• Economic and Environmental Geology
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• v.19 no.3
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• pp.199-218
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• 1986

Arsenopyrite in arsenic and polymetallic ores from calcic Fe-W skarn deposit of the Ulsan mine, Republic of Korea, has been investigated by means of electron microprobe analysis and X-ray diffractometry. As a result, it is revealed that the Ulsan arsenopyrite may be classified into the following three species with different generation on the basis of its mode of occurrence, chronological order during polymetallic mineralization and chemical composition; arsenopyrites I, II and III. 1) Arsenopyrite I-(Ni, Co)-bearing species belonging to the oldest generation, which has crystallized together with (Ni, Co)-arsenides and -sulpharsenides in the early stage of polymetallic mineralization. In rare cases, it contains a negligible amount of antimony. It occurs usually as discrete grains with irregular outline, showing rarely subhedral form, and is diffused in skarn zone. The maximum contents of nickel and cobalt are 10.04 Ni and 2.45 Co (in weight percent). Occasionally, it shows compositional zoning with narrow rim of lower (Ni+Co) content. 2) Arsenopyrite II-arsenian species, in which (Ni+Co) content is almost negligible, may occur widely in arsenic ores, and its crystallization has followed that of arsenopyrite I. It usually shows subhedral to euhedral form and is closely associated with $l{\ddot{o}}llingite$, bismuth, bismuthinite, chalcopyrite, sphalerite, bismuthian tennantite, etc. It is worthy of note that arsenopyrite II occasionally contains particles consisting of both bismuth and bismuthinite. 3) Arsenopyrite III-(Ni, Co)-free, S-excess and As-deficient species is close to the stoichiometric composition, FeAsS. It occurs in late hydrothermal veins, which cut clearly the Fe-W ore pipe and the surrounding skarn zone. It shows euhedral to subhedral form, being extremely coarse-grained, and is closely associated with pyrite, "primary" monoclinic pyrrhotite, galena, sphalerite, etc. Among three species of the Ulsan arsenopyrite, arsenopyrite I does not serve as a geothermometer, because (Ni+Co) content always exceeds 1 weight percent. In spite of the absence of Fe-S minerals as sulphur-buffer assemblage, the presence of $Bi(l)-Bi_2S_3$ sulphur-buffer enables arsenopyrite II to apply successfully to the estimation of either temperature and sulphur fugacity, the results are, $T=460{\sim}470^{\circ}C$, and log $f(S_2)=-7.4{\sim}7.0$. With reference to arsenopyrite III, only arsenopyrite coexisting with pyrite and "primary" monoclinic pyrrhotite may serve to restrict the range of both temperature and sulphur fugacity, $T=320{\sim}440^{\circ}C$, log $f(S_2)=-9.0{\sim}7.0$. These temperature data are consistent with those obtained by fluid inclusion geothermometry on late grandite garnet somewhat earlier than arsenopyrite II. At the beginning of this paper, the geological environments of the ore formation at Ulsan are considered from regional and local geologic settings, and physicochemical conditions are suspected, in particular the formation pressure (lithostatic pressure) is assumed to be 0.5kb (50MPa). The present study on arsenopyrite geothermometry, however, does not bring about any contradictions against the above premises. Thus, the following genetical view on the Ulsan ore deposit previously advocated by two of the present authors (Choi and Imai) becomes more evident; the ore deposit was formed at shallow depth and relatively high-temperature with steep geothermal gradient-xenothermal conditions.

