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Relianceite-(K), a new phosphate–oxalate mineral related to davidbrownite-(NH4) from the Rowley mine, Arizona, USA

Published online by Cambridge University Press:  13 December 2021

Anthony R. Kampf*
Affiliation:
Mineral Sciences Department, Natural History Museum of Los Angeles County, 900 Exposition Boulevard, Los Angeles, California 90007, USA
Mark A. Cooper
Affiliation:
Department of Geological Sciences, University of Manitoba, Winnipeg, Manitoba, R3T 2N2, Canada
Aaron J. Celestian
Affiliation:
Mineral Sciences Department, Natural History Museum of Los Angeles County, 900 Exposition Boulevard, Los Angeles, California 90007, USA
Chi Ma
Affiliation:
Division of Geological and Planetary Sciences, California Institute of Technology, 1200 East California Boulevard, Pasadena, California 91125, USA
Joe Marty
Affiliation:
Mineral Sciences Department, Natural History Museum of Los Angeles County, 900 Exposition Boulevard, Los Angeles, California 90007, USA
*
*Author for correspondence: Anthony R. Kampf, Email: [email protected]

Abstract

Relianceite-(K), K4Mg(V4+O)2(C2O4)(PO3OH)4(H2O)10, is a new mineral species from the Rowley mine, Maricopa County, Arizona, USA. It occurs in an unusual bat-guano-related, post-mining assemblage of phases. Other secondary minerals associated with relianceite-(K) are antipinite, dendoraite-(NH4), fluorite, mimetite, mottramite, rowleyite, salammoniac, struvite, vanadinite, willemite, wulfenite and at least one other new mineral. Crystals of relianceite-(K) are sky blue prisms up to ~0.1 mm in length. The streak is very pale blue and lustre is vitreous, Mohs hardness is 2½, tenacity is brittle and fracture is splintery. The calculated density is 2.111 g⋅cm–3. Relianceite-(K) is optically biaxial (+) with α = 1.528(2), β = 1.529(2), γ = 1.562(2) (white light); 2Vmeas = 22(1)°; orientation Z = b; pleochroism: X = colourless, Y = pale blue, Z = pale blue; X < Y ≈ Z. Electron microprobe analysis gave the empirical formula [K2.21(NH4)1.79]Σ4.00Mg0.96(V4+0.95O)2(C2O4)[P1.03O3.03(OH)0.97]4(H2O)10, with the C, N and H contents constrained by the crystal structure. Raman spectroscopy confirmed the presence of NH4 and C2O4. Relianceite-(K) is monoclinic, Pc, with a = 12.404 (7) Å, b = 9.014 (6), c = 13.260 (8) Å, β = 100.803(10)°, V = 1456 (2) Å3 and Z = 2. The structural unit in the crystal structure of relianceite-(K) (R1 = 0.0540 for 3751 Io > 2σI reflections) is a (V4+O)2(C2O4)(PO3OH)4 chain in which VO6 octahedra are bridged by an oxalate group to form [V2C2O12] dimers, PO3OH tetrahedra form a double bridge between the VO6 octahedra of the dimers, and additional PO3OH tetrahedra decorate the chain. Topologically, this is the same chain found in the structure of davidbrownite-(NH4). The MgO(H2O)5 octahedron can be considered a distant decoration on the chain. The chains are linked to each other through an extensive system of K/NH4–O bonds and hydrogen bonds.

Type
Article
Copyright
Copyright © The Author(s), 2021. Published by Cambridge University Press on behalf of The Mineralogical Society of Great Britain and Ireland

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Footnotes

This paper is part of a thematic set that honours the contributions of Peter Williams

