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Derbylite and graeserite from the Monte Arsiccio mine, Apuan Alps, Tuscany, Italy: occurrence and crystal-chemistry

Published online by Cambridge University Press:  01 September 2020

Cristian Biagioni*
Affiliation:
Dipartimento di Scienze della Terra, Università di Pisa, Via Santa Maria 53, 56126Pisa, Italy
Elena Bonaccorsi
Affiliation:
Dipartimento di Scienze della Terra, Università di Pisa, Via Santa Maria 53, 56126Pisa, Italy
Natale Perchiazzi
Affiliation:
Dipartimento di Scienze della Terra, Università di Pisa, Via Santa Maria 53, 56126Pisa, Italy
Ulf Hålenius
Affiliation:
Department of Geosciences, Swedish Museum of Natural History, Box 50007, SE-10405Stockholm, Sweden
Federica Zaccarini
Affiliation:
Department of Applied Geological Sciences and Geophysics, University of Leoben, Peter Tunner Str. 5, A-8700 Leoben, Austria
*
*Author for correspondence: Cristian Biagioni, Email: cristian.biagioni@unipi.it

Abstract

New occurrences of derbylite, Fex2+Fe3+4–2xTi4+3+xSb3+O13(OH), and graeserite, Fex2+Fe3+4–2xTi4+3+xAs3+O13(OH), have been identified in the Monte Arsiccio mine, Apuan Alps, Tuscany, Italy. Derbylite occurs as prismatic to acicular black crystals in carbonate veins. Iron and Ti are replaced by V (up to 0.29 atoms per formula unit, apfu) and minor Cr (up to 0.04 apfu). Mössbauer spectroscopy confirmed the occurrence of Fe2+ (up to 0.73 apfu), along with Fe3+. The Sb/(As+Sb) atomic ratio ranges between 0.73 and 0.82. Minor Ba and Pb (up to 0.04 apfu) substitute. Derbylite is monoclinic, space group P21/m, with unit-cell parameters a = 7.1690(3), b = 14.3515(7), c = 4.9867(2) Å, β = 104.820(3)° and V = 495.99(4) Å3. The crystal structure was refined to R1 = 0.0352 for 1955 reflections with Fo > 4σ(Fo). Graeserite occurs as prismatic to tabular black crystals, usually twinned, in carbonate veins or as porphyroblasts in schist. Graeserite in the first kind of assemblage is V rich (up to 0.66 apfu), and V poor in the second kind (0.03 apfu). Along with minor Cr (up to 0.06 apfu), this element replaces Fe and Ti. The occurrence of Fe2+ (up to 0.68 apfu) is confirmed by Mössbauer spectroscopy. Arsenic is dominant over Sb and detectable amounts of Ba and Pb have been measured (up to 0.27 apfu). Graeserite is monoclinic, space group C2/m, with unit-cell parameters for two samples: a = 5.0225(7), b = 14.3114(18), c = 7.1743(9) Å, β = 104.878(3)°, V = 498.39(11) Å3; and a = 5.0275(4), b = 14.2668(11), c = 7.1663(5) Å, β = 105.123(4)° and V = 496.21(7) Å3. The crystal structures were refined to R1 = 0.0399 and 0.0237 for 428 and 1081 reflections with Fo > 4σ(Fo), respectively. Derbylite and graeserite are homeotypic. They share the same tunnel structure, characterised by an octahedral framework and cuboctahedral cavities, hosting (As/Sb)O3 groups and (Ba/Pb) atoms.

Type
Article
Copyright
Copyright © The Author(s), 2020. Published by Cambridge University Press on behalf of The Mineralogical Society of Great Britain and Ireland