• Economic and Environmental Geology
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• v.15 no.3
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• pp.155-166
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• 1982

Sulfur isotope compositions (${\delta}^{34}S$) of seventy one sulfide minerals from the Shinyemi ore deposits were determined to range from -10.1 to +5.0‰ with a mean value of +2.1‰. These values are roughly comparable to those of various hydrothermal ore deposits in Korea, about +2.0 to +7.0‰ in ${\delta}^{34}S$, suggesting that they are to be same in source of sulfur. The Shinyemi deposits are grouped into two types; the western bedded skarn orebodies and the eastern small pipes and veins. The ${\delta}^{34}S$ values of sulfide minerals from the bedded orebodies (early mineralization) are ranging from -10.1 to +2.5‰, which is relatively wide in range, whereas those of the pipes and veins. (later mineralization) have a narrow range of ${\delta}^{34}S$ values, +2.7 to +5.0‰, regardless of the kind of sulfide minerals. Isotopic temperature obtained from the sphalerite-galena mineral pairs of the New B orebody appeared to be about 400 to $540^{\circ}C$ are reasonably good agreement with the comparable data of skarn mineral assemblages. It is concluded that the west orebodies were formed in earlier stage at higher temperatures than the east orebodies formed later at lower temperatures. Judging from the various data from the present study, the Shinyemi deposits can be defined as a typical contact metasomatic deposit. The source of sulfur in the hydrothermal solutions is considered to be comagmatic with the Shinyemi granodiorite.

• 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.

• Economic and Environmental Geology
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• v.35 no.1
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• pp.1-12
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• 2002

Manus Basin, located in the equatorial western Pacific, is a back arc basin formed by collision between the IndoAustralian and the Pacific Plates. The basin is host to numerous hydrothermal vent fields and ore deposits. The basement rocks of the Manus Basin consist primarily of dacite and basaltic andesite. Some of the minerals that form the hydrothermal chimneys that were dredged on the Manus basin include pyrite, chalcopyrite, marcasite, sphalerite and galena. The chimneys can be classified into chalcopyrite dominant Cu-rich type and sphalerite dominant Zn-rich type. The concentration of Zn shows good positive correlation with that of Sb, Cd and Ag. The content of Cu, on the other hand, positively correlates with that of Mo, Mn and Co. For samples that were taken from Zn-rich chimney, a strong positive correlation is found between Au and Zn contents. The chimney also shows enrichments of Cd, Mn and Sb. On the other hand, the samples from Cu-rich chimney exhibit strong correlation among Au, Zn and Pb, and are enriched in Mo and Co concentration. Average contents of Au in Cu-rich and Znrich chimneys were 15.9 ppm and 29.0 ppm, respectively. Because of high concentration of Au with Ag and Cu, the ore deposit have high economic potential. Homogenization temperatures and salinities of fluid inclusions in anhydrite and amorphous silica from Zn-rich chimney are estimated to be l74-220$^{\circ}$C and 2.7-3.6 equiv. wt. % NaCI, respectively. These value suggest that ore forming processes were occurred at around 200$^{\circ}$C and that the oxygen fugacity changed from 2: 10$^{-39.5}$bar to -s: 10$^{-40.8}$bar and the sulfur fugacity from -s: 10$^{-14.7}$bar to 10$^{-13.4}$bar during the process. It appears that the temperature at which the ores formed on Cu-rich chimney was higher than that on Zn-rich chimney.

• Journal of the Mineralogical Society of Korea
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• v.23 no.1
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• pp.1-13
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• 2010

