Hostname: page-component-cd9895bd7-jkksz Total loading time: 0 Render date: 2024-12-25T05:06:20.304Z Has data issue: false hasContentIssue false
  • English
  • Français

Short-range constraints on chemical and structural variations in bavenite

Published online by Cambridge University Press:  05 July 2018

A. J. Lussier  and
F. C. Hawthorne
A. J. Lussier
Affiliation:
Department of Geological Sciences, University of Manitoba, Winnipeg, Manitoba, Canada R3T 2N2
F. C. Hawthorne*
Affiliation:
Department of Geological Sciences, University of Manitoba, Winnipeg, Manitoba, Canada R3T 2N2
*
*E-mail: [email protected]
Get access Rights & Permissions [Opens in a new window]

Abstract

Bavenite is an orthorhombic calcium beryllium aluminosilicate, a ≈ 23.2, b ≈ 5.0, c ≈ 19.4 Å, V ≈ 2250 Å3, Z = 4, that crystallizes in the space group Cmcm. The crystal structures of 24 bavenite samples from various localities worldwide were refined to R1 values from 2.4 to 7.5% based on ∼1330 unique reflections collected with Mo-Kα X-radiation on a Bruker P4 CCD single-crystal diffractometer. The composition of each crystal was determined by electron microprobe analysis. There is extensive solid-solution in bavenite according to O(2)OH– + T(4)Si4+ + T(3)Be2+ ⇌ O(2)O2– + T(4)Al3+ + T(3)Si4+, such that the general formula may be written Ca4BexSi9Al4–xO28–x(OH)x, where x ranges from 2.00 to ∼3.00 a.p.f.u. Small amounts of additional Be may be incorporated into bavenite via the substitution T(3)Be + O(2)OH– + Na + T(4)Si2 ⇌ T(3)Si + O(2)O2– + Ca + T(4)Al2. Local (short-range) bond-valence considerations indicate that Short-Range Order (SRO) should be extensive in the bavenite structure, and this is confirmed by Fourier Transform Infrared (FTIR) spectroscopy in the principal OH-stretching region and by 27Al Magic Angle Spinning Nuclear Magnetic Resonance (MAS NMR) spectroscopy. Short-range bond-valence considerations indicate that the T(3)–T(4)–T(3)–T(4) rings of the framework can incorporate any short-range arrangement of cations consonant with their site populations [T(3) = Be,Si; T(4) = Si,Al], and 27Al MAS NMR spectroscopy confirms this, showing the presence of the local clusters T(3)Be–T(4)Al–T(3)Be, T(3)Si–T(4)Al–T(3)Be and T(3)Si–T(4)Al–T(3)Si. Incorporation of Be at the T(3) site is accompanied by local replacement of O2– by (OH)– at the O(2) site and hydrogen bonding to the adjacent O(3) anion; the latter promotes Be → Si substitution at the T(3) tetrahedron adjacent in the b direction. T(3)–T(4)–T(3)–T(4) rings link in the c direction through a T(3)–(1)–(3) linkage [T(1) = Si]. Local bond-valence considerations show that occupancy of both T(3) tetrahedra by Be violates the valence-sum rule, and that the linkage T(3)Be–T(1)Si–T(3)Si provides the constraint whereby Be does not exceed 3 a.p.f.u. in bavenite when incorporated via the substitution O(2)OH– + T(4)Si4+ + T(3)Be2+ ⇌ O(2)O2– + T(4)Al3+ + T(3)Si4+.

Keywords

Bavenitecrystal-structure refinementIR27 Al MAS NMREMPAberylliumend-memberssolid-solution
Type
Research Article
Information
Mineralogical Magazine , Volume 75 , Issue 1 , February 2011 , pp. 213 - 239
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2011

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.)

