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Steverustite, Pb52+(OH)5[Cu+(S6+O3S2–)3](H2O)2, a new thiosulphate mineral from the Frongoch Mine Dump, Devils Bridge, Ceredigion, Wales: description and crystal structure

Published online by Cambridge University Press:  05 July 2018

M. A. Cooper
Affiliation:
Department of Geological Sciences, University of Manitoba, Winnipeg, Manitoba R3T 2N2, Canada
F. C. Hawthorne*
Affiliation:
Department of Geological Sciences, University of Manitoba, Winnipeg, Manitoba R3T 2N2, Canada
E. Moffatt
Affiliation:
Canadian Conservation Institute, 1030 Innes Road, Ottawa, Ontario K1A 0M5, Canada
*

Abstract

Steverustite, ideally Pb52+(OH)5[Cu+(S6+O3S2–)3](H2O)2, is a new supergene mineral from the Frongoch mine dump, Devils Bridge, Ceredigion, Wales. It generally forms fibrous fan-like bundles that occur in small cavities in quartz veins with other supergene species. Crystals are fibrous to acicular, elongated along [010], and are bounded by (h0l) faces too small to index reliably. It is transparent, colourless to white with a white streak, has a vitreous lustre, does not fluoresce under ultraviolet light and is brittle with a splintery fracture. The calculated density is 5.150 g/cm3, and the calculated mean refractive index is 1.94. The mineral is monoclinic, P21/n, a 12.5631(7), b 8.8963(5), c 18.0132(11) Å, β 96.459(1)º, V 2000.5(3) Å3, Z = 4, a:b:c = 1.41217:1:2.02480. The seven strongest lines in the X-ray powder diffraction pattern are as follows: d (Å), I, (h k l): 3.934, 10, (Ī14); 3.934, 8, (Ī11); 3.348, 7, (313); 6.211, 6, (200); 4.797, 6, (211); 3.026, 6, (314); 2.837, 5, (016). Chemical analysis by electron microprobe gave PbO 72.59, SO3 15.78, Cu2O 4.47, S2– 6.32, H2O 4.83, O=S2– –3.15, total 100.84 wt.% where the amount of H2O was determined by crystal-structure analysis. The resulting empirical formula is Pb4.992+Cu0.96+(S6+O3S2–)3.03(OH)4.88(H2O)1.67, based on O + OH + H2O + S2– = 18.67 a.p.f.u. (atoms per formula unit) with H2O = 1.67 a.p.f.u. (from crystal-structure solution and refinement).

The crystal structure of steverustite was solved by direct methods and refined to R1 = 2.7% for 3366 unique (Fo > 4σF) reflections. There are five distinct Pb2+ cations with coordination numbers from [8] to [11], all of which show stereoactive lone-pair behaviour and which form a strongly bonded cluster of composition [Pb5(OH)5]. There is one Cu+ cation triangularly coordinated by three S2– atoms that belong to three thiosulphate groups, forming a Cu+(S6+O3S2–)3 group. The [Pb5(OH)5] units and [Cu(S2O3)3] groups occur at the vertices of interpenetrating 36 nets to form layers of composition [Pb5(OH)5Cu(S2O3)3] parallel to (010) which are linked by weaker bonds. Examination of the stereochemistry of thiosulphate and thionate structures shows that the combination of <S–O> and S–S distances are distinct for these two types of structures.