The Yugeum deposit in Youngduk in Gyungsangbuk-do is emplaced in the Cretaceous granitoids located in the Northeastem Gyeongsang Basin. Gold-bearing quartz veins filling the fracture with a direction of $N19^{\circ}{\sim}38^{\circ}W$ are most abundantly distributed within the Younghae granodiorite body. The formation of quartz veins can be classified into three main stages: barren quartz stage, auriferous quartz vein stage, and finally the extensive sulfide mineralization stage. Various sulfide minerals such as pyrite, chalcopyrite, galena, sphalerite, and arsenopyrite were precipitated during the hydrothermal gold mineralization process. Gold commonly occurs as fine-grained electrum in sulfides with high Au concentration (up to 93 wt%) compared to Ag. During the early gold mineralization stage, the temperature and pressure of the fluids are in the range of $220{\sim}250^{\circ}C$ and 730~1800 bar, and the oxygen fugacity is between $10^{-27}$ and $10^{-31.7}$ atm. On the other hand, the fluids of the late stage mineralization are characterized by temperature of $290{\sim}350^{\circ}C$ and pressure of 206~472 bar, and the oxygen fugacity is in the range of $10^{-26.3}{\sim}10^{-28.6}$ atm. The sulfur isotope compositions of sulfide minerals are in the range of $0.2{\sim}4.2^{\circ}/_{\circ\circ}$, while the ${\delta}^{34}SH_2S$ values range from 1.0 to $3.7^{\circ}/_{\circ\circ}$. The Ag/Au atomic ratios of electrum ranges from 0.15 to 1.10, and Au content is higher than Ag in most electrum. During the main gold mineralization stage at the relatively high temperature condition and with pH from 4.5 to 5.5, the stability of ${AuCl_2}^-$ increased while the stability of ${Au(HS)_2}^-$ decreased. Considering the pressure estimated in this deposit, the temperature of the ore fluid reached higher than $350^{\circ}C$ and ${AuCl_2}^-$ became an important species for the gold transportation. As mineralization proceeded with decreasing temperature and increasing pH and $f_{o2}$, the precipitation of sulfide minerals and accompanying electrum occurred.

• Journal of the Mineralogical Society of Korea
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• v.31 no.4
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• pp.307-323
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• 2018

The Inseong Au-Ag and base metal deposit, located in Chungchengbuk-do, Korea, consists of series of quartz veins filling fissures. The deposit occurs in Hwanggangri meta-sediment formation, a lime pebble-bearing phyllite, in the Okcheon Supergroup. Abundant ore minerals in the deposit are pyrite, arsenopyrite, sphalerite, chalcopyrite and galena. The gangue minerals are quartz, calcite and chlorite. Hydrothermal alteration such as chlorization, silicitication, sericitization and carbonitization can be observed around the quartz veins. 4 vein stages can be distinguished based on its paragenetic sequence, vein structure, alteration features and ore minerals. Microthermometry of the fluid inclusion assemblages occur in the veins are conducted to reconstruct a hydrothermal P-T evolution. Fluid inclusions in clean and barren quartz vein in stage 1 have Th of $270{\sim}342^{\circ}C$ and salinity of 1.7~6.4 (NaCl eqiv.) wt%. Euhedral quartz crystal in stage 2 have Th of $108{\sim}350^{\circ}C$ and salinity of 0.5~7.5 wt%. Barren milky quartz vein in stage 3 have Th of $174{\sim}380^{\circ}C$ and salinity of 0.8~7.5 wt%. Calcite vein in stage 4 have Th of $103{\sim}265^{\circ}C$ and salinity of 0.7~6.4 wt%. Calculated paleodepth about 0.5~1.5 km (hydrostatic pressure) indicate epithermal ore-forming condition. Shallow depth but relatively high-T hydrothermal fluids possibly create a steep geothermal gradient, sufficient for base metal precipitation in the Inseong deposit.

• Korean Journal of Mineralogy and Petrology
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• v.34 no.1
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• pp.1-14
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• 2021

