_{\circ},\;calcite:\;late\;stage\;I=-87\~-76\%_{\circ}$)) and carbon ($-6.8\~-4.6\%_{\circ}$ (calcite: late stage I)) isotope compositions indicated that hydrothermal fluids may be magmaticorigin with some degree of mixing of another meteoric water for paragenetic time.
So, Chil-Sup;Yun, Seong-Taek;Choi, Sang-Hoon;Kim, Se-Hyun;Kim, Moon-Young
Economic and Environmental Geology
/
v.25
no.2
/
pp.115-131
/
1992
Late Cretaceous (90.5 Ma), epithermal gold-silver vein mineralization of the Weolseong and Samchang mines in the Sulcheon area, 60 km southeast of Taejeon, can be separated into two distinct stages (I and II) during which fault-related fissures in Precambrian gneiss and Cretaceous (102 Ma) porphyritic granite were filled. Fluid inclusion and mineralogical data suggest that quartz-sulfide-electrum-argentite-forming stage I evolved from initial high temperatures $({\approx}340^{\circ}C})$ to later lower temperatures $({\approx}140^{\circ}C})$ at shallow depths of about 400 to 700 m. Ore fluid salinities were in the range between 0.2 and 6.6 wt. % eq. NaCl. A simple statistic model for fluid-fluid mixing indicates that the mixing ratio (the volumetric ratio between deep hydrothermal fluids and meteoric water) systematically decreased with time. Gold-silver deposition occurred at temperatures of $230{\pm}40^{\circ}C$ mainly as a result of progressive cooling of ore-forming fluids through mixing with less-evolved meteoric waters. Measured and calculated hydrogen and oxygen isotope values of hydrothermal fluids indicate meteoric water dominance, approaching unexchanged meteoric water values. The geologic, mineralogic, and geochemical data from the Weolseong and Samchang mines are similar to those from other Korean epithermal gold-silver vein deposits.
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.
Kim, Kyu-Han;Jeong, Yun-Jeong;Jeong, Chan-Ho;Keisuke, Nagao
Economic and Environmental Geology
/
v.41
no.1
/
pp.15-32
/
2008
The hydrochemical and isotopic (stable isotopes and noble gas isotopes) analyses for hot spring waters, cold groundwaters and surface water samples from the Seokmodo hot spring area of the Ganghwa province were carried out to characterize the hydrogeochemical characteristics of thermal waters and to interpret the source of thermal water and noble gases and the geochemical evolution of hot spring waters in the Seokmodo geothermal system. The hot spring waters and groundwaters show a weakly acidic condition with the pH values ranging from 6.42 to 6.77 and 6.01 to 7.71 respectively. The outflow temperature of the Seokmodo hot spring waters ranges from $43.3^{\circ}C\;to\;68.6^{\circ}C$. Relatively high values of the electrical conductivities which fall between 60,200 and $84,300{\mu}S/cm$ indicate that the hot spring waters were mixed with seawater in the subsurface geothermal system. The chemical compositions of the Seokmodo hot spring waters are characterized by Na-Ca-Cl water type. On the other hand, cold groundwaters and surface waters can be grouped into three types such as the Na(Ca)-$HCO_3$, Na(Ca)-$SO_4$ and Ca-$HCO_3$ types. The ${\delta}^{18}O\;and\;{\delta}D$ values of hot spring waters vary from -4.41 to -4.47%o and -32.0 to -33.5%o, respectively. Cold groundwaters range from -7.07 to -8.55%o in ${\delta}^{18}O$ and from -50.24 to -59.6%o in ${\delta}D$. The oxygen and hydrogen isotopic data indicate that the hot spring waters were originated from the local meteoric water source. The enrichments of heavy isotopes ($^{18}O\;and\;^2H$) in the Seokmodo hot spring waters imply that the thermal water was derived from the diffusion Bone between fresh and salt waters. The ${\delta}^{34}S$ values ranging from 23.1 to 23.5%o of dissolved sulfate are very close to the value of sea water sulfate of ${\delta}^{34}$S=20.2%o in this area, indicating the origin of sulfate in hot springs from sea water. The $^3H/^4He$ ratio of hot spring waters varies from $1.243{\times}10^{-6}\;to\;1.299{\times}10^{-6}cm^3STP/g$, which suggests that He gas in hot spring waters was partly originated from a mantle source. Argon isotopic ratio $(^{40}Ar/^{36}Ar=298{\times}10^{-6}cm^3STP/g)$ in hot spring waters corresponds to the atmospheric value.
