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Lead-antimony sulfosalts from Tuscany (Italy). XIX. Crystal chemistry of chovanite from two new occurrences in the Apuan Alps and its 8 Å crystal structure

Published online by Cambridge University Press:  02 January 2018

Cristian Biagioni  and
Yves Moëlo
Cristian Biagioni*
Affiliation:
Dipartimento di Scienze della Terra, Università di Pisa, Via S. Maria 53, I-56126 Pisa, Italy
Yves Moëlo
Affiliation:
Institut des Matériaux Jean Rouxel, UMR 6502, CNRS, Université de Nantes, 2, rue de la Houssinière, 44322 Nantes Cedex 3, France
*
*E-mail: biagioni@dst.unipi.it
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Abstract

Two new occurrences of the lead oxy-sulfosalt chovanite have been identified at the Monte Arsiccio and Pollone mines, Apuan Alps, Tuscany, Italy. Chovanite from Monte Arsiccio occurs as black acicular crystals, up to 5 mm long, associated with rouxelite, robinsonite, sphalerite, valentinite,baryte, dolomite, quartz and Ba-rich K-feldspar ('hyalophane') in metadolostone vugs. Its unit-cell parameters are a = 48.38(5), b = 4.11(4), c = 34.18(4) Å, β = 106.26(2)°, V = 6521(64) Å3, space group C2/m. Very weakreflections indicate the doubling of the b parameter. Electron-microprobe data gave (wt.%): Ag 0.28, Tl 1.51, Pb 45.57, Sb 31.00, As 1.09, S 19.73, Se 0.05, Cl 0.02, sum 99.25. On the basis of ∑Me = 58 apfu, its formula is Ag0.30Tl0.86Pb25.56Sb29.59As1.69S71.52Se0.07Cl0.05.Adding one oxygen atom, it is close to the formula TlPb26(Sb,As)31S72O. Chovanite from Pollone occurs as thick black acicular crystals, up to 1 cm long, associated with baryte and quartz. The high-diffraction quality of the available material allowed the solutionand refinement of the 8 Å crystal structure in the space group P21/c, with unit-cell parameters a = 34.052(3), b = 8.2027(7), c = 48.078(4) Å, β = 106.258(4)°, V = 12891.9(19) Å3. The refinement convergedto R1 = 9.14% on the basis of 19,853 observed reflections with Fo > 4σ(Fo). Electron-microprobe data gave (wt.%): Ag 0.12, Tl 0.54, Pb 48.34, Bi 0.20, Sb 26.71, As 3.37, S 20.23, Cl 0.07, sum 99.57. It corresponds to the formulaAg0.13Tl0.30Pb26.94Bi0.10Sb25.33As5.20S72.85Cl0.20, close to the idealized formula Pb28(Sb,As)30S72O, with a single oxygen atom bound to two (Sb/As) atoms alternating witha vacancy along b as in scainiite and in other Pb oxy-sulfosalts. The crystal chemistry of this 8 Å crystal structure is detailed, taking into account its modular description, the (Sb,As)mSn polymerization, its topological derivation from pellouxite,and the oxygen non-stoichiometry.

Keywords

chovaniteleadthalliumantimonyarsenicoxy-sulfosaltcrystal structureMonte Arsiccio minePollone mineApuan AlpsTuscanyItaly
Type
Research Article
Information
Mineralogical Magazine , Volume 81 , Issue 4 , August 2017 , pp. 811 - 831
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2017

