Hostname: page-component-cd9895bd7-fscjk Total loading time: 0 Render date: 2024-12-26T20:58:42.487Z Has data issue: false hasContentIssue false
  • English
  • Français

A single-crystal neutron and X-ray diffraction study of a Li, Be-bearing brittle mica

Published online by Cambridge University Press:  05 July 2018

G. D. Gatta ,
G. Nénert ,
G. Guastella ,
P. Lotti ,
A. Guastoni  and
S. Rizzato
G. D. Gatta*
Affiliation:
Dipartimento di Scienze della Terra, Università degli Studi di Milano, Via Botticelli 23, I-20133 Milan, Italy
G. Nénert
Affiliation:
Institut Laue-Langevin, BP 156, 38042 Grenoble Cedex 9, France
G. Guastella
Affiliation:
Agenzia delle Dogane e dei Monopoli, Direzione Regionale per la Lombardia, Laboratorio e Servizi Chimici, Via Marco Bruto 14, I-20138 Milan, Italy
P. Lotti
Affiliation:
Dipartimento di Scienze della Terra, Università degli Studi di Milano, Via Botticelli 23, I-20133 Milan, Italy
A. Guastoni
Affiliation:
Dipartimento di Geoscienze, Università degli Studi di Padova, Via Gradenigo 6, I-35131 Padua, Italy
S. Rizzato
Affiliation:
Dipartimento di Chimica, Università degli Studi di Milano, Via Golgi 19, I-20133 Milan, Italy
*
*E-mail: [email protected]
Get access Rights & Permissions [Opens in a new window]

Abstract

The crystal chemistry of a meso-octahedral Li,Be-bearing mica from the Harding pegmatite (Dixon, Taos County, New Mexico, USA) has been investigated by constant-wavelength single-crystal neutron diffraction at 20 K, single-crystal X-ray diffraction at 100 K and inductively coupled plasma-atomic emission spectrometry (ICP-AES). The chemical composition based on ICP-AES analysis leads to the following chemical formula (calculated on the basis of 12 oxygen atoms): Ca(Na0.26K0.04Ca0.69)∑0.99M(Li0.29Mg0.03Fe0.023+Al1.78)∑2.12T(Al1.73Be0.16Si2.11)S4.00O12H2.53. The apparent excess of H is probably due to the fact that the fraction of H2O was assumed by difference to 100 wt.%, and slightly overestimated. On the basis of the previous experimental findings on Li,Be-bearing mica, X-ray (at 100 K) and neutron (at 20 K) structure refinements were performed in the space groups Cc and C2/c. The neutron structure refinement in the space group Cc offers a view about the (Al,Be,Si)-tetrahedral ordering: the best fit of the refinement was reached with the T1 and T4 sites occupied by (Be + Al) and T2 and T3 fully occupied by Si. This leads to a final population of T(Al1.88Be0.12Si2.00)∑4.00 p.f.u., in reasonable agreement with the chemical analysis. The neutron refinement provides unambigous evidence of the occurrence of Li at the M1 site. The refined fraction of Li at the M1 site ranges between 0.27 and 0.29 a.p.f.u., in excellent agreement with the chemical analysis. The presence of Li, at least at a significant level, at the M2 (and M3) site can be ruled out, as a full site occupancy with the scattering length of Al was obtained. The location of the H sites and the complex hydrogen-bonding scheme are described. A comparison between the structure features of this Li,Be-mica and other brittle micas is carried out.

Keywords

brittle micasbityiteneutron diffractionX-ray diffractionstructure refinementICP-AES
Type
Research Article
Information
Mineralogical Magazine , Volume 78 , Issue 1 , February 2014 , pp. 55 - 72
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2014

