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.
Mesothermal gold vein minerals of the Seolhwa mine were deposited in a single stage of massive quartz veins which filled the mainly NE-trending fault shear zones exclusively in the granitoid of the Gyeonggi Massif. The Seolhwa mesothermal gold mineralization is spatially associated with the Jurassic granitoid of 161 Ma. The vein quartz contains three main types of fluid inclusions at 25$^{\circ}$C: 1) low-salinity (< 5 wt.% NaCl), liquid CO$_{2}$-bearing, type IV inclusion; 2) gas-rich (> 70 vol.%), aqueous type II inclusions; 3) aqueous type I inclusions (0${\sim}$15 wt.% NaCl) containing small amounts of CO$_{2}$. The H$_{2}$O-CO$_{2}-CH$_{4}$-N$_{2}$-NaCl inclusions represent immiscible fluids trapped earlier along the solvurs curve at temperatures from 430$^{\circ}$ to 250$^{\circ}$C and pressures of 1 kbars. Detailed fluid inclusion chronologies may suggest a progressive decrease in pressure during the auriferous mineralization. The aqueous inclusion fluids represent either later fluids evelved through extensive fluid unmixing (CO$_{2}-CH$_{4}$ effervescence) from a homogeneous H$_{2}$O-CO$_{2}-CH$_{4}$-N$_{2}$-NaCl fluid due to decreases in temperature and pressure, or the influence of deep circulated meteoric waters possibly related to uplift and unloading of the mineralizing suites. The initial fluids were homogeneous containing H$_{2}$O-CO$_{2}-CH$_{4}$-N$_{2}$-NaCl components and the following properties: the initital temperature of >250$^{\circ}$ to 430$^{\circ}$C, X$_{CO}\;_{2}$ of 0.16 to 0.62, 5 to 14 mole% CH$_{4}$, 0.06 to 0.3 mole% N$_{2}$ and salinities of 0.4 to 4.9 wt.% NaCl. The T-X data for the Seolhwa gold mine may suggest that the Seolhwa auriferous hydrothermal system has been probably originated from adjacent granitic melt which facilitated the CH$_{4}$ formation and resulted in a reduced fluid state evidenced by the predominance of pyrrhotite. The dominance of negative ${\delta}\;^{34}$S values of sulfides (-0.6 to 1.4$%_o$o) are consistent with their deep igneous source.
The Boguk cobalt mine is located within the Cretaceous Gyeongsang Sedimentary Basin. Major ore minerals including cobalt-bearing minerals (loellingite, cobaltite, and glaucodot) and Co-bearing arsenopyrite occur together with base-metal sulfides (pyrrhotite, chalcopyrite, pyrite, sphalerite, etc.) and minor amounts of oxides (magnetite and hematite) within fracture-filling $quartz{\pm}actinolite{\pm}carbonate$ veins. These veins are developed within an epicrustal micrographic granite stock which intrudes the Konchonri Formation (mainly of shale). Radiometric date of the granite (85.98 Ma) indicates a Late Cretaceous age for granite emplacement and associated cobalt mineralization. The vein mineralogy is relatively complex and changes with time: cobalt-bearing minerals with actinolite, carbonates, and quartz gangues (stages I and II) ${\rightarrow}$ base-metal sulfides, gold, and Fe oxides with quartz gangues (stage III) ${\rightarrow}$ barren carbonates (stages IV and V). The common occurrence of high-temperature minerals (cobalt-bearing minerals, molybdenite and actinolite) with low-temperature minerals (base-metal sulfides, gold and carbonates) in veins indicates a xenothermal condition of the hydrothermal mineralization. High enrichment of Co in the granite (avg. 50.90 ppm) indicates the magmatic hydrothermal derivation of cobalt from this cooling granite stock, whereas higher amounts of Cu and Zn in the Konchonri Formation shale suggest their derivations largely from shale. The decrease in temperature of hydrothermal fluids with a concomitant increase in fugacity of oxygen with time (for cobalt deposition in stages I and II, $T=560^{\circ}C-390^{\circ}C$ and log $fO_2=$ >-32.7 to -30.7 atm at $350^{\circ}C$; for base-metal sulfide deposition in stage III, $T=380^{\circ}-345^{\circ}C$ and log $fO_2={\geq}-30.7$ atm at $350^{\circ}C$) indicates a transition of the hydrothermal system from a magmatic-water domination toward a less-evolved meteoric-water domination. Sulfur isotope data of stage II sulfide minerals evidence that