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Footnotes

Associate Editor: Elena Zhitova

References

Berlepsch, P. and Armbruster, T. (1998) The crystal structure of Pb2+–bearing graeserite, Pb0.14(Fe,Ti)7AsO12+x(OH)2–x, a mineral of the derbylite group. Schweizerische Mineralogische und Petrographische Mitteilungen, 78, 19.Google Scholar
Biagioni, C., Pasero, M., Hålenius, U. and Bosi, F. (2019) Bianchiniite, IMA 2019–022. CNMNC Newsletter No. 50. Mineralogical Magazine, 83, 615620.Google Scholar
Brese, N.E. and O'Keeffe, M. (1991) Bond-valence parameters for solids. Acta Crystallographica, B47, 192197.CrossRefGoogle Scholar
Bruker AXS Inc. (2016) APEX 3. Bruker Advanced X-ray Solutions, Madison, Wisconsin, USA.Google Scholar
Grey, I.E., Madsen, I.C. and Harris, D.C. (1987) Barian tomichite, Ba0.5(As2)0.5Ti2(V,Fe)5O13(OH), its crystal structure and relationship to derbylite and tomichite. American Mineralogist, 72, 201208.Google Scholar
Harris, D.C., Hoskins, B.F., Grey, I.E., Criddle, A.J. and Stanley, C.J. (1989) Hemloite, (As,Sb)2(Ti,V,Fe,Al)12O23OH: a new mineral from the Hemlo gold deposit, Hemlo, Ontario, and its crystal structure. The Canadian Mineralogist, 27, 427440.Google Scholar
Hussak, E. and Prior, G.T. (1895) Lewisite and zirkelite, two new Brazilian minerals. Mineralogical Magazine, 11, 8088.CrossRefGoogle Scholar
Hussak, E. and Prior, G.T. (1897) On derbylite, a new antimono-titanate of iron, from Tripuhy, Brazil. Mineralogical Magazine, 11, 176179.CrossRefGoogle Scholar
Krivovichev, S.V. (2012) Derivation of bond-valence parameters for some cation–oxygen pairs on the basis of empirical relationships between r 0 and b. Zeitschrift für Kristallographie, 227, 575579.CrossRefGoogle Scholar
Krzemnicki, M.S. and Reusser, E. (1996) Graeserite, Fe4Ti3AsO13(OH), a new mineral species of the derbylite group from the Monte Leone Nappe, Binntal region, Western Alps, Switzerland. The Canadian Mineralogist, 36, 10831088.Google Scholar
Majzlan, J., Drahota, P. and Filippi, M. (2014) Parageneses and crystal chemistry of arsenic minerals. Pp. 17184 in: Environmental Geochemistry, Mineralogy, and Microbiology (Bowell, R.J., Alpers, C.N., Jamieson, H.E., Nordstrom, D.K. and Majzlan, J., editors). Reviews in Mineralogy and Geochemistry, 79. Mineralogical Society of America and the Geochemical Society, Chantilly, Virginia, USA.Google Scholar
Megaw, H.D. (1968) A simple theory of the off centre displacement of cations in octahedral environments. Acta Crystallographica, B24, 149153.CrossRefGoogle Scholar
Mellini, M., Orlandi, P. and Perchiazzi, N. (1983) Derbylite from Buca della Vena mine, Apuan Alps, Italy. The Canadian Mineralogist, 21, 513516.Google Scholar
Mellini, M., Orlandi, P. and Vezzalini, G. (1986) V-bearing derbylite from the Buca della Vena mine, Apuan Alps, Italy. Mineralogical Magazine, 50, 328330.CrossRefGoogle Scholar
Mills, S.J., Christy, A.G., Chen, E.C.-C. and Raudsepp, M. (2009) Revised values of the bond valence parameters for [6]Sb(V)–O and [3–11]Sb(III)–O. Zeitschrift für Kristallographie, 224, 423431.CrossRefGoogle Scholar
Moëlo, Y., Makovicky, E., Mozgova, N.N., Jambor, J.L., Cook, N., Pring, A., Paar, W.H., Nickel, E.H., Graeser, S., Karup-Møller, S., Balić-Žunić, T., Mumme, W.G., Vurro, F., Topa, D., Bindi, L., Bente, K. and Shimizu, M. (2008) Sulfosalt systematics: a review. Report of the sulfosalt sub-committee of the IMA Commission on Ore Mineralogy. European Journal of Mineralogy, 20, 746.CrossRefGoogle Scholar
Moore, P.B. and Araki, T. (1976) Derbylite, Fe43+Ti34+Sb3+O13(OH), a novel close-packed oxide structure. Neues Jahrbuch für Mineralogie Abhandlungen, 126, 292303.Google Scholar
Nickel, E.H. and Grey, I.E. (1979) Tomichite, a new oxide mineral from Western Australia. Mineralogical Magazine, 43, 469471.CrossRefGoogle Scholar
Prescher, C., McCammon, C. and Dubrovinsky, L. (2012) MossA: a program for analyzing energy-domain Mössbauer spectra from conventional and synchrotron sources. Journal of Applied Crystallography, 45, 329331.CrossRefGoogle Scholar
Shannon, R.D. (1976) Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallographica, A32, 751767.CrossRefGoogle Scholar
Sheldrick, G.M. (2015) Crystal structure refinement with SHELXL. Acta Crystallographica, C71, 38.Google Scholar
Wilson, A.J.C. (editor)(1992) International Tables for X-ray Crystallography. Volume C: Mathematical, Physical and Chemical Tables. Kluwer Academic, Dordrecht, The Netherlands.Google Scholar
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