The role of uranyl complex decomposition and redox conditions in the precipitation of hydrothermal uranium deposits: Insights from chlorite mineralogy and geochemistry in the Shazhou uranium deposit, Xiangshan, SE China
Authors: Cui Ji-Qiang , Yang Shui-Yuan , Jiang Shao-Yong , Wang Hao , Zhang Ruo-Xi , Tang Xiang-Sheng , Yan Yong-Jie 
Published: April 2023

Uranium precipitation involves the decomposition of uranyl complexes and the reduction of hexavalent uranium, which can occur sequentially or simultaneously within one redox reaction. The redox condition of hydrothermal fluid plays a vital role in controlling the migration and precipitation of uranium in hydrothermal uranium deposits. However, little attention has been paid to the role of uranyl complex decomposition in uranium precipitation. In this study, chlorite mineralogy and geochemistry were examined to clarify the process of uranium precipitation in the Shazhou deposit, Xiangshan uranium orefield, Southeast China. Based on comprehensive petrographic and mineral chemistry studies of chlorites obtained from altered granite porphyries and uranium ores, five types of chlorites were identified: (1) chlorite present in the form of pseudomorphous biotite, which was produced by the hydrothermal alteration of biotite in rocks that underwent hematitization and chloritization (Chl-I); (2) chlorite filling the cleavage cracks in biotite in rocks that underwent hematitization and chloritization (Chl-II); (3) chlorite occurring in pyrite veins (Chl-III); (4) chlorite intergrown with pitchblende in ore veins (Chl-IV); and (5) chlorite occurring in calcite veins (Chl-V). Chlorite geothermometry revealed that the formation temperatures of the five types of chlorites ranged from 219 °C to 254 °C. Mineral chemistry analyses revealed that the five types of chlorites formed in a reductive fluid environment, where the oxygen fugacity at different stages is similar, with log fO2 values ranging from −41.6 to −39.1. Uranium precipitation started only in stage Chl-IV. The examination of the mineral assemblage revealed that the ore-forming fluid was rich in F−, HPO32−, and CO32−. Comprehensive investigation of chemistry and physicochemical conditions of the ore-forming fluid revealed that oxidized uranium (UO22+) could be complexed with HPO42− and F−, and uranyl phosphate and the uranyl fluoride complexes were the main uranium species when uranium precipitation and the decomposition occurred at stage Chl-IV. However, the assessment of oxygen fugacity of the solution equilibria between the UO2(s) and the uranyl phosphate and uranyl fluoride complexes revealed that the reducibility of the fluid favoring the reduction of uranyl ions (UO22+) to U4+ was insufficient to reduce the uranyl phosphate and uranyl fluoride complexes. This indicates that the breakup of uranyl phosphate and the uranyl fluoride complexes to release uranyl ions should occur first at stage Chl-IV, reducing uranyl ions to U4+, and leading to uranium precipitation. Hence, the decomposition of uranyl complexes played an important role in uranium precipitation. With the increase in pH, uranyl phosphate and the uranyl fluoride complexes gradually decomposed and became reducible. Moreover, the decrease in ligand concentration was conducive to the decomposition of uranyl phosphate and the uranyl fluoride complexes. During the formation of the Shazhou deposit, the fluid boiling process induced the loss of volatiles, such as CO2, CH4, HF, and H2S, leading to an increase in pH and decrease in HPO42−, F−, and CO32− concentrations in the fluid. These factors also led to the decomposition of uranyl fluoride and the uranyl phosphate complexes and the precipitation of fluorapatite and calcite. Uranium was then reduced by the action of Fe2+ and S− (pyrite) from a hexavalent to a tetravalent, and finally, uranium was precipitated to form uranium ores.