early, Co-bearing hydrothermal fluids derived originally from an igneous source with a ${\delta}^{34}S_{{\Sigma}S}$ value near 3 to 5‰. The remarkable increase in ${\delta}^{34}S_{H2S}$ values of hydrothermal fluids with time from cobalt deposition in stage II (3-5‰) to base-metal sulfide deposition in stage III (up to about 20‰) also indicates the change of the hydrothermal system toward the meteoric water domination, which resulted in the leaching-out and concentration of isotopically heavier sulfur (sedimentary sulfates), base metals (Cu, Zn, etc.) and gold from surrounding sedimentary rocks during the huge, meteoric water circulation. We suggest that without the formation of the later, meteoric water circulation extensively through surrounding sedimentary rocks the Boguk cobalt deposits would be simple veins only with actinolite + quartz + cobalt-bearing minerals. Furthermore, the formation of the meteoric water circulation after the culmination of a magmatic hydrothermal system resulted in the common occurrence of high-temperature minerals with later, lower-temperature minerals, resulting in a xenothermal feature of the mineralization.
The Xiaoxinancha Cu-Au deposit in the Jilin province, located in NNE 800 km of Beijing, is hosted by diorite. The ore mineralization of Xiaoxinancha Cu-Au deposit show a stockwork occurrence that is concentrated on the potassic and phyllic alteration zones. The Xiaoxinancha Cu-Au deposit in the south is being mined with its reserves grading 0.8% Cu, 3.64 g/t Au and 16.8 g/t Ag and in the north, grading 0.63% Cu, 3.80 g/t Au and 6.8 glt Ag. The alteration assemblage occurs as a supergene blanket over deposit. Hydrothermal alteration at the Xiaoxinancha Cu-Au deposit is centered about the stock and was extensively related to the emplacement of the stock. Early hydrothermal alteration was dominantly potassic and followed by propylitic alteration. Chalcocite, often associated with hematite, account for the ore-grade copper, while chalcopyrite, bornite, quartz, epidote, chlorite and calcite constitute the typical gangue assemblage. Other minor opaque phases include pyrite, marcasite, native gold, electrum, hessite, hedleyite, volynskite, galenobismutite, covellite and goethite. Fluid inclusion data indicate that the formation of this porphyry copper deposit is thought to be a result of cooling followed by mixing with dilute and cooler meteoric water with time. In stage II vein, early boiling occurred at 497$^{\circ}$C was succeeded by the occurrence of halite-bearing type III fluid inclusion with homogenization temperature as much as 100$^{\circ}$C lower. The salinities of type 1II fluid inclusion in stage II vein are 54.3 to 66.9 wt.% NaCI + KCI equiv. at 383$^{\circ}$ to 495$^{\circ}$C, indicating the formation depth less than 1 km. Type I cupriferous fluids in stage III vein have the homogenization temperatures and salinity of 168$^{\circ}$ to 365$^{\circ}$C and 1.1 to 9.0 wt.% NaCI equiv. These fluid inclusions in stage III veins were trapped in quartz veins containing highly fractured breccia, indicating the predominance of boiling evidence. This corresponds to hydrostatic pressure of 50 to 80 bars. The $\delta$$^{34}S$ value of sulfide minerals increase slightly with paragenetic time and yield calculated $\delta$$^{34}S_{H2S}$ values of 0.8 to 3.7$\textperthousand$. There is no mineralogical evidence that fugacity of oxygen decreased, and it is thought that the oxygen fugacity of the mineralizing fluids have been buffered through reaction with magnetite. We interpreted the range of the calculated $\delta$$^{34}S_{H2S}$ values for sulfides to represent the incorporation of sulfur from two sources into the Xiaoxinancha Cu-Au hydrothermal fluids: (1) an isotopically light source with a $\delta$$^{34}S$ value of I to 2$\textperthousand$, probably a Mesozoic granitoid related to the ore mineralization. We can infer from the fact that diorite as the host rock in the Xiaoxinancha Cu-Au deposit area intruded plagiogranite; (2) an isotopically heavier source with a $\delta$$^{34}S$ value of > 4.0$\textperthousand$, probably the local porphyry.