The Unsang gold deposit has been one of the three largest deposits (Daeyudong, Kwangyang) in Korea. The geology of this deposit consists of series of host rocks including Precambrian metasedimentary rock and Jurassic Porphyritic granite. The deposit consists of Au-bearing quartz veins which filled fractures along fault zones in Precambrian metasedimentary rock and Jurassic Porphyritic granite, which suggests that it is an orogenic-type deposit. Quartz veins are classified as 1) galena-quartz vein type, 2) pyrrhotite-quartz vein type, 3) pyrite-quartz vein type, 4) pegmatic quartz vein type, 5) muscovite-quartz vein type and 6) simple quartz vein type based on mineral assembles. The studied quartz vein is pyrite-quartz vein type which occurs as sericitization, chloritization and silicification. The white mica from stylolitic seams of laminated quartz vein occurs as fine or medium aggregate associated with white quartz, pyrite, chlorite, rutile, monazite, apatite, K-feldspar, zircon and calcite. The structural formular of white mica from laminated quartz vein is (K0.98-0.86Na0.02-0.00Ca0.01-0.00Ba0.01-0.00 Sr0.00)1.00-0.88(Al1.70-1.57Mg0.22-0.09Fe0.23-0.10Mn0.00Ti0.04-0.02Cr0.01-0.00V0.00Ni0.00)2.06-1.95 (Si3.38-3.17Al0.83-0.62)4.00O10(OH2.00-1.91F0.09-0.00)2.00. It indicated that white mica of laminated quartz vein has less K, Na and Ca, and more Si than theoretical dioctahedral micas. Compositional variations in white mica from laminated quartz vein are caused by phengitic or Tschermark substitution [(Al3+)VI+(Al3+)IV <-> (Fe2+ or Mg2+)VI+(Si4+)IV] and direct (Fe3+)VI <-> (Al3+)VI substitution. The structural formular of chlorite from laminated quartz vein is((Mg1.11-0.80Fe3.69-3.14Mn0.01-0.00Zn0.01-0.00K0.07-0.01Na0.01-0.00Ca0.04-0.01Al1.66-1.09)5.75-5.69 (Si3.49-2.96Al1.04-0.51)4.00O10 (OH)8. It indicated that chlorite of laminated quartz vein has more Si than theoretical chlorite. Compositional variations in chlorite from laminated quartz vein are caused by phengitic or Tschermark substitution (Al3+,VI+Al3+,IV <-> (Fe2+ or Mg2+)VI+(Si4+)IV) and octahedral Fe2+ <-> Mg2+ (Mn2+) substitution. Therefore, laminated quartz vein and alteration minerals of the Unsan Au deposit was formed during ductile shear stage of orogeny.

• Economic and Environmental Geology
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• v.51 no.3
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• pp.213-222
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• 2018

Metasediment-hosted Pb-Zn mineralized zone has been found in Dyusembay of Kazakhstan. Its petrological properties, metal index, alteration index and redox-sensitivity are compared with those of SEDEX type deposit. Mineralization is developed along foliation of host rock (graphitic phyllite) and controlled by folds and faults; major ore minerals including pyrite, pyrrhotite, sphalerite, and galena are disseminated or interlayered with fine-grained quartz. The margin of the mineralized zone is metamorphosed accompanying sericite and chlorite. Hydrothermal brecciation and Pb-Zn mineralization formed in quartz-calcite stockworks are confirmed at the around of Maytyubin granitoid intrusions. The mineralization is classified into three types according to those of occurrence, paragenesis, chemical composition and isotopic characteristics. Type 1 whose fine-grained pyrite, pyrrhotite and sphalerite are formed in parallel yet discontinuous to well-developed foliations of the host rock; its geochemistry is similar to those of the earlier stage in SEDEX-type mineralization. In case of type 2, the ore minerals of which are concentrated being parallel to a foliation by regional metamorphism, and most of them associated with quartz and muscovite (${\pm}$ biotite) paragenetically. Type 3 is formed in the hydrothermal breccia zone whose ore minerals are controlled by foliation and breccia and developed in quartz ${\pm}$ calcite veins having a form such as stratification, stockwork or veinlets. Host rocks in the mineralized zone indicate homogeneous metamorphic grade and there is no specific alteration zonation. Also, all types (type 1, type 2, and type 3) represent similar REEs patterns, it can be interpreted that these are originated from a same source. Sulphides occurred in mineralized zone indicate a limited range of sulphur isotope values (type 2, ${\delta}^{34}S=-13.3{\sim}-11.7$‰; type 3, ${\delta}^{34}S=-13.9{\sim}-8.2$‰), and a result of geothermometry presents different temperature ranges: type 2($251{\pm}38^{\circ}C{\sim}277{\pm}40^{\circ}C$); type 3($360{\pm}2^{\circ}C$ to $537{\pm}29^{\circ}C$). It is estimated to be due to the effect of metamorphism and Maytyubin granitoid intrusions, respectively. In addition, ternary chart of thorium, scandium, and zircon for discrimination of tectonic setting and redox sensitivity using V/Mo values indicate that hydrothermal sediments put on reduction environment after precipitation, before being affected by metamorphism and intrusion activity. Geochemical data are plotted on a distal trend of SEDEX-type with discrimination plot using SEDEX index. As a result, petrological-geochemical properties demonstrate that Dyusembay Pb-Zn mineralized zone is comparable to distal-type of SEDEX deposit.

