• Economic and Environmental Geology
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• v.39 no.6 s.181
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• pp.643-651
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• 2006

The Pb-Ag-Bi-S system minerals such as galena-matildite solid solutions, cosalite and heyrovskyite occur in the Nakdong As-Bi deposits. Galena-matildite solid solutions commonly coexisting with native bismuth fill in microfractures of pyrite grains and form irregular shapes. Cosalite forms composite grains including native bismuth, heyrovskyite and Bi-Te-S system minerals in the matrix of quartz vein. Matildite from the Nakdong deposits has an end member composition, $Ag_{1.07-1.11}Bi_{1.12-1.20}S_2$, and an excess concentration of $0.3{\sim}2.4$ mole % $Bi_2S_3$ compared to the stoichiomeoic value. PbS concentrations in $PbS-AgBiS_2$ solid solutions do not exceed 54 mole %. The average chemical composition of cosalite in the study area is $Pb_{1.79}Bi_{2.29}Ag_{0.12}S_5$. Pb is slightly depleted compared to the ideal composition, but the concentrations of Ag and Cu reach as much as 1.47 wt.% and 0.27 wt.%, respectively. Heyrovskyite has the chemical formula of $Pb_{5.01}Ag_{0.26}Bi_{2.70}S_9$ suggesting that there occurs the coupled substitution of $2Bi^{3+}$ for $3Pb^{2+}$ as well as that of $Ag^++Bi^{3+}$ for $2Pb^{2+}$. The genetic condition of Pb-Ag-Bi-S system minerals can be confined to the temperature of $220{\sim}270^{\circ}C$ and the pressure below 200 bars.

• Economic and Environmental Geology
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• v.48 no.1
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• pp.1-13
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• 2015

The geology of the Seungryung Zn deposit, located in the Muzu basin, consists of Precambrian leucocratic granitic gneiss, Cretaceous clastic rocks, pyroclastic rocks, and intrusive rocks. The deposit shows a weakly skarnized hydrothermal replacement ore developed along limestone bed in the gneiss. The mineralization can be divided into three stages: the early skarnization producing garnet and pyroxene, the main mineralization in the middle stage precipitating most metallic minerals such as magnetite, sphalerite, chalcopyrite, pyrrhotite, Pb-Ag-Bi-S system minerals, and the late stage for altered or low temperature minerals such as chlorite and marcasite. Pb-Ag-Bi-S system minerals include heyrovskite-eskimoite solid solution, lillianite-gustavite solid solution, and vikingite. Chalcopyrite diseases are quite common in sphalerite showing bead chains and dusting textures. The ${\delta}^{34}S$ values of sulfides minerals are concentrated within the narrow range of 3.4~4.1‰ for pyrite, 3.3~4.3‰ for sphalerite, 4.0~4.3‰ for chalcopyrite, and 2.8‰ for galena, suggesting that most sulfur is of igneous origin. Sulfur isotope geothermometry is calculated to be $346{\sim}431^{\circ}C$, implying that the mineralization occurred at relatively high temperature. FeS contents of sphalerite are relatively high in the range of 6.58~20.16 mole% (avg. 16.58 mole%) with the enrichment of Mn compared to Cd, similarly to representative skarn Pb-Zn deposits in South Korea. On the contrary, sphalerite from Au-Ag deposits in the Seolcheon mineralized zone around the Seungryung deposit is enriched in Cd, showing similar feature like representative epithermal Au-Ag deposits. This suggests that around the related igneous rocks, magnetite and sphalerite were produced at high temperature in the Seungryung deposit, and with decreasing temperature and compositional change of mineralizing fluids, Au-Ag mineralization proceeded in the Seolcheon mineralized zone.

• Economic and Environmental Geology
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• v.28 no.1
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• pp.9-17
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• 1995