Kim, Geon-Young;Koh, Yong-Kwon;Choi, Byoung-Young;Shin, Seon-Ho;Kim, Doo-Haeng
Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
/
v.6
no.4
/
pp.307-327
/
2008
Geochemical study on the rocks and minerals of the Gyeongju low and intermediate level waste repository was carried out in order to provide geochemical data for the safety assessment and geochemical modeling. Polarized microscopy, X-ray diffraction method, chemical analysis for the major and trace elements, scanning electron microscopy(SEM), and stable isotope analysis were applied. Fracture zones are locally developed with various degrees of alteration in the study area. The study area is mainly composed of granodiorite and diorite and their relation is gradational in the field. However, they could be easily distinguished by their chemical property. The granodiorite showed higher $SiO_2$ content and lower MgO and $Fe_2O_3$ contents than the diorite. Variation trends of the major elements of the granodiorite and diorite were plotted on the same line according to the increase of $SiO_2$ content suggesting that they were differentiated from the same magma. Spatial distribution of the various elements showed that the diorite region had lower $SiO_2,\;Al_2O_3,\;Na_2O\;and\;K_2O$ contents, and higher CaO, $Fe_2O_3$ contents than the granodiorite region. Especially, because the differences in the CaO and $Na_2O$ distribution were most distinct and their trends were reciprocal, the chemical variation of the plagioclase of the granitic rocks was the main parameter of the chemical variation of the host rocks in the study area. Identified fracture-filling minerals from the drill core were montmorillonite, zeolite minerals, chlorite, illite, calcite and pyrite. Especially pyrite and laumontite, which are known as indicating minerals of hydrothermal alteration, were widely distributed in the study area indicating that the study area was affected by mineralization and/or hydrothermal alteration. Sulfur isotope analysis for the pyrite and oxygen-hydrogen stable isotope analysis for the clay minerals indicated that they were originated from the magma. Therefore, it is considered that the fracture-filling minerals from the study area were affected by the hydrothermal solution as well as the simply water-rock interaction.