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References

Bálintova, T., Števko, M. and Ozdín, D. (2006) Sulphosalts of lillianite homologous series from Chyžné occurrence (Slovakia). Mineralogia Polonica — Special Papers, 28, 19–21.Google Scholar
Biagioni, C., Moëlo, Y and Orlandi, P. (2014a) Lead-antimony sulfosalts from Tuscany (Italy). XV (Tl,Ag)-bearing rouxelite from Monte Arsiccio mine: occurrence and crystal chemistry. Mineralogical Magazine, 78, 651–661.CrossRefGoogle Scholar
Biagioni, C., Orlandi, P., Moëlo, Y and Bindi, L. (2014b) Lead-antimony sulfosalts from Tuscany (Italy). XVI. Carducciite, (AgSb)Pb6(Sb,As)8S20, a new Sb-rich derivative of rathite from the Pollone mine, Valdicastello Carducci: occurrence and crystal structure. Mineralogical Magazine, 78, 1775–1793.CrossRefGoogle Scholar
Biagioni, C., Dini, A., Orlandi, P., Moëlo, Y., Pasero, M. and Zaccarini, F. (2016a) Lead-antimony sulfosalts from Tuscany (Italy). XX. Members of the jordanite-geocronite series from the Pollone mine, Valdicastello Carducci: occurrence and crystal structures. Minerals, 6, 1–14.CrossRefGoogle Scholar
Biagioni, C., Moëlo, Y., Orlandi, P. and Stanley, C.J. (2016b) Lead-antimony sulfosalts from Tuscany (Italy). XVII. Meerschautite, (Ag,Cu)5 5Pb42 4(Sb, As)45 ISJJ2O0 8, a new expanded derivative of owy-heeite from the Pollone mine, Valdicastello Carducci: occurrence and crystal structure. Mineralogical Magazine, 80, 675–690.CrossRefGoogle Scholar
Brese, N.E. and O'Keeffe, M. (1991) Bond-valence parameters for solids. Acta Crystallographica, B47, 192–197.CrossRefGoogle Scholar
Bruker AXS Inc. (2004) APEX2. Bruker Advanced X-ray Solutions, Madison, Wisconsin, USA.Google Scholar
Costagliola, P., Benvenuti, M., Tanelli, G., Cortecci, G. and Lattanzi, P. (1990) The barite-pyrite-iron oxides deposit of Monte Arsiccio (Apuane Alps). Geological setting, mineralogy, fluid inclusions, stable isotopes and genesis. Bollettino della Società Geologica Italiana, 109, 267–277.Google Scholar
Costagliola, P., Benvenuti, M., Lattanzi, P. and Tanelli, G. (1998) Metamorphogenic barite-pyrite (Pb-Zn-Ag) veins at Pollone, Apuane Alps, Tuscany: vein geometry, geothermobarometry, fluid inclusions and geochemistry. Mineralogy and Petrology, 62, 29–60.CrossRefGoogle Scholar
Doussier, C., Moëlo, Y, Leone, P. and Meerschaut, A. (2007) (Mn-PbJPbj-Sb-S-CV/), a new oxy-chloro-sulfide with ∼2 nm-spaced (Mn,Pb)Cl4 single chains within a waffle-type crystal-structure. Journal of Solid State Chemistry, 180, 2323–2334.CrossRefGoogle Scholar
Hawthorne, F.C. (2014) The structure hierarchy hypothesis. Mineralogical Magazine, 78, 957–1027.CrossRefGoogle Scholar
Krivovichev, S.V (2012) Derivation of bond-valence parameters for some cation-oxygen pairs on the basis of empirical relationships between r0 an. b. Zeitschrift für Kristallographie, 227, 575–579.CrossRefGoogle Scholar
Makovicky, E. (1985) Cyclically twinned sulphosalt structures and their approximate analogues. Zeitschrift für Kristallographie, 173, 1–23.Google Scholar
Makovicky, E. (1993) Rod-based sulphosalt structures derived from the SnS and PbS archetype. European Journal of Mineralogy, 5, 545–591.CrossRefGoogle Scholar
Makovicky, E. (1995) The building principles and classification of sulphosalts based on the SnS archetype. Fortschritte der Mineralogie, 63, 45–89.Google Scholar
Makovicky, E. (1997) Modular crystal chemistry of sulphosalts and other complex sulfides. Pp. 237–271 in: Modular Aspects of Minerals (S. Merlino, editor). European Mineralogical Union, Notes in Mineralogy, 1. Eötvös University Press, Budapest.Google Scholar
Makovicky, E. and Topa, D. (2009) The crystal structure of sulfosalts with the boxwork architecture and their new representative, Pb15-2xSb14+2xS36Ox . The Canadian Mineralogist, 47, 3–24.CrossRefGoogle Scholar
Makovicky, E., Topa, D. and Mumme, W.G. (2006) The crystal structure of dadsonite. The Canadian Mineralogist, 44, 1499–1512.CrossRefGoogle Scholar