References

Berry, L.G. (1963) The composition of bavenite. American Mineralogist, 48, 1166–1168.Google Scholar
Beus, A.A. (1966) Geochemistry of Beryllium and Genetic Types of Beryllium Formations. Izd-vo Akademii Nauk, SSSR, Moscow (in Russian).Google Scholar
Bondi, M., Griffin, W.L., Mattioli, V. and Mottana, A. (1983) Chiavennite, CaMnBe2Si5O13(OH)2.2H2O, a new mineral from Chiavenna (Italy). American Mineralogist, 68, 623–627.Google Scholar
Brown, G.E. and Gibbs, G.V. (1969) Oxygen coordination and the Si-O bond. American Mineralogist, 54, 1528–1539.Google 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. and Altermatt, D. (1985) Bond-valence parameters obtained from a systematicanalysis of the inorganic crystal structure database. Acta Crystallographica, B41, 244–247.CrossRefGoogle Scholar
Burns, P.C. and Hawthorne, F.C. (1994) Structure and hydrogen bonding in preobrazhenskite, a complex heteropolyhedr alborate. The Canadian Mineralogist, 32, 387–396.Google Scholar
Cannillo, E., Coda, A. and Fagani, G. (1966) The crystal structure of bavenite. Acta Crystallographica, 20, 301–309.CrossRefGoogle Scholar
Černý, P. (1968) Alteration of beryl in pegmatites; the process and its products. Neues Jahrbuch für Mineralogie Abhandlungen, 108, 166–180.Google Scholar
Černý, P. (2002) Mineralogy of beryliium in granitic pegmatites. Pp. 405–444 in: Beryllium: Mineralogy, Petrology,and Geochemistry (Grew, E.S., editor). Reviews in Mineralogy and Geochemistry, 50, Mineralogica l Society of America and Geochemical Society, Washington, D.C.CrossRefGoogle Scholar
Della Ventura, G., Robert, J.-L., Hawthorne, F.C. and Prost, R. (1996) Short-range disorder of Si and Ti in the tetrahedral double-chain unit of synthetic Tibearing potassium-richterite. American Mineralogist, 81, 56–60.CrossRefGoogle Scholar
Della Ventura, G., Robert, J.-L. and Hawthorne, F.C. (1998) Characterization of OH-F short-range order in potassium-fluor-richterite by infrared spectroscopy in the OH-stretching region. The Canadian Mineralogist, 36, 181–185.Google Scholar
Della Ventura, G., Hawthorne, F.C., Robert, J.-L., Delbove, F., Welch, M.F. and Raudsepp, M. (1999) Short-range order of cations in synthetic amphiboles along the richterite-pargasite join. European Journal of Mineralogy, 11, 79–94.CrossRefGoogle Scholar
Della Ventura, G., Oberti, R., Hawthorne, F.C. and Bellatreccia, F. (2007) FTIR spectroscopy of Ti-rich pargasites from Lherz and the detection of O2– at the anionicO3 site in amphiboles. American Mineralogist, 92, 1645–1651.CrossRefGoogle Scholar
Groat, L.A., Hawthorne, F.C. and Rossman, G.R. (1995) The infrared spectroscopy of vesuvianite in the OH region. The Canadian Mineralogist, 33, 609–626.Google Scholar
Hawthorne, F.C. (1997) Short-range order in amphiboles: a bond-valence approach. The Canadian Mineralogist, 35, 201–216.Google Scholar
Hawthorne, F.C. and Della Ventura, G. (2007) Short-range order in amphiboles. Pp. 173–222 in: Amphiboles: Crystal Chemistry, Occu rrence and Health Issues (Hawthorne, F.C., Oberti, R. Della Ventura, G. and Mottana, A., editors). Reviews in Mineralogy and Geochemistry, 67, Mineralogical Society of America and Geochemical Society, Washington, D.C.Google Scholar
Hawthorne, F.C. and Grice, J.D. (1990) Crystal structure analysis as a chemical analytical method: application to light elements. The Canadian Mineralogist, 28, 693–702.Google Scholar
Hawthorne, F.C. and Huminicki, D.M.C. (2002) The crystal chemistry of beryllium. Pp. 333–403 in: Beryllium: Mineralogy,Petrology,and Geochemistry (Grew, E.S., editor). Reviews in Mineralogy and Geochemistry, 50, Mineralogical Society of America and Geochemical Society, Washington, D.C.CrossRefGoogle Scholar
Hawthorne, F.C., Ungaretti, L. and Oberti, R. (1995) Site populations in minerals: terminology and presentation of results of crystal-structure refinement. The Canadian Mineralogist, 33, 907–911.Google Scholar
Hawthorne, F.C., Oberti, R. and Sardone, N. (1996a) Sodium at the A site in clinoamphiboles: the effects of composition on patterns of order. The Canadian Mineralogist, 34, 577–593.Google Scholar
Hawthorne, F.C., Della Ventura, G. and Robert, J.-L. (1996b) Short-range order of (Na,K) and Al in tremolite: An infrared study. American Mineralogist, 81, 782–784.Google Scholar
Hawthorne, F.C., Welch, M.D., Della Ventura, G., Liu, S., Robert, J.-L. and Jenkins, D.M. (2000) Shortrange order in syntheticaluminous tremolites: An infrared and triple-quantum MAS NMR study. American Mineralogist, 85, 1716–1724.CrossRefGoogle Scholar
Hawthorne, F.C., Della Ventura, G., Oberti, R., Robert, J.-L. and Iezzi, G. (2005) Short-range order in minerals: amphiboles. The Canadian Mineralogist, 43, 1895–1920.CrossRefGoogle Scholar
Hawthorne, F.C., Oberti, R. and Martin, R.F. (2006) Short-range order in amphiboles from the Bear Lake diggings, Ontario. The Canadian Mineralogist, 44, 1171–1179.CrossRefGoogle Scholar
Janeczek, J. (1985) Typomorphism of pegmatite minerals in the Strzegom-Sobotka granite massif. Geologia Sudetica, 20, 1–68.(in Polish).Google Scholar
Kharitonov, Yu.A., Kuz’min, E.A., Ilyukhin, V.V. and Belov, N.V. (1971) The crystal structure of bavenite. Journal of Structural Chemistry, 12, 72–76.CrossRefGoogle Scholar
Peterson, O.V., Micheelsen, H.I. and Leonardsen, E.S. (1995) Bavenite, Ca4Be3Al[Si9O25(OH)3], from the Ilimaussaq alkaline complex, South Greenland. Neues Jahrbuch für Mineralogie Monatshefte, 21, 321–335.Google Scholar
Shannon, R.D. (1976) Revised effective ionic radii and systematicstudies of interatomicdistanc es in halides and chalcogenides. Acta Crystallographica, A32, 751–757.CrossRefGoogle Scholar
Skogby, H. and Rossman, G.R. (1991) The intensity of amphibole OH bands in the infrared absorption spectrum. Physics and Chemistry of Minerals, 1, 64–68.Google Scholar
Switzer, G. and Reichen, L.E. (1960) Re-examination of pilinite and its identification with bavenite. American Mineralogist, 45, 757–762.Google Scholar
Tennyson, C. (1960) Berylliummineralien und ihre pegmatitische Paragenese in den Graniten von Tittling/Bayerischer Wald. Neues Jahrbuch für Mineralogie Abhandlungen, 94, 1253–1265.Google Scholar