Hostname: page-component-cd9895bd7-8ctnn Total loading time: 0 Render date: 2024-12-26T15:11:53.007Z Has data issue: false hasContentIssue false
  • English
  • Français

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

Published online by Cambridge University Press:  03 September 2019

Anthony R. Kampf Open the ORCID record for Anthony R. Kampf [Opens in a new window] ,
Mark A. Cooper ,
George R. Rossman ,
Barbara P. Nash ,
Frank. C. Hawthorne  and
Joe Marty
Anthony R. Kampf*
Affiliation:
Mineral Sciences Department, Natural History Museum of Los Angeles County, 900 Exposition Boulevard, Los Angeles, California90007, USA
Mark A. Cooper
Affiliation:
Department of Geological Sciences, University of Manitoba, Winnipeg, Manitoba, R3T 2N2, Canada
George R. Rossman
Affiliation:
Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, California91125, USA
Barbara P. Nash
Affiliation:
Department of Geology and Geophysics, University of Utah, Salt Lake City, Utah84112, USA
Frank. C. Hawthorne
Affiliation:
Department of Geological Sciences, University of Manitoba, Winnipeg, Manitoba, R3T 2N2, Canada
Joe Marty
Affiliation:
5199 East Silver Oak Road, Salt Lake City, Utah84108, USA
*
*Author for correspondence: Anthony R. Kampf, Email: akampf@nhm.org
Get access Rights & Permissions [Opens in a new window]

Abstract

Davidbrownite-(NH4), (NH4,K)5(V4+O)2(C2O4)[PO2.75(OH)1.25]4·3H2O, 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 that include a variety of vanadates, phosphates, oxalates and chlorides, some containing NH4+. Other secondary minerals found in association with davidbrownite-(NH4) are antipinite, fluorite, mimetite, mottramite, quartz, rowleyite, salammoniac, struvite, vanadinite, willemite and wulfenite. Crystals of davidbrownite-(NH4) are light green–blue needles or narrow blades up to ~0.2 mm long. The streak is white, the lustre is vitreous, Mohs hardness is ca. 2, tenacity is brittle and fracture is splintery. There are two good cleavages in the [010] zone, probably {100} and {001}. The measured density is 2.12(2) g cm–3. Davidbrownite-(NH4) is optically biaxial (+) with α = 1.540(2), β = 1.550(5) and γ = 1.582(2) (white light); 2V = 58.5(5)°; moderate r > v dispersion; and orientation Z = b and Y ≈ a. Pleochroism: X = pale blue, Y = nearly colourless, Z = light blue; and Y < X < Z. Electron microprobe analysis gave the empirical formula [(NH4)3.11K1.73Na0.09]Σ4.93[(V4+1.92Mg0.01Al0.02)Σ1.95O2](C2O4) [(P3.94As0.12)Σ4.06O10.94(OH)5.06]·3H2O, with the C and H content provided by the crystal structure. Raman and infrared spectroscopy confirmed the presence of NH4 and C2O4. Davidbrownite-(NH4) is monoclinic, P21/c, with a = 10.356(6), b = 8.923(5), c = 13.486(7) Å, β = 92.618(9)°, V = 1244.9(12) Å3 and Z = 2. The crystal structure of davidbrownite-(NH4) (R1 = 0.0524 for 2062 Io > 2σI reflections) consists of a chain structural unit with the formula {(V4+O)2(C2O4)[PO2.75(OH)1.25]4}5–, and a disordered interstitial complex containing five large monovalent cations (NH4+ and K+) and three H2O groups pfu. Strong hydrogen bonds form links within and between the chains.

