• Economic and Environmental Geology
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• v.56 no.1
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• pp.55-63
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• 2023

Variations in geochemical and mineralogical properties of the ferromanganese(Fe-Mn) crust reflect environmental changes. In the present study, geochemical and mineralogical analyses, including micro X-ray fluorescence and X-ray diffraction, were utilized to reconstruct the paleo-ocean environment of western Pacific Magellan seamount cluster. Samples of the Fe-Mn crust were collected using an epibenthic sledge from the open seamount XX (151° 51.12' 7.2" E and 16° 8.16' 9.6" N, 1557 meters below sea level) in the Western Pacific Magellan Seamount. According to the structure and phosphating status, the Fe-Mn crust of the OSM-XX can be divided into the following: phosphatizated (L4-L5), massive non-phosphatizated (L3), and porous non-phosphatizated (L1-L2) portions. All ferromanganese layers contain vernadite, and owing to the presence of carbonate fluorapatite (CFA), the phosphatizated portion (L4-L5) is rich in Ca and P. The massive non-phosphatizated section (L3) contains high Mn, Ni, and Co, whereas the porous non-phosphatizated portion (L1-L2), which comprises detrital quartz and feldspar, is rich in Fe. Variations in properties of the Fe-Mn crust from the OSM-XX reflect changes in the nearby marine environment. The formation of this crust started at approximately 51.87 Ma, and precipitation of the CFA during the global phosphatization event that occurred at approximately 36-32 Ma highlights an elevated sea level and low temperature during the associated period. The high Mn, Ni, and Co concentrations and elevated Mn/Fe ratios of samples from the massive phosphatizated portion indicate that the oxygen minimum zone (OMZ) was enhanced, and reducing conditions prevailed during the crust formation. The high Fe and low Mn/Fe ratios in the porous portion indicate a weak OMZ and dominantly oxidizing conditions. These data reflect environmental changes following the end of the Mi-1 glacial period in the Miocene-Oligocene boundary. Subsequently, Mn/Fe and Co/Mn ratios increased slightly in the outermost part of Fe-Mn crust because of the enhanced bottom current and OMZ associated with the continued cooling from approximately 9 Ma. However, the reduced carbonate dissolution rate in the Pacific Ocean from approximately 6 Ma decreased the growth rate of the Fe-Mn crust.

• 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.