• Economic and Environmental Geology
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• v.56 no.6
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• pp.847-870
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• 2023

The safe disposal of high-level radioactive waste requires accurate predictions of the long-term geochemical behavior of radionuclides. To achieve this, the present study was conducted to model geochemical behaviors of uranium (U), plutonium (Pu), and palladium (Pd) under different hydrogeochemical conditions that represent deep groundwater in Korea. Geochemical modeling was performed for five types of South Korean deep groundwater environment: high-TDS saline groundwater (G1), low-pH CO₂-rich groundwater (G2), high-pH alkaline groundwater (G3), sulfate-rich groundwater (G4), and dilute (fresh) groundwater (G5). Under the pH and Eh (redox potential) ranges of 3 to 12 and ±0.2 V, respectively, the solubility and speciation of U, Pu, and Pd in deep groundwater were predicted. The result reveals that U(IV) exhibits high solubility within the neutral to alkaline pH range, even in reducing environment with Eh down to -0.2 V. Such high solubility of U is primarily attributed to the formation of Ca-U-CO₃ complexes, which is important in both G2 located along fault zones and G3 occurring in granitic bedrocks. On the other hand, the solubility of Pu is found to be highly dependent on pH, with the lowest solubility in neutral to alkaline conditions. The predominant species are Pu(IV) and Pu(III) and their removal is predicted to occur by sorption. Considering the migration by colloids, however, the role of colloid formation and migration are expected to promote the Pu mobility, especially in deep groundwater of G3 and G5 which have low ionic strengths. Palladium (Pd) exhibits the low solubility due to the precipitation as sulfides in reducing conditions. In oxidizing condition, anionic complexes such as Pd(OH)₃^-, PdCl₃(OH)₂^-, PdCl₄^2-, and Pd(CO₃)₂^2- would be removed by sorption onto metal (hydro)oxides. This study will improve the understanding of the fate and transport of radionuclides in deep groundwater conditions of South Korea and therefore contributes to develop strategies for safe high-level radioactive waste disposal.

• 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.

• Economic and Environmental Geology
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• v.35 no.3
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• pp.211-220
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• 2002

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.