Journal of the Korean Society of Groundwater Environment
/
v.7
no.1
/
pp.32-46
/
2000
Hydrogeochemical and isotope ($\delta$$^{18}$ O, $\delta$D, $^3$H, $\delta$$^{13}$ C, $\delta$$^{34}$ S, $^{87}$ Sr/$^{86}$ Sr) studies of various kinds of waters (thermal groundwater, deep groundwater, shallow groundwater, and surface water) from the Yusung area were carried out in order to elucidate their geochemical characteristics such as distribution and behaviour of major/minor elements, geochemical evolution, reservoir temperature, and water-rock interaction of the thermal groundwater. Thermal groundwater of the Yusung area is formed by heating at depth during deep circlulation of groundwater and is evolved into Na-HCO$_3$type water by hydrolysis of silicate minerals with calcite precipitation and mixing of shallow groundwater. High NO$_3$contents of many thermal and deep groundwater samples indicate that the thermal or deep groundwaters were mixed with contaminated shallow groundwater and/or surface water. $\delta$$^{18}$ O and $\delta$D are plotted around the global meteoric water line and there are no differences between the various types of water. Tritium contents of shallow groundwater, deep groundwater and thermal groundwater are quite different, but show that the thermal groundwater was mixed with surface water and/or shallow groundwater during uprising to surface after being heated at depths. $\delta$$^{13}$ C values of all water samples are very low (average -16.3$\textperthousand$%o). Such low $\delta$$^{13}$ C values indicate that the source of carbon is organic material and all waters from the Yusung area were affected by $CO_2$ gas originated from near surface environment. $\delta$$^{34}$ S values show mixing properties of thermal groundwater and shallow groundwater. Based on $^{87}$ Sr/$^{86}$ Sr values, Ca is thought to be originated from the dissolution of plagioclase. Reservoir temperature at depth is estimated to be 100~1$25^{\circ}C$ by calculation of equilibrium method of multiphase system. Therefore, the thermal groundwaters from the Yusung area were formed by heating at depths and evolved by water-rock interaction and mixing with shallow groundwater.
The hydrothermal vein type deposits which comprise the Kasihan, Jompong and Gempol mineralized areas are primarily copper and zinc deposits, but they are also associated with lead and/or gold mineralization. The deposits occur within the Tertiary sedimentary and volcanic rocks in the Southern Mountain zone of the eastern Java island, Indonesia. Mineralization can be separated into two or three distinct stages (pre-and/or post- ore mineralization stages and main ore mineralization stage) which took place mainly along pre-existing fault breccia zones. The main phase of mineralization (the main ore stage) can be usually classified into three substages (early, middle and late) according to ore mineral assemblages, paragenesis, textures and their chemical compositions. Ore mineralogy and paragenesis of the three areas in the district are different from each other. Pyrite, pyrrhotite (/arsenopyrite), iron-rich (up to 20.5 mole % FeS) sphalerite and (Cu-)Pb-Bi sulfosalts are characteristic of the deposits in the Kasihan (/Jompong) area. On the other hand, pyrite + hematite + magnetite + iron-poor (2.7 to 3.6 mole % FeS) sphalerite assemblage is restricted to the Gempol area. Fluid inclusion data suggest that fluids of the main ore stage evolved from initial high temperatures (near $350^{\circ}C$) to later lower temperatures (near $200^{\circ}C$) with salinities ranging from 0.8 to 10.1 equiv. wt. percent NaCl. Each area represents a separate hydrothermal system: the mineralization at Kasihan and Jompong were largely due to early fluid boiling coupled with later cooling and dilution, whereas the mineralization at Gempol was mainly resulted from cooling and dilution by an influx of cooler meteoric waters. Fluid inclusion evidence of boiling indicates that pressures of ${\geq}95$ to 255 bars (${\geq}95$ bars for the Gempol area: $\approx$ 120 to 170 bars for the Jompong area: $\approx$ 140 to 255 bars for the Kasihan area) during portions of main ore stage mineralization. Equilibrium thermodynamic interpretation indicates that the evolution trends of the temperature versus fS2 variation of ore stage fluids in the Pacitan district follow two fashions: ore fluids at Kasihan and Jompong changed from the pyrite-pyrrhotite sulfidation stage towards pyritehematite- magnetite state, whereas those at Gempol evolved nearly along pyrite-hematite-magnetite reaction curve with decreasing temperature. The sulfur isotope compositions of sulfide minerals are consistent with an igneous source of sulfur with a ${\delta}^{34}S_{{\Sigma}s}$ value of about 3.3 per mil. The oxygen and hydrogen isotopic compositions of the fluids in each area indicate a progressive shift from the dominance of highly exchanged meteoric water at early hydrothermal systems towards an un- or less-exchanged meteoric water at later hydrothermal systems.
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.
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.
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