Type
Research Article
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2009

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References

Benedetti, M. and Boulegue, J. (1991) Mechanism of gold transfer and deposition in a supergene environment. Geochimica et Cosmochimica Acta, 55, 1539—1547.CrossRefGoogle Scholar
Bick, D.E., Parkinson, A.J., Briggs, C.S. and Fellows, R. (1996) Frongoch lead and zinc mine. British Mining 30 (revised edition). Northern Mining Research Society, UK.Google Scholar
Bindi, L., Bonazzi, P., Dei, L. and Zoppi, A. (2005) Does the bazhenovite structure really contain a thiosulfate group? A structural and spectroscopic study of a sample from the type locality. American Mineralogist, 90, 1556—1562.CrossRefGoogle Scholar
Braithwaite, R.S., Kampf, A.R., Pritchard, R.G. and Lamb, R.P. (1993) The occurrence of thiosulfates and other unstable sulfur species as natural weathering products of old smelting slags. Mineralogy and Petrology, 47, 255—261.Google Scholar
Brese, N.E. and O’Keeffe, M. (1991) Bond-valence parameters for solids. Acta Crystallographica B, 47, 192—197.Google Scholar
Brown, I.D. (1981) The bond valence method. An empirical approach to chemical structure and bonding. Pp. 1—30 in: Structure and Bonding in Crystals, Vol. 2 (M. O’Keeffe and A. Navrotsky, editors). Academic Press, New York.Google Scholar
Bruker Analytical X-ray Systems (1997) SHELXTL Reference Manual 5.1., Bruker AXS Inc., Madison, Wisconsin, USA.Google Scholar
Chesnokov, B.V., Polyakov, V.O. and Bushmakin, A.F. (1987) Bazhenovite CaS5-CaS2O3-6Ca(OH)2-20H2O — a new mineral. Zapiski Vsesoyuznogo Mineralogicheskogo Obshchestva, 116, 737—743 (in Russian).Google Scholar
Cooper, M.A. and Hawthorne, F.C. (1999) The structure topology of sidpietersite, , a novel thiosulphate structure. The Canadian Mineralogist, 37, 1275 — 1282.Google Scholar
El Bali, B., Lachkar, M., Sghyar, M., Rachid, O., Alaoui, T.A. and Bolte, M. (2002) Ennea-ammonium dibromide tetra(thiosulfato)argentate. Acta Crystallographica E, Structure Reports Online, 58, 37—38.CrossRefGoogle Scholar
Green, D.I., Rust, S.S. and Mason, J.S. (1996) Classic British Mineral Localities: Frongoch Mine, Dyfed. UK Journal of Mines and Minerals, 17, 29—39.Google Scholar
Hawthorne, F.C. (1992) The role of OH and H2O in oxide and oxysalt minerals. Zeitschrift fur Kristallographie, 201, 183—206.Google Scholar
Kucha, H., Osuch, W. and Elsen, J. (1996) Viaeneite, (Fe,Pb)4S8O, a new mineral with mixed sulphur valencies from Engis, Belgium. European Journal of Mineralogy, 8, 93 — 102.CrossRefGoogle Scholar
Morosin, B. and Larsen, A.C. (1969) The crystal structures of copper tetrammine complexes. B. Na4[Cu(NH3)4][Cu(S2O3)2]2.NH3. Acta Crystallograpica B, 25, 1417—1419.Google Scholar
Pouchou, J.L. and Pichoir, F. (1985) “PAP” ϕ(pz) procedure for improved quantitative microanalysis. Pp. 104—106 in: Microbeam Analysis — 1985. San Francisco Press, San Francisco, California, USA.Google Scholar
Roberts, A.C., Cooper, M.A., Hawthorne, F.C., Criddle, A.J., Stanley, C.J., Key, C.L. and Jambor, J.L. (1999) Sidpietersite, , a new thiosulfate-bearing mineral from Tsumeb, Namibia. The Canadian Mineralogist, 37, 1269—1273.Google Scholar
Ruben, H., Zalkin, A., Faltens, M.O. and Templeton, D.H. (1974) Crystal structure of sodium gold(I) thiosulfate dihydrate, Na3Au(S2O3)2.2H2O. Inorganic Chemistry, 13, 1836—1839.CrossRefGoogle Scholar
Sheldrick, G.M. (1998) SADABS User Guide. University of Göttingen, Germany.Google Scholar
Stomberg, R., Svensson, I.B. and Tomlinson, A.A. (1973) The crystal structure and spectra of Na4(Ni(NH3)4)(Ag(S2O3)2)2(NH3)3. Acta Chemica Scandivica, 27, 1192—1202.Google Scholar
Webster, J.G. (1987) Thiosulfate in surficial geothermal waters, North Island, New Zealand. Applied Geochemistry, 2, 579—584.CrossRefGoogle Scholar
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