The Kamkye Cu-Pb-Zn-Au-Ag deposits occur as quartz veins that filled fault-related fractures of NW system developed in the Cretaceous Gyeongsang basin. Three major stages of mineral deposition are recognized: (1) the stage I associated with wall rock alteration, such as sericite, chlorite, epidote and pyrite, (2) the early stage II of base-metal mineralization such as pyrite, hematite, and small amounts of sphalerite and chalcopyrite. and the middle to late stage II of Cu-As-Sb-Au-Ag-S mineralization, such as sphalerite, chalcopyrite, galena with tetrahedrite, tennantite, pearceite, Pb-Bi-Cu-S system, argentite and electrum. (3) the stage III of supergene mineralization, such as covellite, chalcocite and malachite. K-Ar dating of alteration sericite is a late Cretaceous ($74.0{\pm}1.6Ma$) and it may be associated with granitic activity of nearby biotite granite and quartz porphyry. Fluid inclusion data suggest a complex history of boiling, cooling and dilution of ore fluids. Stage II mineralization occurred at temperatures between 370 to $220^{\circ}C$ from fluids with salinities of 8.4 to 0.9 wt.% NaCl. Early stage II($320^{\circ}C$, 2.0 wt.% NaCl) may be boiled due to repeated fracturing which opened up the hydrothermal system to the land surface, and which resulted in a base-metal sulfide. Whilst the fractures were opened to the surface, mixing of middle-late stage II ore fluids with meteoric waters resulted in deposition of Cu-As-Sb-Au-Ag minerals from low temperature fluids(${\leq}290^{\circ}C$). Boiling of ore fluids may be occured at a pressure of 112 bar and a depth of 412 m. Equilibrium thermodynamic interpretation of sphalerite-tetraherite assemblages in middle stage II indicates that the ore-forming fluid had log fugacities of $S_2$ of -6.6~-9.4 atm.

• 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.

• Economic and Environmental Geology
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• v.25 no.4
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• pp.417-433
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• 1992

Lead-zinc-copper deposits of the Jeonheung and the Oksan mines around Euiseong area occur as hydrothermal quartz and calcite veins that crosscut Cretaceous sedimentary rocks of the Gyeongsang Basin. The mineralization occurred in three distinct stages (I, II, and III): (I) quartz-sulfides-sulfosalts-hematite mineralization stage; (II) barren quartz-fluorite stage; and (III) barren calcite stage. Stage I ore minerals comprise pyrite, chalcopyrite, sphalerite, galena and Pb-Ag-Bi-Sb sulfosalts. Mineralogies of the two mines are different, and arsenopyrite, pyrrhotite, tetrahedrite and iron-rich (up to 21 mole % FeS) sphalerite are restricted to the Oksan mine. A K-Ar radiometric dating for sericite indicates that the Pb-Zn-Cu deposits of the Euiseong area were formed during late Cretaceous age ($62.3{\pm}2.8Ma$), likely associated with a subvolcanic activity related to the volcanic complex in the nearby Geumseongsan Caldera and the ubiquitous felsite dykes. Stage I mineralization occurred at temperatures between > $380^{\circ}C$ and $240^{\circ}C$ from fluids with salinities between 6.3 and 0.7 equiv. wt. % NaCl. The chalcopyrite deposition occurred mostly at higher temperatures of > $300^{\circ}C$. Fluid inclusion data indicate that the Pb-Zn-Cu ore mineralization resulted from a complex history of boiling, cooling and dilution of ore fluids. The mineralization at Jeonheung resulted mainly from cooling and dilution by an influx of cooler meteoric waters, whereas the mineralization at Oksan was largely due to fluid boiling. Evidence of fluid boiling suggests that pressures decreased from about 210 bars to 80 bars. This corresponds to a depth of about 900 m in a hydrothermal system that changed from lithostatic (closed) toward hydrostatic (open) conditions. Sulfur isotope compositions of sulfide minerals (${\delta}^{34}S=2.9{\sim}9.6$ per mil) indicate that the ${\delta}^{34}S_{{\Sigma}S}$ value of ore fluids was ${\approx}8.6$ per mil. This ${\delta}^{34}S_{{\Sigma}S}$ value is likely consistent with an igneous sulfur mixed with sulfates (?) in surrounding sedimentary rocks. Measured and calculated hydrogen and oxygen isotope values of ore-forming fluids suggest meteoric water dominance, approaching unexchanged meteoric water values. Equilibrium thermodynamic interpretation indicates that the temperature versus $fs_2$ variation of stage I ore fluids differed between the two mines as follows: the $fs_2$ of ore fluids at Jeonheung changed with decreasing temperature constantly near the pyrite-hematite-magnetite sulfidation curve, whereas those at Oksan changed from the pyrite-pyrrhotite sulfidation state towards the pyrite-hematite-magnetite state. The shift in minerals precipitated during stage I also reflects a concomitant $fo_2$ increase, probably due to mixing of ore fluids with cooler, more oxidizing meteoric waters. Thermodynamic consideration of copper solubility suggests that the ore-forming fluids cooled through boiling at Oksan and mixing with less-evolved meteoric waters at Jeonheung, and that this cooling was the main cause of copper deposition through destabilization of copper chloride complexes.

• Economic and Environmental Geology
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• v.27 no.2
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• pp.147-160
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• 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.