Hostname: page-component-cd9895bd7-8ctnn Total loading time: 0 Render date: 2024-12-23T23:27:28.410Z Has data issue: false hasContentIssue false
  • English
  • Français

Uroxite and metauroxite, the first two uranyl oxalate minerals

Published online by Cambridge University Press:  02 September 2019

Anthony R. Kampf Open the ORCID record for Anthony R. Kampf [Opens in a new window] ,
Jakub Plášil ,
Barbara P. Nash ,
Ivan Němec  and
Joe Marty
Anthony R. Kampf*
Affiliation:
Mineral Sciences Department, Natural History Museum of Los Angeles County, 900 Exposition Boulevard, Los Angeles, CA90007, USA
Jakub Plášil
Affiliation:
Institute of Physics ASCR, v.v.i., Na Slovance 1999/2, 18221Prague 8, Czech Republic
Barbara P. Nash
Affiliation:
Department of Geology and Geophysics, University of Utah, Salt Lake City, Utah84112, USA
Ivan Němec
Affiliation:
Department of Inorganic Chemistry, Faculty of Science, Charles University, Hlavova 8, 128 43Prague 2, Czech Republic
Joe Marty
Affiliation:
5199 East Silver Oak Road, Salt Lake City, UT84108, USA
*
*Author for correspondence: Anthony R. Kampf, Email: [email protected]
Get access Rights & Permissions [Opens in a new window]

Abstract

Uroxite (IMA2018-100), [(UO2)2(C2O4)(OH)2(H2O)2]⋅H2O, and metauroxite (IMA2019-030), (UO2)2(C2O4)(OH)2(H2O)2, are the first two uranyl oxalate minerals. Uroxite was found in the Markey mine, Red Canyon, San Juan County, Utah, USA and in the Burro mine, Slick Rock district, San Miguel County, Colorado, USA. Metauroxite was found only in the Burro mine. Both minerals are post-mining secondary phases found in efflorescent crusts on mine walls. Uroxite occurs as light yellow striated blades exhibiting moderate neon-green fluorescence, ca 2 Mohs hardness with good {101} and {010} cleavages. Calculated density = 4.187 g/cm3. Optics are: biaxial (–), α = 1.602(2), β = 1.660(2), γ = 1.680(2) (white light), 2Vmeas. = 59(1)°, 2Vcalc = 59.1°, moderate r > v dispersion, orientation Y = b, Z ∧ a = 35° in obtuse β and it is nonpleochroic. Metauroxite occurs as light yellow crude blades and tablets exhibiting weak green–grey fluorescence, ca 2 Mohs hardness with good {001} cleavage. Calculated density = 4.403 g/cm3. Approximate optics are: α′ = 1.615(5) and γ′ = 1.685(5). Electron probe microanalysis provided UO3 79.60, C2O3 10.02, H2O 10.03, total 99.65 wt.% for uroxite and UO3 82.66, C2O3 10.40, H2O 7.81, total 100.87 wt.% for metauroxite; C2O3 and H2O are based on the structures. Uroxite is monoclinic, P21/c, a = 5.5698(2), b = 15.2877(6), c = 13.3724(9) Å, β = 94.015(7)°, V = 1135.86(10) Å3 and Z = 4. Metauroxite is triclinic, P${\bar 1}$, a = 5.5635(3), b = 6.1152(4), c = 7.8283(4) Å, α = 85.572(5), β = 89.340(4), γ = 82.468°, V = 263.25(3) Å3 and Z = 1. The strongest reflections of the powder XRD pattern [d, Å (I, %)(hkl)] are for uroxite: 10.05(38)(011), 5.00(100)(022, ${\bar 1}$11), 4.75(23)(031), 4.43(51)(120, ${\bar 1}$02), 3.567(33)(131), 3.341(29)(033, ${\bar 1}$32, 004), 2.623(28)(${\bar 2}$02, 015, ${\bar 1}$43, 220) and for metauroxite: 6.06(45)(010), 5.52(33)(100), 4.97(34)(011), 4.52(100)(0${\bar 1}$1, 101), 3.888(80)(111, 002, ${\bar 1}$10), 3.180(51)(${\bar 1}$02, 0${\bar 1}$2), 2.604(32)(${\bar 2}$01, ${\bar 1}$${\bar 2}$1). In the structure of uroxite (R1 = 0.0333 for 2081 I > 2σI reflections), UO7 pentagonal bipyramids share corners forming [U4O24] tetramers, which are linked by C2O4 groups to form corrugated sheets. In the structure of metauroxite (R1 = 0.0648 for 1602 I > 2σI reflections) UO7 pentagonal bipyramids share edges forming [U2O12] dimers, which are linked by C2O4 groups to form zigzag chains.

