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Shinkolobweite, from the Shinkolobwe Mine, Democratic Republic of Congo: A New Mineral Containing Uranium in the Rare Pentavalent Oxidation State

Journal Article · · Canadian Journal of Mineralogy and Petrology
DOI:https://doi.org/10.3749/2300003· OSTI ID:2419176
ABSTRACT

Shinkolobweite, Pb1.333[U5+O(OH)(UO2)5O4.67(OH)5.33](H2O)5, is a new lead uranyl oxide-hydroxide hydrate mineral containing hexavalent and pentavalent uranium from the Shinkolobwe mine, Democratic Republic of Congo. Crystals of shinkolobweite are dark reddish-brown prisms up to 0.5 mm in length, occurring on a matrix of massive uraninite associated with fourmarierite, rutherfordine, soddyite, and sklodowskite. Crystals are translucent with subadamantine luster and light bronze-yellow streak, are flattened on {010}, are elongated on [001], and exhibit the forms {100}, {010}, {101}, and . The mineral is non-fluorescent under both longwave and shortwave ultraviolet illumination. It has a Mohs hardness of ∼2 and exhibits brittle tenacity with perfect cleavage on {010}, imperfect cleavage on {100}, and even fracture. The calculated density is 5.853 g/cm3 based on the empirical formula. Electron probe microanalysis provided the empirical formula Pb1.290U6+4.876U5+1.166O27H16.633 based on 27 O apfu and U5+:U6+ determined by X-ray photoelectron spectroscopy. Shinkolobweite is orthorhombic, superspace group Pnnm(0b0)000, a = 14.4808(4), b = 7.0681(8), c = 11.9423(3) Å, V = 1222.32(15) Å3, modulation wave vector [0 1/3 0], and Z = 2. The structure was refined from 8959 reflections to a final R1 = 0.0736 for all reflections. Uranyl oxide-hydroxide sheets in shinkolobweite adopt the β-U3O8 topology and possess (3 + 1) commensurately modulated ordering that results from the long-range ordering of U5+ and U6+ in the sheet, as well as the position and occupancy of interlayer Pb2+ cations. Observations of a topological transition between α-U3O8 and β-U3O8 type sheets in shinkolobweite supplements our understanding of U5+ mineral oxidation and stability.

Research Organization:
University of Notre Dame, IN (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
DOE Contract Number:
FG02-07ER15880
OSTI ID:
2419176
Journal Information:
Canadian Journal of Mineralogy and Petrology, Journal Name: Canadian Journal of Mineralogy and Petrology Journal Issue: 5 Vol. 61; ISSN 2817-1713
Publisher:
Mineralogical Association of Canada
Country of Publication:
United States
Language:
English

References (33)

Dating of U-rich heterogenite: New insights into U deposit genesis and U cycling in the Katanga Copperbelt journal February 2014
Pentavalent uranyl complexes journal August 2009
Pentavalent Uranium Oxide via Reduction of [UO 2 ] 2+ Under Hydrothermal Reaction Conditions journal November 2008
SUPERFLIP – a computer program for the solution of crystal structures by charge flipping in arbitrary dimensions journal July 2007
Neutron diffraction investigation of U 3 O 8 journal June 1964
On the determination of uraniumoxygen bond lengths in dioxouranium(VI) compounds by Raman spectroscopy journal February 1989
La sayrite, (Pb2[(UO2)5O6(OH)2].4H2O, nouveau minéral ; propriétés et structure cristalline journal January 1983
XPS spectra of uranyl minerals and synthetic uranyl compounds. I: The U 4f spectrum journal May 2009
Crystal structure of richetite revisited: Crystallographic evidence for the presence of pentavalent uranium journal September 2017
Comprehensive derivation of bond-valence parameters for ion pairs involving oxygen journal September 2015
Pentavalent uranium chemistry—synthetic pursuit of a rare oxidation state journal January 2009
Nollmotzite, Mg[U V (U VI O 2 ) 2 O 4 F 3 ]·4H 2 O, the first natural uranium oxide containing fluorine journal June 2018
The new K, Pb-bearing uranyl-oxide mineral kroupaite: Crystal-chemical implications for the structures of uranyl-oxide hydroxy-hydrates journal April 2020
High-Resolution X-Ray Photoemission Spectrum of the Valence Bands of Gold journal June 1972
Nanometre-size products of uranium bioreduction journal September 2002
Investigations of Crystal-Chemical Variability in lead Uranyl Oxide Hydrates. ii. Fourmarierite journal June 2000
A Revised and Expanded Structure Hierarchy of Natural and Synthetic Hexavalent Uranium Compounds journal January 2016
The (3+3) commensurately modulated structure of the uranyl silicate mineral swamboite-(Nd), Nd0.333[(UO2)(SiO3OH)](H2O)2.41 journal December 2017
Twinning and incommensurate modulation in baumoite, Ba0.5[(UO2)3O8Mo2(OH)3](H2O)~3, the first natural Ba uranyl molybdate journal April 2019
Wyartite; crystallographic evidence for the first pentavalent-uranium mineral journal September 1999
Gauthierite, KPb[(UO2)7 O5 (OH)7]· 8H2 O, a new uranyl-oxide hydroxy-hydrate mineral from Shinkolobwe with a novel uranyl-anion sheet-topology [Gauthierite, KPb[(UO2)7 O5 (OH)7]· 8H2 O, a new uranyl-oxide hydroxy-hydrate mineral from Shinkolobwe with a novel uranyl-anion sheet-topology] journal March 2017
THE CRYSTAL STRUCTURE OF DEHYDRATED WYARTITE, Ca (CO3) [U5+ (U6+O2)2 O4 (OH)] (H2O)3 journal December 2006
Spriggite, Pb 3 [(UO 2 ) 6 O 8 (OH) 2 ] (H 2 O) 3 , a new mineral with β-U 3 O 8 –type sheets: Description and crystal structure journal February 2004
Hidden and apparent twins in uranyl-oxide minerals agrinierite and rameauite: a demonstration of metric and reticular merohedry journal November 2021
Structural formula of uraninite journal August 1992
Mica Surfaces Stabilize Pentavalent Uranium journal May 2005
The crystal structure of ianthinite, [U24+(UO2)4O6(OH)4(H2O)4](H2O)5: a possible phase for Pu4+ incorporation during the oxidation of spent nuclear fuel journal October 1997
Crystal structure of the uranyl-oxide mineral rameauite [Crystal structure of the uranyl-oxide mineral rameauite] journal January 2016
The Gladstone dale Compatibility of Minerals and its use in Selecting Mineral Species for Further Study journal October 2007
Correlation of O-H stretching frequencies and O-H…O hydrogen bond lengths in minerals journal August 1999
Beam induced reduction of U(VI) during X-ray photoelectron spectroscopy: The utility of the U4f satellite structure for identifying uranium oxidation states in mixed valence uranium oxides journal February 2007
Uranium-Series Ages of Secondary Uranium Minerals with Applications to the Long-Term Evolution of Spent Nuclear Fuel journal January 1995
Bioreduction of Uranium:  Environmental Implications of a Pentavalent Intermediate journal August 2005

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