Geochemical composition, stable isotopes $({\delta}^{18}O,\;{\delta}D,\;{\delta}^{34}S)$ and noble gases(He, Ne and Ar) of nine hot spring water and three groundwater for five hot springs(Jukam, Hwasun, Dokog, Jirisan, Beunsan) from the Honam area were analyzed to investigate the hydrogeochemical characteristics and the hydrogeochemical evolution of the hot spring waters, and to interpret the source of sulfur, helium and argon dissolved in the hot spring waters. The hot spring waters show low water temperature ranging from 23.0 to $30.5^{\circ}C$ and alkaline characteristics of pH 7.67 to 9.98. Electrical conductivity of hot spring waters is $153{\sim}746{\mu}S/cm$. Groundwaters in this area were characterized by the acidic to neutral pH range$(5.85{\sim}7.21)$, the wide electrical conductivity range $(44{\sim}165{\mu}S/cm)$. The geochemical compositions of hot spring and groundwaters can be divided into three water types: (1) $Na-HCO_3$ water type, (2) Na-Cl water type and (3) $Ca-HCO_3$ water type. The hot spring water of $Ca-HCO_3$ water type in early stage have been evolved through $Ca(Na)-HCO_3$ water type into $Na-HCO_3$ type in final stage. In particular, Jurim alkaline(pH 9.98) hot spring water plotted at the end point of $Na-HCO_3$ type in the Piper diagram is likely to arrive into the final stage in geochemical evolution process. Hydrogen and oxygen isotopic data of the hot spring water samples indicate that the hot spring waters originated from the local meteoric water showing latitude and altitude effects. The ${\delta}^{34}S$ value for sulfate of the hot spring waters varies widely from 0.5 to $25.9%o$. The sulfur source of most hot spring waters in this area is igneous origin. However, The ${\delta}^{34}S$ also indicates the sulfur of JR1 hot water is originated from marine sulfur which might be derived ken ancient seawater sulfates. The $^3He/^4He\;and\;^4He/^{20}Ne$ ratios of the hot spring waters range from $0.0143{\times}10^{-6}\;to\;0.407{\times}10^{-6}\;and\;6.49{\sim}584{\times}10^{-6}$, respectively. The hot spring waters are plotted on the mixing line between air and crustal components. It means that the He gas in the hot spring waters was mainly originated from crustal sources. However, the JR1 hot spring water show a little mixing ratio of the helium gas of mantle source. The $^{40}Ar/^{36}Ar$ ratios of hot spring water are in the range from $292.3{\times}10^{-6}\;to\;304.1{\times}10^{-6}$, implying the atmospheric argon source.
The antimony deposits of the Hyundong mine, located in the northeastern part of the Sobaegsan massif, occur as hydrothermal quartz+carbonate veins and stockworks which fill the fault fractures developed in Precambrian metamOlphic rocks (mainly, granitic gneiss). Hydrothermal alteration occurs commonly in the vicinity of mineralized veins and is characterized by sericitization and silicification. A K-Ar age of alteration sericite is 139.2$\pm$ 4.4 Ma, implying the early Cretaceous age of mineralization, possibly in association with intrusion of nearby acidic dikes (mainly, quartz porphyry). The hydrothermal mineralization occurred in five mineralization stages. These are: (I) stage I, characterized by deposition of chalcedonic quartz; (2) stage II, deposition of quartz with base-metal sulfides and stibnite; (3) stage III, deposition of quartz and carbonates (calcite, dolomite, ankerite, rhodochrosite) with various antimony-bearing minerals such as stibnite, polybasite, berthierite, native antimony, gudmundite and ullmannite; (4) stage IV, deposition of calcite with stibnite; and (5) stage V, deposition of barren calcite. Antimony occurs mostly as stibnite within stages II to IV veins, which has various habits including disseminated, veinlets and euhedral coarse crystals. Fluid inclusion studies indicate that hydrothermal mineralization at Hyundong occurred from the fluids with temperature and salinity of $330^{\circ}$C to 120 and 5.3 wI. % equiv. NaCI. The temperature and salinity of ore fluids systematically decreased with elapsed time in the course of mineralization, possibly due to the influx of larger amounts of meteoric groundwater. The deposition of antimony-bearing minerals occurred at low temperatures «$250^{\circ}$C), mainly due to the cooling and dilution of fluids. Based on the evidence of fluid boiling during the early stage II mineralization, the mineralization occurred under low pressure conditions (about 80 bars, corresponding to depths of about 350 m under hydrostatic pressure regime). Thermodynamic considerations of ore . mineral assemblages indicate that antimony deposition also occurred as the results of decreases in temperature and sulfur fugacity of hydrothermal fluids. Calculated sulfur isotope composition of ore fluids ($\delta^{34}S_{\Sigma s}$=5.4 to 7.8$\textperthousand$) indicates an igneous source of sulfur.
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.