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

Brigatti, M.F. and Guggenheim, S. (2002) Mica crystal chemistry and the influence of pressure, temperature, and solid solution on atomistic models. Pp. 1–98 in: Micas: Crystal Chemistry and Metamorpic Petrology (A. Mottana, F.P. Sassi, J.B. Thompson, Jr. and S. Guggenheim, editors). Reviews in Mineralogy and Geochemistry, 46. Mineralogical Society of America, Washington DC and The Geochemical Society, St Louis, Missouri, USA.CrossRefGoogle Scholar
Brookins, D.G., Chakoumakos, B.C., Cook, C.W., Ewing, R.C., Landis, G.P. and Register, M.E. (1979) The Harding pegmatite: summary of recent research. New Mexico Geological Society Guidebook, 30th Field Conference, Santa Fe County.Google Scholar
Bruker, (2008) APEX2, SAINT and SADABS, Bruker AXS Inc., Madison, Wisconsin, USA.Google Scholar
Busing, W.R. and Levy, H.A. (1964) The effect of thermal motion on the estimation of bond lengths from diffraction measurements. Act a Crystallographica, 17, 142–146.CrossRefGoogle Scholar
Courtois, P., Fernandez-Diaz, M.T., Nénert, G., Andersen, K.H., Freund, A.K., Gsell, S., Fischer, M., Schreck, M., Link, P. and Meven, M. (2013) Performances of the first diamond neutron monochromator at ILL. Proceeding of the International Workshop on Neutron Optics and Detectors (NOPD 2013), 2-5 July 2013, Munich (Ismaning), Germany.Google Scholar
EN ISO 21587-1 (2007) Chemical analysis of aluminosilicate refractory products (alternative to the X-ray fluorescence method) Part 1: Apparatus, reagents, dissolution and gravimetric silica. International Organization for Standardization (http://www.iso.org/iso/home.htm), p. 11.Google Scholar
EN ISO 21587-2 (2007) Chemical analysis of aluminosilicate refractory products (alternative to the X-ray fluorescence method) Part 2: Wet chemical analysis. International Organization for Standardization (http://www.iso.org/iso/home.htm), p. 19.Google Scholar
EN ISO 21587-3 (2007) Chemical analysis of aluminosilicate refractory products (alternative to the X-ray fluorescence method) Part 3: Inductively coupled plasma and atomic absorption spectrometry methods. International Organization for Standardization (http://www.iso.org/iso/home.htm), p. 21.Google Scholar
EN ISO 26845 (2008) Chemical analysis of refractories. General requirements for wet chemical analysis, atomic absorption spectrometry (AAS) and inductively coupled plasma atomic emission spectrometry (ICP-AES) methods. International Organization for Standardization (http://www.iso.org/iso/home.htm), p. 14.Google Scholar
EPA 3052 (1996) Microwave assisted acid digestion of siliceous and organically based matrices. Environmental Protection Agency, 3000 Series Methods (http://www.epa.gov/osw/hazard/testmethods/sw846/pdfs/3052.pdf), p. 20.Google Scholar
EPA 6010c (2007) Inductively Coupled Plasma-Atomic emission Spectrometry. U.S. Environmental Protection Agency, Test Methods for Evaluating Solid Waste, Physical/Chemical Methods SW-846 (http://www.epa.gov/wastes/hazard/testmethods/sw846/pdfs/6010c.pdf ), p. 34.Google Scholar
Farmer, V.C. and Velde, B. (1973) Effects of structural order and disorder on the infrared spectra of brittle micas. Mineralogical Magazine, 39, 282–288.CrossRefGoogle Scholar
Farrugia, L.J. (1999) WinGX suite for small-molecule single-crystal crystallography. Journal of Applied Crystallography, 32, 837–838.CrossRefGoogle Scholar
Ferraris, G. and Ivaldi, G. (2002) Structural features of micas. Pp. 117–154 in: Micas: Crystal Chemistry and Metamorpic Petrology (A. Mottana, F.P. Sassi, J.B. Thompson, Jr. and S. Guggenheim, editors). Reviews in Mineralogy and Geochemistry, 46. Mineralogical Society of America, Washington DC and The Geochemical Society, St Louis, Missouri, USA.CrossRefGoogle Scholar
Gallagher, M.J. and Hawkes, J.R. (1966) Beryllium minerals from Rhodesia and Uganda. Bulletin of the Geological Survey of Great Britain, 25, 59–75.Google Scholar
Gatta, G.D., Nestola, F., Bromiley, G.D. and Mattauch, S. (2006a) The real topological configuration of the extra-framework content in alkali-poor beryl: a multi-methodological study. American Mineralogist, 91, 29–34.CrossRefGoogle Scholar
Gatta, G.D., Nestola, F., Bromiley, G.D. and Loose, A. (2006b) New insight into crystal chemistry of topaz: A multi-methodological study. American Mineralogist, 91, 1839–1846.CrossRefGoogle Scholar
Gatta, G.D., McIntyre, G.J., Sassi, R., Rotiroti, N. and Pavese, A. (2011a) Hydrogen-bond and cation partitioning in 2M1-muscovite: A single-crystal neutron-diffraction study at 295 and 20 K. American Mineralogist, 96, 34–41.CrossRefGoogle Scholar
