Mineralogy, Crystallography and Structural Complexity of Natural Uranyl Silicates

Naturally occurring uranyl silicates are common constituents of the oxidized parts (i.e., supergene zone) of various types of uranium deposits. Their abundance reflects the widespread distribution of Si4+ in the Earth’s crust and, therefore, in groundwaters. Up to date, 16 uranyl silicate minerals are known. Noteworthy is that the natural uranyl silicates are not extremely diverse regarding their crystal structures; it is a result of possible concentrations (activity) of Si4+ in aqueous solutions derived from dissolution of primary Si minerals or the composition of late hydrothermal fluids. Therefore, in natural systems, we distinguish in fact among two groups of uranyl silicate minerals: uranophane and weeksite-group. They differ in U:Si ratio (uranophane, 1:1; weeksite, 2:5) and they form under different conditions, reflected in distinctive mineral associations. An overview of crystal-chemistry is provided in this paper, along with the new structure data for few members of the uranophane group. Calculations of the structural complexity parameters for natural uranyl silicates are commented about as well as other groups of uranyl minerals; these calculations are also presented from the point of view of the mineral paragenesis and associations.

High-T, High-P Hydrothermal Synthesis of Uranium Silicates and Germanates

Most uranium minerals can be classified as oxidized species in which U is fully oxidized to U(VI), and reduced species, in which U occurs primarily as U(IV). Uranyl silicates are an important group of uranium(VI) minerals in the altered zones of many uranium deposits [1]. Uranyl silicates have also received attention because they form when spent nuclear fuel interacts with water containing silicon under oxidizing conditions. One naturally occurring uranium(IV) silicate exists, namely coffinite (USiO4), which is the most important ore mineral for uranium after uraninite. Numerous synthetic uranium(VI) silicates and germanates containing organic amines or alkali metals as countercations have also been reported [2]. In contrast to the uranium(VI) compounds, the chemistry of materials containing uranium(V) is considerably less developed owing to the tendency of U(V) to either oxidize to U(VI) or disproportionate to U(IV) and U(VI). We have synthesized a pentavalent-uranium silicate and a germanate by a high-temperature, high-pressure hydrothermal method in gold ampoules contained in a high-pressure reaction vessel at ca. 600 °C and 170 MPa [3a,b]. Following the synthesis of the U(V) compounds, a number of mixed-valence uranium silicates and germanates have been synthesized, for example, a mixed-valence uranium(IV,V) silicate, Cs2K(UO)2Si4O12 [3c], a uranium(IV,VI) germanate, Cs8U(UO2)3(Ge3O9)3·3H2O [3d], uranium(V,VI) silicates and germanates, A3(U2O4)Ge2O7 (A = Rb, Cs) and [Na9F2][(UO2)3(Si2O7)2] [3e,f], and a uranium(IV,V,VI) silicate, Na7UO2(UO)2(UO2)2Si4O16 [3g] in which three oxidation states of uranium co-exist in one compound. In addition, tetravalent-uranium compounds, Cs2USi6O15 and Cs4UGe8O20 [3h,i], were also synthesized. All members in the family of uranium silicates and germanates with the oxidation states of uranium from +4 to +6 have been observed. In this presentation the high-temperature, high-pressure hydrothermal synthesis, crystal structures, and XPS spectroscopy of these interesting compounds will be reported.