The gold-silver deposits in the Casado district were formed in the sheeted and stockwork quartz veins which fill the fault fractures in volcanic rocks. K-Ar dating of alteration sericite (about 70 Ma) indicates a Late Cretaceous age for ore mineralization. These veins are composed of quartz, adularia, carbonate, and minor of pyrite, sphalerite, chalcopyrite, galena, Ag-sulfosalts (argentite, pearceite, Ag-As-Sb-S system), and electrum. These veins are characterized by chalcedonic, comb, crustiform and feathery textures. Based on the hydrothermally altered mineral assemblages, regional alteration zoning associated with mineralization in the Gasado district is defined as four zones; advanced argillic (kaolin mineral-alunite-quartz), argillic (kaolin mineral-quartz), phyllic (quartz-sericite-pyrite) and propylitic (chlorite-carbonate-quartz-feldspar-pyroxene) zone. Phyllic and propylitic zones is distributed over the study area. However, advanced argillic zone is restricted to the shallow surface of the Lighthouse vein. Compositions of electrum ranges from 14.6 to 53.7 atomic % Au, and the depositional condition for mineralization are estimated in terms of both temperature and sulfur fugacity: T=245。$~285^{\circ}C$, logf $s_2$=$10^{-10}$ ~ $10^{-12}$ Fluid inclusion and stable isotope data show that the auriferous fluids were mixed with cool and dilute (158。~253$^{\circ}C$ and 0.9~3.4 equiv. wt. % NaCl) meteoric water ($\delta^{18}$$O_{water}$=-10.1~8.0$\textperthousand$, $\delta$D=-68~64$\textperthousand$). These results harmonize with the hot-spring type of the low-sulfidation epithermal deposit model, and strongly suggest that Au-Ag mineralization in the Gasado district was formed in low-sulfidation alteration type environment at near paleo-surface.
Rocks in the Cheongsong mine area consist of Precambrian gneiss, Cretaceous sedimentry rocks and late Cretaceous quartz porphyry. The Cheongsong deposit is composed of many hydrothermal quartz veins of strikes $N30^{\circ}{\sim}60^{\circ}W$, dips $60{\sim}85^{\circ}E$ which fill WNW fault system. Pyrite and hematite occur within transparent quartz near margins of early stage II, and milky quartz of middle stage II coexists with sphalerite, chalcopyrite and galena coexisting with Cu-Pb-Bi minerals in center part of stage II quartz veins. Stage III calcite vein filled cracks or fractures of earlier quartz veins contains native copper and chalcopyrite. Supergene minerals are chalcocite, covellite, malanchite and chrysocolla. Alteration minerals are sericite, chlorite, argillite, epitode and pyrite. Ranges of salinities and homogenization temperatures for fluid inclusions in the individual periods of stage II are: 3.7 to 7.8 wt.% eq. NaCl and 200 to $380^{\circ}C$ in transparent quartz of early stage II; 0.7 to 6.4 wt.% eq. NaCl and 200 to $320^{\circ}C$ in milky quartz of middle stage II; 0.0 to 0.9 wt.% eq. NaCl and 250 to $320^{\circ}C$ in calcite of late stage II. Those of stage III calcite range about 0 wt.% eq. NaCl, and from 140 to $260^{\circ}C$, respectively. The relationship between salinities and temperatures shows decrease tendency with paragenetic time from stage II to III. The ${\delta}^{18}O_{H_2O}$ value is 0.5‰ in stage I, range from 0.5 to -0.4‰ in stage II, and from -3.2 to -3.7‰ in stage III. Calcite in the stage II and stage III has ${\delta}^{13}C$ values of -5.0‰ and -4.5 to -4.9‰, respectively. There is a decrease in sulfur fugacity values with paragenetic time of stage II, from $10^{-6.3}$ atm for early mineralization, to $10^{-6.5}$ atm for middle stage, to $10^{-8.0}$ atm for late mineralization of stage II. The results of stable isotope and fluid inclusion indicate that ore fluids reacted with meteoric water and wall rock in the Cheongsong hydrothermal system.
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