Guest Associate Editor: Clara Magalhães

References

Ferraris, G. and Ivaldi, G. (1988) Bond valence vs. bond length in O···O hydrogen bonds. Acta Crystallographica, B44, 341344.CrossRefGoogle Scholar
Frost, R.L. (2004) Raman spectroscopy of natural oxalates. Analytica Chimica Acta, 517, 207214.CrossRefGoogle Scholar
Frost, R.L., Palmer, S.J. and Pogson, R.E. (2011) Raman spectroscopy of newberyite Mg(PO3OH)⋅3H2O: A cave mineral. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 79, 11491153.CrossRefGoogle ScholarPubMed
Gagné, O.C. and Hawthorne, F.C (2015) Comprehensive derivation of bond-valence parameters for ion pairs involving oxygen. Acta Crystallographica, B71, 562578.Google Scholar
García-Rodríguez, L., Rute-Pérez, Á., Piñero, J.R. and González-Silgo, C. (2000) Bond-valence parameters for ammonium-anion interactions. Acta Crystallographica, B56, 565569.CrossRefGoogle Scholar
Gunter, M.E., Weaver, R., Bandli, B.R., Bloss, F.D., Evans, S.H. and Su, S.C. (2004) Results from a McCrone spindle stage short course, a new version of EXCALIBR, and how to build a spindle stage. The Microscope, 52, 2339.Google Scholar
Hardcastle, F.D. and Wachs, I.E. (1991) Determination of vanadium-oxygen bond distances and bond orders by Raman spectroscopy. Journal of Physical Chemistry, 95, 50315041.CrossRefGoogle Scholar
Kampf, A.R., Cooper, M.A., Nash, B.P., Cerling, T., Marty, J., Hummer, D.R., Celestian, A.J., Rose, T.P. and Trebisky, T.J. (2017) Rowleyite, [Na(NH4,K)9Cl4][V5+,4+2(P,As)O8]6n[H2O,Na,NH4,K,Cl], a new mineral with a mesoporous framework structure. American Mineralogist, 102, 10371044.Google Scholar
Kampf, A.R., Cooper, M.A., Rossman, R.R., Nash, B.P., Hawthorne, F.C. and Marty, J. (2019a) Davidbrownite-(NH4), (NH4,K)5(V4+O)2(C2O4)[PO2.75(OH)1.25]4⋅3H2O, a new phosphate-oxalate mineral from the Rowley mine, Arizona, USA. Mineralogical Magazine, 83, 869877.CrossRefGoogle Scholar
Kampf, A.R., Celestian, A.J., Nash, B.P. and Marty, J. (2019b) Phoxite, (NH4)2Mg2(C2O4)(PO3OH)2(H2O)4, the first phosphate-oxalate mineral. American Mineralogist, 104, 973979.CrossRefGoogle Scholar
Kampf, A.R., Cooper, M.A., Celestian, A.J., Nash, B.P. and Marty, J. (2021a) Thebaite-(NH4), (NH4,K)3Al(C2O4)(PO3OH)2(H2O), a new phosphate-oxalate mineral from the Rowley mine, Arizona, USA. Mineralogical Magazine, 85, 379386.CrossRefGoogle Scholar
Kampf, A.R., Cooper, M.A., Celestian, A.J., Ma, C. and Marty, J. (2021b) Relianceite-(K), IMA 2020-102. CNMNC Newsletter 61; Mineralogical Magazine, 85, https://doi.org/10.1180/mgm.2021.48.Google Scholar
Kampf, A.R., Celestian, A.J., Nash, B.P. and Marty, J. (2021c) Allantoin and natrosulfatourea, two new bat–guano minerals from the Rowley mine, Maricopa County, Arizona, U.S.A. The Canadian Mineralogist, 59, 603–616.CrossRefGoogle Scholar
Kampf, A.R., Cooper, M.A., Celestian, A., Ma, C. and Marty, J. (2022) Dendoraite-(NH4), a new phosphate-oxalate mineral related to thebaite-(NH4) from the Rowley mine, Arizona, USA. Mineralogical Magazinet, 86, https://doi.org/10.1180/mgm.2021.98.Google Scholar
Kouvatas, C., Alonzo, V., Bataille, T., Le Pollès, L., Roiland, C., Louarn, G. and Le Fur, E. (2017) Synthesis, crystal structure of the ammonium vanadyl oxalatophosphite and its controlled conversion into catalytic vanadyl phosphates. Journal of Solid State Chemistry, 253, 7377.CrossRefGoogle Scholar
Ma, Q. and He, H. (2012) Synergistic effect in the humidifying process of atmospheric relevant calcium nitrate, calcite and oxalic acid mixtures. Atmospheric Environment, 50, 97102.CrossRefGoogle Scholar
Mandarino, J.A. (2007) The Gladstone–Dale compatibility of minerals and its use in selecting mineral species for further study. The Canadian Mineralogist, 45, 13071324.CrossRefGoogle Scholar
Mohaček-Grošev, V., Grdadolnik, J., Stare, J. and Hadži, D. (2009) Identification of hydrogen bond modes in polarized Raman spectra of single crystals of α-oxalic acid dihydrate. Journal of Raman Spectroscopy, 40, 16051614.CrossRefGoogle Scholar
Rudolph, W.W. and Irmer, G. (2007) Raman and infrared spectroscopic investigations on aqueous alkali metal phosphate solutions and density functional theory calculations of phosphate–water clusters. Applied Spectroscopy, 61, 13121327.CrossRefGoogle ScholarPubMed
Schindler, M., Hawthorne, F.C. and Baur, W.H. (2000) Crystal chemical aspects of vanadium: polyhedral geometries, characteristic bond valences, and polymerization of (VOn) polyhedra. Chemistry of Materials, 12, 12481259.CrossRefGoogle Scholar
Sergeeva, A.V., Zhitova, E.S and Bocharov, V.N. (2019) Infrared and Raman spectroscopy of tschermigite, (NH4)Al(SO4)2⋅12H2O. Vibrational Spectroscopy, 105, 102983.CrossRefGoogle Scholar
Sheldrick, G.M. (2015) Crystal structure refinement with SHELX. Acta Crystallographica, C71, 38.Google Scholar
Števko, M., Sejkora, J., Uher, P., Cámara, F., Škoda, R. and Vaculovič, T. (2018) Fluorarrojadite-(BaNa), BaNa4CaFe13Al(PO4)11(PO3OH)F2, a new member of the arrojadite group from Gemerská Poloma, Slovakia. Mineralogical Magazine, 82, 863876.CrossRefGoogle Scholar
Wilson, W.E. (2020) The Rowley mine, Painted Rock Mountains, Maricopa County, Arizona. Mineralogical Record, 51, 181226.Google Scholar
Yakovenchuk, V.N., Pakhomovsky, Y.A., Konopleva, N.G., Panikorovskii, T.L. Bazai, A., Mikhailova, J.A., Bocharov, V.N., Ivanyuk, G.Yu. and Krivovichev, S.V. (2018) Batagayite, CaZn2(Zn,Cu)6(PO4)4(PO3OH)3⋅12H2O, a new phosphate mineral from Këster tin deposit (Yakutia, Russia): occurrence and crystal structure. Mineralogy and Petrology, 112, 591601.CrossRefGoogle Scholar
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