Trace element immobilization by uranyl minerals in granite-hosted uranium ores: Evidences from the Xiazhuang ore field of Guangdong province, China

Abstract

The oxidative alteration of uraninite and the fate of trace elements (Y, LREE, Zr, and Th) in a granite-hosted uranium ore deposit in north Guangdong province, China, were investigated to understand the geochemical behavior of spent UO2fuel and associated fission products and transuranium elements under oxidizing conditions. In light of the paragenetic relationship of the alteration products, two alteration series of uraninite were identified: one is the silicate series with a mineral paragenesis of uraninite → uranyl oxide hydrates → Si-rich uranyl phase → uranophane (Ca[(UO2)(SiO3OH)]2(H2O)5), and the other is the phosphate series with a mineral paragenesis of uraninite → uranyl oxide hydrates → autunite (Ca[(UO2)(PO4)]2(H2O)6) → yingjiangite ((K2,Ca)(UO2)7(PO4)4(OH)6(H2O)6). In contrast to the wide distribution and abundance of uranophane and the uranyl phosphate minerals, uranyl oxides were only occasionally found in the ore samples, suggesting that the uranyl silicates and phosphates should be the predominant alteration products of UO2under oxidizing conditions, although uranyl oxide hydrates would be the solubility-limiting phase of uranium in the very early stage of alteration. Furthermore, the interlayer cation of the uranyl phases in the Xiazhuang uranium ore field is dominated by Ca2+, indicating that the release of uranium and other radionuclides will be limited mainly by uranophane and autunite during the oxidative alteration of spent UO2fuel in underground repositories where enhanced calcium concentration is expected due to cement/water reactions.Compositionally, the cation atomic ratios in uranyl phases often deviate considerably from their respective stoichiometric values as indicated by the nominal formulae, but the compositional variation does not result in significant structural change as indicated by X-ray diffraction patterns. This observation indicates that the structure of U6+minerals may easily be adjusted to accommodate impurity elements including crystallographically compatible radionuclides. Compared with the primary uraninites, the secondary minerals are slightly enriched in light REE, but significantly depleted in Y3+probably due to its cation-radius mismatch with interlayer Ca2+. The apparent enrichment of Zr4+in uranophane and uranyl phosphates relative to uraninite may result from the coupled substitutions: Zr4+↔ U6+and REE3+↔ Ca2+(K+). Because an adequate charge-balance mechanism and significant distortion of the coordination polyhedra are required for the substitution An4+↔ U6+, this type of substitution may not be common.