Keywords

davidbrownite-(NH4)new mineral speciesphosphateoxalatehydrogen bondingcrystal structureRowley mineArizona, USA
Type
Article
Information
Mineralogical Magazine , Volume 83 , Issue 6 , December 2019 , pp. 869 - 877
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: David Hibbs

References

Beran, A., Armstrong, J. and Rossman, G.R. (1992) Infrared and electron microprobe analysis of ammonium ions in hyalophane feldspar. European Journal of Mineralogy, 4, 847–850.CrossRefGoogle Scholar
Brown, I.D. (2002) The Chemical Bond in Inorganic Chemistry. The Bond Valence Model. Oxford University Press, Oxford, UK.Google Scholar
Brown, I.D. (2016) The Chemical Bond in Inorganic Chemistry: The Bond Valence Model. 2nd Edition. Oxford University Press, Oxford.CrossRefGoogle Scholar
Chukanov, N.V., Pekov, I.V., Olysych, L.V., Zubkova, N.V. and Vigasina, M.F. (2011) Crystal chemistry of cancrinite-group minerals with an AB-type framework: A review and new data. II. IR spectroscopy and its crystal-chemical implications. The Canadian Mineralogist, 49, 1151–1164.CrossRefGoogle Scholar
Colin, J.F., Bataille, T., Ashbrook, S.E., Audebrand, N., Le Pollès, L., Pivan, J.Y. and Le Fur, E. (2006) Na2[(VO)2(HPO4)2C2O4]·2H2O: crystal structure determination from combined powder diffraction and solid-state NMR. Inorganic Chemistry, 45, 6034–6040.CrossRefGoogle ScholarPubMed
Do, J., Bontchev, R.P. and Jacobson, A.J. (2000) A hydrothermal investigation of the ½V2O5–H2C2O4/H3PO4/NH4OH system: synthesis and structures of (NH4)VOPO4·1.5H2O, (NH4)0.5VOPO4·1.5H2O, (NH4)2[VO(H2O)3]2[VO(H2O)][VO(PO4)2]2·3H2O, and (NH4)2[VO(HPO4)]2(C2O4)·5H2O. Inorganic Chemistry, 39, 3230–3237.CrossRefGoogle Scholar
Do, J., Bontchev, R.P. and Jacobson, A.J. (2001) Vanadyl oxalatophosphate compounds (C2H10N2)[VO(HPO4)]2(C2O4) and (CH6N3)2[[VO(HPO4)]2(C2O4) and their thermal transformation to (VO)2P2O7 via VOHPO4. Chemistry of Materials, 13, 2601–2607.CrossRefGoogle Scholar
Edwards, H.G.M., Farwell, D.W., Rose, S.J. and Smith, D.N. (1991) Vibrational spectra of copper(II) oxalate dihydrate, CuC2O4·2H2O, and dipotassium bis-oxalato copper(II) tetrahydrate, K2Cu(C2O4)2·4H2O. Journal of Molecular Structure, 249, 233–243.CrossRefGoogle Scholar
Frost, R.L. and Weier, M.L. (2003) Raman spectroscopy of natural oxalates at 298 and 77 K. Journal of Raman Spectroscopy, 34, 776–785.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
García-Rodríguez, L., Rute-Pérez, Á., Piñero, J.R. and González-Silgo, C. (2000) Bond-valence parameters for ammonium-anion interactions. Acta Crystallographica, B56, 565–569.CrossRefGoogle Scholar
Gunter, M.E., Bandli, B.R.., Bloss, F.D., Evans, S.H., Su, S.C. and Weaver, R. (2004) Results from a McCrone spindle stage short course, a new version of EXCALIBR, and how to build a spindle stage. The Microscope, 52, 23–39.Google Scholar
Hammer, V.M.F., Libowitzky, E. and Rossman, G.R. (1998) Single-crystal IR spectroscopy of very strong hydrogen bonds in pectolite, NaCa2[Si3O8(OH)], and serandite, NaMn2[Si3O8(OH)]. American Mineralogist, 83, 569–576.CrossRefGoogle Scholar
Hawthorne, F.C. (1985) Towards a structural classification of minerals: the viMivT2Øn minerals. American Mineralogist, 70, 455–473.Google Scholar