• Economic and Environmental Geology
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• v.12 no.3
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• pp.147-176
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• 1979

The Yeonhwa II zinc-lead mine is characterized by a dozen of moderately dipping tabular orebodies of skarn and zinc-lead sulfides, developed in accordance with the ENE-trending bedding thrusts and bedding planes of the Pungchon Limestone and underlying Myobong Formation, mostly along the contacts of a ENE-trending sill and a NW-trending dike of quartz mononite porphyry. The orebodies occur in three groups: (1) the footwall Wolgok orebodies with respect to the sill, (2) the hangingwall Wolgok orebodies, and (3) the Seongok orebodies extended from dike contacts into carbonate beds. Mineral compositions of these orebodies are dominated by calc-silicates (skarn) associated with ore minerals of sphalerite, galena, and chalcopyrite, as well as sulfide gangue of pyrrhotite. A pair of exo- and endo-skerns in the Wolgok footwall contact aureole between the Pungchon Limestone and quartz monzonite porphyry on the -120 level represents a well-developed symmetrical pattern of mineral zoning: a garnet/quartz zone in the center of exoskarn, two zones of pyroxene with ore minerals on both sides of the garnet/quartz zone, further outwards-an epidote/chlorite-bearing hornfelsic zone in the Myobong slate beyond a zone of unaffected limestone, and an epidote-dominated zone of endo skarn on the opposite side toward fresh quartz monzonite porphyry. These features indicate a combination of two effects on the skarn formation: (1) differences in composition of the host rocks(sedimentary and ignous), and (2) progressive outward migration of inner zones on outer zones on the course of metasomatic replacement of the pre-existing minerals. Microprobe analyses of garnet, pyroxene, pyroxenoids, epidote, and chlorite for nine major elements on a total of 23 mineral grains revealed that: the pyroxenes are hedenbergitic, in most zones, with a gradual decrease of Fe- and Mn-contents toward the central zone, whereas the garnets are andraditic in outer zones, but are grossularitic in the central zone. This indicates a reverse relationship of Fe-contents between pyroxene and garnet across the exoskarn zones. Pyroxenoids are lacking in wollastonite but are dominated by pyroxmangite, rhodonite and bustamite, indicating a Mn-rich nature in bulk chemistry. Pseudomorphic fluorite after garnet occurs abundantly reflecting a fluorine-enhanced evidence of the skarn-forming fluids. Epidote contains 0.19-0.25mole fraction of pistacite, and chlorite is Mn-rich but is Mg-poor. Sulfide mineralization took place with the most Fe-rich pyroxene rather than with garnet as indicated by the fact that the highest value of hedenbergite mole fraction occurs in the ore-bearing pyroxene zone. The Yeonhwa II ores are characterized by high zinc and low lead in metal grade, with minor quantity of copper content in almost constant grade. The hangingwall Wolgok and Seongok orebodies, that formed in a more open environment with respect to their local configurations of geologic setting, are more variable in metal grades and ratios, than are the footwall Wolgok orebodies formed in a more closed condition in a narrow interval of sedimentary beds.

• 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.