Keywords

uroxitemetauroxitenew mineraluranyl oxalatecrystal structureBurro mineColoradoUSAMarkey mineUtahUSA
Type
Article
Information
Mineralogical Magazine , Volume 84 , Issue 1 , February 2020 , pp. 131 - 141
Copyright
Copyright © Mineralogical Society of Great Britain and Ireland 2019

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

Footnotes

Associate Editor: Peter Leverett

References

Abraham, F., Arab-Chapelet, B., Rivenet, M., Tamain, C. and Grandjean, S. (2014) Actinide oxalates, solid state structures and applications. Coordination Chemistry Reviews, 266, 28–68.CrossRefGoogle Scholar
Bartlett, J.R. and Cooney, R.P. (1989) On the determination of uranium-oxygen bond lengths in dioxouranium(VI) compounds by Raman spectroscopy. Journal of Molecular Structure, 193, 295–300.CrossRefGoogle Scholar
Brown, I.D. (2002) The Chemical Bond in Inorganic Chemistry. The Bond Valence Model. Oxford University Press, Oxford.Google Scholar
Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G.L., Giacovazzo, C., Mallamo, M., Mazzone, A., Polidori, G. and Spagna, R. (2012) SIR2011: a new package for crystal structure determination and refinement. Journal of Applied Crystallography, 45, 357–361.CrossRefGoogle Scholar
Burns, P.C. (2005) U6+ minerals and inorganic compounds: insights into an expanded structural hierarchy of crystal structures. The Canadian Mineralogist, 43, 1839–1894.CrossRefGoogle Scholar
Burns, P.C., Ewing, R.C. and Hawthorne, F.C. (1997) The crystal chemistry of hexavalent uranium: polyhedron geometries, bond-valence parameters, and polymerization of polyhedra. The Canadian Mineralogist, 35, 1551–1570.Google Scholar
Carter, W.D. and Gualtieri, J.L. (1965) Geology and uranium–vanadium deposits of the La Sal quadrangle, San Juan County, Utah, and Montrose County, Colorado. United States Geological Survey Professional Paper, 508.CrossRefGoogle Scholar
Čejka, J. (1999) Infrared and thermal analysis of the uranyl minerals. Pp. 521–622 in: Uranium: Mineralogy, Geochemistry, and the Environment (Burns, P.C. and Finch, R., editors). Reviews in Mineralogy, 38. Mineralogical Society of America, Washington, DC.CrossRefGoogle Scholar
Chenoweth, W.L. (1993) The Geology and Production History of the Uranium Deposits in the White Canyon Mining District, San Juan County, Utah. Utah Geological Survey Miscellaneous Publication, 93–3.Google Scholar
Colmenero, F. (2019) Structural, spectroscopic, and thermodynamic characterization of ammonium oxalate monohydrate mineral using theoretical solid-state methods. Journal of Physics and Chemistry of Solids, 125, 31–42.CrossRefGoogle Scholar
Duvieubourg, L., Nowogrocki, G., Abraham, F. and Grandjean, S. (2005) Hydrothermal synthesis and crystal structures of new uranyl oxalate hydroxides: α- and β-[(UO2)2(C2O4)(OH)2(H2O)2] and [(UO2)2(C2O4)(OH)2(H2O)2]⋅H2O. Journal of Solid State Chemistry, 178, 3437–3444.CrossRefGoogle Scholar
Ferraris, G. and Ivaldi, G. (1988) Bond valence vs. bond length in O⋅⋅⋅O hydrogen bonds. Acta Crystallographica, B44, 341–344.CrossRefGoogle Scholar