Gatta, G.D., Merlini, M., Rotiroti, N., Curetti, N. and Pavese, A. (2011b) On the crystal chemistry and elastic behavior of a phlogopite 3T. Physics and Chemistry of Minerals, 38, 655–664.CrossRefGoogle Scholar
Gatta, G.D., Merlini, M., Liermann, H.-P., Rothkirch, A., Gemmi, M. and Pavese, A. (2012) The thermoelastic behavior of clintonite up to 10 GPa and 1,000°C. Physics and Chemistry of Minerals, 39, 385–397.CrossRefGoogle Scholar
Gilli, G. and Gilli, P. (2009) The Nature of the Hydrogen Bond. Oxford University Press, Oxford, UK, 313 pp.CrossRefGoogle Scholar
Guggenheim, S. and Bailey, S.W. (1975) Refinement of the margarite structure in subgroup symmetry. American Mineralogist, 60, 1023–1029.Google Scholar
Guggenheim, S. and Bailey, S.W. (1978) The refinement of the margarite structure in subgroup symmetry; correction, further refinement, and comments. American Mineralogist, 63, 186–187.Google Scholar
Jahns, R.H. and Ewing, R.C. (1976) The Harding mine Taos County New Mexico. New Mexico Geological Society Guidebook, 27th Field Conference, Vermejo Park.Google Scholar
Jarvis, I. and Jarvis, K.E. (1992a) Inductively coupled plasma-atomic emission spectrometry in exploration geochemistry. Journal of Geochemical Exploration, 44, 139–200.CrossRefGoogle Scholar
Jarvis, I. and Jarvis, K.E. (1992b) Plasma spectrometry in the earth sciences: techniques, applications and future trends. Chemical Geology, 95, 1–33.CrossRefGoogle Scholar
JCGM 100 (2008) Joint Committee for Guides in Metrology. Evaluation of measurement data – Guide to the expression of uncertainty in measurement (http://www.bipm.org/utils/common/documents/jcgm/JCGM_100_2008_E.pdf), 134 pp.Google Scholar
Joswig, W., Takéuchi, Y. and Fuess, H. (1983) Neutrondiffraction study on the orientation of hydroxyl groups in margarite. Zeitschrift für Kristallographie, 165, 295–303.CrossRefGoogle Scholar
Joswig, W., Amthauer, G. and Takéuchi, Y. (1986) Neutron diffraction and Mössbauer spectroscopic study of clintonite (xanthophyllite). American Mineralogist, 71, 1194–1197.Google Scholar
Kutukova, E.I. (1959) Beryllium containing margarite from the Middle Urals (in Russian). Akadamii Nauk SSSR Mineralogicheskic Trudy, 8, 128–131.Google Scholar
Lacroix, A. (1908) Les minéraux de fìlons de pegmatite à tourmaline lithique de Madagascar. Bulletin de la Société Française et de Minéralogie, 31, 218–247.CrossRefGoogle Scholar
Larson, A.C. (1967) Inclusion of secondary extinction in least-squares calculations. Acta Crystallographica, 23, 664–665.CrossRefGoogle Scholar
Lehmann, M.S., Kuhs, W., McIntyre, G.J., Wilkinson, C. and Allibon, J. (1989) On the use of a small twodimensional position-sensitive detector in neutron diffraction. Journal of Applied Crystallography, 22, 562–568.CrossRefGoogle Scholar
Lin, J.-C. and Guggenheim, S. (1983) The crystal structure of a Li,Be-rich brittle mica: a dioctahedraltrioctahedral intermediate. American Mineralogist, 68, 130–142.Google Scholar
Montgomery, A. (1953) Pre-Cambrian geology of the Picuris Range, north-central New Mexico. New Mexico Bureau Mines & Mineral Resources Bulletin, 30, 89 pp.Google Scholar
Rowledge, H.P. and Hayton, J.D. (1947) Two new beryllium minerals from Londonderry. Journal and Proceedings of the Royal Society of Western Australia, 33, 45–52.Google Scholar
Sears, V.F. (1986) Neutron scattering lengths and crosssections. Pp. 521–550 in: Neutron Scattering, Methods of Experimental Physics, Vol. 23A, (K. Sköld and D.L. Price, editors). Academic Press, New York.Google Scholar
Sheldrick, G.M. (1997) SHELX-97 – A program for crystal structure refinement. University of Göttingen, Göttingen, Germany.Google Scholar
Sheldrick, G.M. (2008) A short history of SHELX. Acta Crystallographica, A64, 112–122.CrossRefGoogle Scholar
Strunz, H. (1956) Bityit, ein berylliumglimmer. Zeitschrift für Kristallographie, 107, 325–330.CrossRefGoogle Scholar
Takéuchi, Y. (1965) Structure of brittle micas. Clays and Clay Minerals, 13, 1–25.CrossRefGoogle Scholar
Wilkinson, C., Khamis, H.W., Stansfield, R.F.D. and McIntyre, G.J. (1988) Integration of single-crystal reflections using area multidetectors. Journal of Applied Crystallography, 21, 471–478.CrossRefGoogle Scholar
Wilson, A.J.C. and Prince, E. (1999) International Tables for Crystallography Vol. C, Mathematical, Physical and Chemical Tables, second edition. Kluwer, Dordrecht, The Netherlands.Google Scholar