Hawthorne, F.C. (1997) Structural aspects of oxide and oxysalt minerals. Pp. 373–429 in: Modular Aspects of Minerals (Merlino, S., editor). European Mineralogical Union Notes in Mineralogy, Vol. 1, Eötvös University Press, Budapest, Hungary.Google Scholar
Hawthorne, F.C. (2012) A bond-topological approach to theoretical mineralogy: crystal structure, chemical composition and chemical reactions. Physics and Chemistry of Minerals, 39, 841–874.CrossRefGoogle Scholar
Hawthorne, F.C. and Schindler, M. (2008) Understanding the weakly bonded constituents in oxysalt minerals. Zeitschrift für Kristallographie, 223, 41–68.Google 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]6·n[H2O,Na,NH4,K,Cl], a new mineral with a mesoporous framework structure. American Mineralogist, 102, 1037–1044.Google Scholar
Kampf, A.R., Celestian, A.J., Nash, B.P. and Marty, J. (2019 a) Phoxite, (NH4)2Mg2(C2O4)(PO3OH)2(H2O)4, the first phosphate-oxalate mineral. American Mineralogist, 104, 973–979.CrossRefGoogle Scholar
Kampf, A.R., Cooper, M.A., Rossman, G.R., Nash, B.P., Hawthorne, F.C. and Marty, J. (2019 b) Davidbrownite, IMA 2018-129. CNMNC Newsletter No. 47, February 2019, page 146; Mineralogical Magazine, 83, 143–147.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, 73–77.CrossRefGoogle 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
Mandarino, J.A. (2007) The Gladstone–Dale compatibility of minerals and its use in selecting mineral species for further study. The Canadian Mineralogist, 45, 1307–1324.CrossRefGoogle Scholar
Nagarathinam, M., Saravanan, K., Phua, E.J.H., Reddy, M.V., Chowdari, B.V.R. and Vittal, J.J. (2012) Redox-active metal-centered oxalato phosphate open framework cathode materials for lithium ion batteries. Angewandte Chimie International Edition, 51, 5866–5870.CrossRefGoogle ScholarPubMed
Orive, J., Sivasamy, R., Fernández de Luis, R., Mosquera, E. and Arriortua, M.I. (2018) K2Mn2II(H2O)2C2O4(HPO3)2: a new 2D manganese(II) oxalatophosphite with double-layered honeycomb sheets stabilized by potassium ions. CrystEngComm, 20, 301–311.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 (Heinrich, K.F.J. and Newbury, D.E., D.E., editors). Plenum Press, New York.Google Scholar
Sheldrick, G.M. (2015) Crystal structure refinement with SHELX. Acta Crystallographica, C71, 3–8.Google Scholar
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, 1248–1259.CrossRefGoogle Scholar
Schindler, M. and Hawthorne, F.C. (2001) A bond-valence approach to the structure, chemistry, and paragenesis of hydroxyl-hydrated oxysalt minerals. I. Theory. The Canadian Mineralogist, 9, 1225–1242.CrossRefGoogle Scholar
Takagi, S., Mathew, M. and Brown, W.E. (1980) phosphate ion with three ‘symmetric’ hydrogen bonds: The structure of Ca2(NH4)H7(PO4)4·2H2O. Acta Crystallographica, B36, 766–771.CrossRefGoogle Scholar
Tsai, Y.-M., Wang, S.-L., Huang, C.-H. and Lii, K.-H. (1999) Synthesis and structural characterization of the first organically templated vanadyl(IV) arsenato- and phosphato-oxalates: (C4H12N2)[VO(C2O4)HXO4] (X = As, P). Inorganic Chemistry, 38, 4183–4187.CrossRefGoogle Scholar
Wilson, W.E., and Miller, D.K. (1974) Minerals of the Rowley mine. Mineralogical Record, 5, 10–30.Google Scholar
Supplementary material: File

Kampf et al. supplementary material

Kampf et al. supplementary material

Download Kampf et al. supplementary material(File)
File 385.6 KB