Meerschaut, A., Palvadeau, P., Moëlo, Y and Orlandi, P. (2001) Lead-antimony sulfosalts from Tuscany (Italy). IV Crystal structure of pillaite, Pb9Sb10S23ClO0.5, an expanded monoclinicderivativeof hexagonalBi (Bi2S3)9I3, from the zinkenite group. European Journal of Mineralogy, 13, 779–790.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)-Oand[3,11]Sb(III)-O.Zeitschrift für Kristallographie, 224, 423–431.CrossRefGoogle Scholar
Moëlo, Y., Meerschaut, A., Orlandi, P. and Palvadeau, P. (2000) Lead-antimony sulfosalts from Tuscany (Italy): II-Crystal structure of scainiite, Pb14Sb30S54O5, an expanded monoclinic derivative of Ba12Bi24S48 hexagonal sub-type (zinkenite group). European Journal of Mineralogy, 12, 835–846.CrossRefGoogle Scholar
Moëlo, Y., Orlandi, P., Guillot-Deudon, C., Biagioni, C., Paar, W. and Evain, M. (2011) Lead-antimony sulfosalts from Tuscany (Italy). XI. The new mineral species parasterryite, Ag4Pb20(Sb14 5As9 5)Σ24S58, and associated sterryite, Cu(Ag,Cu)3Pb19(Sb,As)Σ22(As-As)S56, from the Pollone mine, Tuscany, Italy. The Canadian Mineralogist, 49, 623–638.CrossRefGoogle Scholar
Moëlo, Y., Guillot-Deudon, C., Evain, M., Orlandi, P. and Biagioni, C. (2012) Comparative modular analysis of two complex sulfosalt structures: sterryite, Cu(Ag, Cu)3Pb19(Sb,As)22(As—As)S56, and parasterryite, Ag4Pb20(Sb,As)24S58 . Acta Crystallographica, B68, 480–92.CrossRefGoogle Scholar
Orlandi, P., Moëlo, Y., Meerschaut, A. and Palvadeau, P. (1999) Lead-antimony sulfosalts from Tuscany (Italy). I. Scainiite, Pb14Sb30S54O5, the first Pb-Sb oxy-sulfosalt, from Buca della Vena mine. European Journal of Mineralogy, 11, 949–954.CrossRefGoogle Scholar
Orlandi, P., Moëlo, Y., Meerschaut, A. and Palvadeau, P. (2001) Lead-antimony sulfosalts from Tuscany (Italy). III. Pillaite, Pb9Sb10S23ClO0.5, a new Pb-Sb oxy-chloro-sulfosalt,fromBuca della Vena mine. European Journal of Mineralogy, 13, 605–610.CrossRefGoogle Scholar
Orlandi, P., Moëlo, Y., Meerschaut, A., Palvadeau, P. and Léone, P. (2004) Lead-antimony sulfosalts from Tuscany (Italy). VI. Pellouxite, ∼ (Cu,Ag)2 Pb21Sb23S55ClO, a new oxy-chloro-sulfosalt from Buca della Vena mine, Apuan Alps. European Journal of Mineralogy, 16, 839–844.CrossRefGoogle Scholar
Orlandi, P., Moëlo, Y., Meerschaut, A., Palvadeau, P. and Léone, P. (2005) Lead-antimony sulfosalts from Tuscany (Italy). VIII. Rouxelite, Cu2HgPb22Sb28S64(O,S)2, a new sulfosalt from Buca della Vena mine, Apuan Alps: definition and crystal structure. The Canadian Mineralogist, 43, 919–933.CrossRefGoogle Scholar
Palvadeau, P., Meerschaut, A., Orlandi, P. and Moëlo, Y. (2004) Lead-antimony sulfosalts from Tuscany (Italy). VII. Crystal structure of pellouxite, ∼ (Cu,Ag)2 Pb21Sb23S55ClO, an expanded monoclinic derivative of Ba12Bi24S48 hexagonal sub-type (zinkenite group). European Journal of Mineralogy, 16, 845–855.CrossRefGoogle Scholar
Pinto, D., Bonaccorsi, E., Balic-Zunic, T and Makovicky, E. (2008) The crystal structure of vurroite, Pb20Sn2(Bi, As)22S54Cl6: OD-character, polytypism, twinning, and modular description. American Mineralogist, 93, 713–727.CrossRefGoogle Scholar
Sejkora, J., Ozdín, D., Laufek, F., Plášil, J. and Litochleb, J. (2011) Marrucciite, a rare Hg-sulfosalt from the Gelnica ore deposit (Slovak Republic), and its comparison with the type occurrence at Buca della Vena mine (Italy). Journal ofGeosciences, 56, 399–408.Google Scholar
Sheldrick, G.M. (2008) A short history of SHELX. Acta Crystallographica, A64, 112–122.CrossRefGoogle Scholar
Topa, D., Sejkora, J., Makovicky, E., Pršek, J., Ozdín, D., Putz, H., Dittrich, H. and Karup-Møller, S. (2012) Chovanite, Pb15_2xSb14+2xS36Ox (x∼0.2), a new sul-phosalt species from the Low Tatra Mountains, Western Carpathians, Slovakia. European Journal of Mineralogy, 24, 727–740.CrossRefGoogle Scholar
Topa, D., Keutsch, F.N., Makovicky, E., Kolitsch, U. and Paar, W. (2015) Polloneite, IMA 2014-093. CNMNC Newsletter No. 24, April 2015, page 249. Mineralogical Magazine, 79, 247–251.Google Scholar
Wilson, A.J.C. (1992) International Tables for Crystallography Volume C. Kluwer, Dordrecht, The Netherlands.Google Scholar
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