Uranotungstite, the only natural uranyl tungstate: Crystal structure revealed from 3D electron diffraction

Author(s)
Gwladys Steciuk, Uwe Kolitsch, Viktor Goliáš, Radek Skoda, Jakub Plasil, Franz Xaver Schmidt
Abstract

Uranotungstite is an uranyl-tungstate mineral that was until recently only partially characterized with a formula originally given as (Fe2+,Ba,Pb)(UO2)2(WO4)(OH)4·12H2O and an unknown crystal structure. This mineral has been reinvestigated by electron microprobe analysis coupled with three-dimensional electron diffraction. According to the electron microprobe data, the holotype material from the Menzenschwand uranium deposit (Black Forest, Germany) has the empirical formula (Ba0.35Pb0.27)ς0.62[(U6+O2)2(W60.98+ Fe30.26+ □0.75)O4.7(OH)2.5(H2O)1.75](H2O)1.67 (average of 8 points calculated on the basis of 2U apfu; H2O content derived from the structure). According to the precession-assisted 3D ED data, holotype uranotungstite from Menzenschwand is monoclinic, P21/m, with a = 6.318(5) Å, b = 7.388(9) Å, c = 13.71(4) Å, β = 99.04(13)°, and V = 632(2) Å3 (Z = 2). The structure refinement of the 3D ED data using the dynamical approach (Robs = 0.0846 for 3287 independent observed reflections) provided a structure model composed of heteropolyhedral sheets. A β-U3O8-type sheet of idealized composition [(UO2)2W6+Fe30.25+ □0.75O4.75(OH)1.5(H2O)1.75]0.25- is composed of UO7 polyhedra linked by (W,Fe)O5 polyhedra in which the W:Fe ratio is variable as well as the bulk occupancy of this site; the W site may also host a minor proportion of Cu, Mg, or V. In uranotungstite, the interlayer spaces between adjacent U-W-O sheets host water on one side and, on the other side, a partially occupied cation site mostly occupied by Ba and, to a lesser extent, Pb, as well as a partially occupied H2O site. This work is the first structural description of a natural uranyl-tungstate mineral and confirms the great structural and chemical flexibility of β-U3O8 type of sheets.

Organisation(s)
Department of Mineralogy and Crystallography
External organisation(s)
Czech Academy of Sciences, Naturhistorisches Museum Wien (NHM), Charles University Prague, SMNS, Masaryk University
Journal
American Mineralogist
Volume
107
Pages
1709-1716
No. of pages
8
ISSN
0003-004X
DOI
https://doi.org/10.2138/am-2022-8112
Publication date
09-2022
Peer reviewed
Yes
Austrian Fields of Science 2012
105116 Mineralogy, 105113 Crystallography
Keywords
ASJC Scopus subject areas
Geochemistry and Petrology, Geophysics
Portal url
https://ucris.univie.ac.at/portal/en/publications/uranotungstite-the-only-natural-uranyl-tungstate-crystal-structure-revealed-from-3d-electron-diffraction(3de38e7e-a6e5-4c36-b86e-e200a192f2dc).html