Gagné, O.C. and Hawthorne, F.C (2015) Comprehensive derivation of bond-valence parameters for ion pairs involving oxygen. Acta Crystallographica, B71, 562–578.Google Scholar
Giesting, P.A., Porter, N.J. and Burns, P.C. (2006). Uranyl oxalate hydrates: structures and IR spectra. Zeitschrift für Kristallographie – Crystalline Materials, 221, 252–259.Google Scholar
Higashi, T. (2001) ABSCOR. Rigaku Corporation, Tokyo.Google Scholar
Kampf, A.R., Plášil, J., Kasatkin, A.V., Marty, J. and Čejka, J. (2017) Klaprothite, péligotite and ottohahnite, three new sodium uranyl sulfate minerals with bidentate UO7–SO4 linkages from the Blue Lizard mine, San Juan County, Utah, USA. Mineralogical Magazine, 81, 753–779.CrossRefGoogle Scholar
Kampf, A.R., Plášil, J., Nash, B.P., Němec, I. and Marty, J. (2018) Uroxite, IMA 2018-100. CNMNC Newsletter No. 46, December 2018, page 1376; Mineralogical Magazine, 82, 1369–1379.Google Scholar
Kampf, A.R., Plášil, J., Nash, B.P. and Marty, J. (2019) Metauroxite, IMA 2019-030. CNMNC Newsletter No. 50; Mineralogical Magazine, 83, 615–620, doi: 10.1180/mgm.2019.46Google Scholar
Libowitzky, E. (1999) Correlation of O–H stretching frequencies and O–H⋅⋅⋅O hydrogen bond lengths in minerals. Monatshefte für Chemie, 130, 1047–1059.Google Scholar
Loiseau, T., Mihalcea, I., Henry, N. and Volkringer, C. (2014) The crystal chemistry of uranium carboxylates. Coordination Chemistry Reviews, 266, 69–109.CrossRefGoogle Scholar
Mancilla, N., D'Antonio, M.C., González-Baróc, A.C. and Baranc, E.J. (2009) Vibrational spectra of lead(II) oxalate. Journal of Raman spectroscopy, 40, 2050–2052.CrossRefGoogle Scholar
Mandarino, J.A. (1981) The Gladstone–Dale relationship – Part IV: The compatibility concept and its application. The Canadian Mineralogist, 19, 441–550.Google Scholar
Péligot, E. (1942) Recherches sur l'uranium. Annales de chimie et de physique, 5(5), 5–51.Google Scholar
Peterson, K.I. and Pullman, D.P. (2016) Determining the structure of oxalate anion using infrared and Raman spectroscopy coupled with Gaussian calculations. Journal of Chemical Education, 93, 1130–1133.CrossRefGoogle Scholar
Pouchou, J.-L., and Pichoir, F. (1991) Quantitative analysis of homogeneous or stratified microvolumes applying the model “PAP.” Pp. 3l–75 in: Electron Probe Quantitation (K.F.J. Heinrich and D.E. Newbury, editors). Plenum Press, New York.CrossRefGoogle Scholar
Shawe, D.R. (2011) Uranium-vanadium deposits of the Slick Rock district, Colorado. United States Geological Survey Professional Paper, 576-F.CrossRefGoogle Scholar
Sheldrick, G.M. (2015) Crystal Structure refinement with SHELX. Acta Crystallographica, C71, 3–8.Google Scholar
Shippey, T.A. (1980) Vibrational studies of calcium oxalate monohydrate (whewellite) and an anhydrous phase of calcium oxalate. Journal of Molecular Structure, 63, 157–166.CrossRefGoogle Scholar
Supplementary material: File

Kampf et al. supplementary material

Kampf et al. supplementary material 1

Download Kampf et al. supplementary material(File)
File 50.1 KB
Supplementary material: File

Kampf et al. supplementary material

Kampf et al. supplementary material 2

Download Kampf et al. supplementary material(File)
File 163.6 KB