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print 2570-7337
online 2570-7345

Theisite, sabelliite and tyrolite from the Cu deposit La Mina Delfina, Ortiguero (Spain)


Keywords

Abstract

Orthorhombic Cu5Zn5[(As,Sb)O4]2(OH)14, mineral theisite, was found in the mine dump material of the abandoned Cu deposit La Mina Delfina, Ortiguero, Spain. Theisite occurs there as turquoise blue flattened crystals with pearly luster forms radial and spherical aggregates up to 6 mm in size in limestone in association with sabelliite and tyrolite. Theisite is orthorhombic, the unit-cell parameters refined from X-ray powder diffraction data are: a 8.231(1), b 7.121(1), c 14.906(1) Å and V 873.7(2) Å3. Chemical analyses of theisite correspond to empirical formula (Cu5.12Zn4.81Ca0.03Mg0.03Ni0.01)Σ10.00 [(AsO4)1.74(SbO4)0.65(PO4)0.02(SiO4)0.05] Σ 2.46(OH)12.68 on the basis of (Cu+Zn+Ca+Mg+Ni+Co) = 10 apfu. Rare sabelliite forms thin tabular crystals up to 50 μm in length composed light blue hemispherical aggregates up to 1 mm accross with pearly luster. Sabelliite is trigonal (space group P-3) with unit-cell parameters a 8.2116(7), c 7.3261(6) Å and V 427.82(7) Å3. Its chemical compositon is possible to express by empirical formula (Cu1.83Zn0.14Ni0.03)Σ2.00Zn1.00[(AsO4)0.72(SbO4)0.19(SiO4)0.05(PO4)0.01]Σ 0.97(OH)3.15. Abundant tyrolite was found as emerald green to bluish green aggregates up to 1 cm in size, it is monoclinic (space group P21/c) with following unit-cell parameters: a 25.557(3), b 5.5672(7), c 10.465(1) Å, β 98.07(5)o and V 1589.5(3) Å3 and empirical formula (Ca2.22Cu8.60Zn0.18) Σ 11.00[(AsO4)3.91(SO4) 0.04(SiO4)0.02(PO4)0.01] Σ 3.98(CO3)1.07(OH)8.11H2O. Tentative interpretation of Raman spectra of theisite and tyrolite is given in the paper.

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References

Bernárdes Gómez MJ, Guisado di Monti JC (2000) La Mina Delfina. Přístup 1. srpna 2017 na adrese https://www.concejodecabrales.com/esp/articulos/mina_delfina.html

Bittarello E, Cámara F, Ciriotti ME (2015) Ottensite, brizziite and mopungite from Pereta mine (Tuscany, Italy): new occurrences and crystal structure refinement of mopungite. Mineral Petrol 109: 431-442

Blas Cortina, MA (1989) La Minería Prehistórica del cobre en las montañas astur-leonesas en Minería y metalurgia en las antiguas civilizaciones mediterráneas y europeas. I Coloquio Internacional Asociado, Madrid 143-153

Bonazzi P, Olmi F (1989) Theisite from Forno (Alpi Apuane) and from Sa Duchessa (Sardinia), Italy. N Jb Mineral Mh 241–244

Burnham Ch W (1962) Lattice constant refinement. Carnegie Inst Washington Year Book 61: 132-135

Čejka J, Sejkora J, Macek I, Malíková R, Wang L, Scholz R, Xi W, Frost RL (2015) Raman and infrared study of turqoise minerals. Spectrochim Acta A 149: 273-182

Drátovský M, Karlíček J (1981) Lithium and sodium antimonates. Chemické Zvěsti 35: 629-640

Frost RL, Bahfenne S (2010a) A review of the vibrational spectroscopis studies of arsenite, antimonite and antimonate minerals. Appl Spectrosc Rev 45: 101-129

Frost RL, Bahfenne S (2010b) Raman spectroscopic study of the antimonate mineral bottinoite Ni[Sb2(OH)12].6H2O and in comparison with brandholzite Mg[Sb5+2(OH)12].6H2O. J Raman Spectrosc 41: 1353-1356

Frost RL, Čejka J, Sejkora J, Ozdín D, Bahfenne S, Keeffe EC (2009) Raman spectroscopic study of the antimonate mineral brandholzite Mg[Sb2(OH)12].6H2O. J Raman Spectrosc 40: 1907-1910

Frost RL, Rintoul L, Bahfenne S (2011) Single crystal Raman spectroscopy of brandholzite Mg[Sb(OH)6]2.6H2O and bottinoite Ni[Sb(OH)6]2.6H2O and the polycrystalline Raman spectrum of mopungite Na[Sb(OH)6]. J Raman Spectrosc 42: 1147-1153

Frost RL, Scholz R, López A (2015) Raman and infrared spectroscopic characterization of the arsenate-bearing mineral tangdanite – and its comparison with the discredited mineral clinotyrolite. J Raman Spectrosc 46: 920-926

Chukanov NV (2014) Infrared spectra of mineral species. Extended Library Vol.1, Springer Dordrecht

Kloprogge JT, Frost RL (2000) Raman microscopy study of tyrolite: A multi-anion arsenate mineral. Appl Spectrosc 54: 517-521

Kolitsch U, Slade PG, Tiekink ERT, Pring A (1999) The structure of antimonian dussertite and the role of antimony in oxysalt minerals. Mineral Mag 63: 17-26

Krivovichev SV, Chernyschev DV, Dobelin N, Armbruster T, Kahlenberg V, Kaindl R, Tessadri R, Kaltenhauser G (2006) Crystal chemistry and polytypism of tyrolite sample: Brixlegg, Schwaz, Tyrol, Austria. Am Mineral 91: 1378-1384

Laugier J, Bochu B (2004) LMGP-Suite of Programs for the interpretation of X-ray experiments. ENSP/Laboratoire des Matériaux et du Génie Physique, Grenoble, France

Libowitzky E (1999) Correlation of O-H stretching frequencies and O-H···O hydrogen bond lenghts in minerals. Monatsh Chem 130: 1047-1059

Ma Z, Li G, Chukanov NV, Poirier G, Shi N (2014) Tangdanite, a new mineral species from the Yunan Province, China and the discreditation of clinotyrolite. Mineral Mag 78: 559-569

Nakamoto K (2009) Infrared and Raman spectra of inorganic and coordination compounds, Part A, Theory and applications in inorganic chemistry, Wiley Hoboken

Nuche R (Ed) (2002) Patrimonio Geológico de Asturia, Cantabria y País Vasco. Madrid 500

O’Brien W (2016) Prehistoric Copper Mining in Europe, 5500–500 BC. Archaeological Journal 173(2): 358–359

Olmi F, Sabelli C, Trosti-Ferroni R (1995a) The crystal structure of sabelliite. Eur J Mineral 7: 1331-1338

Olmi F, Santucci A, Trosti-Ferroni R (1995b) Sabelliite, a new copper-zinc arsenate-antimonate mineral from Sardinia, Italy. Eur J Mineral 7: 1325-1330

Ondruš P (1993) ZDS - A computer program for analysis of X-ray powder diffraction patterns. Materials Science Forum, 133-136, 297-300, EPDIC-2. Enchede

Pouchou JL, Pichoir F (1985) “PAP” (φρZ) procedure for improved quantitative microanalysis. In: Microbeam Analysis (J. T. Armstrong, ed.). San Francisco Press, San Francisco, pp 104-106

Ross SD (1974) Phosphates and other oxy-anions of Group V. In: The infrared spectra of minerals (v.C. Farmer, ed.), The Mineralogical Society London

Siebert H (1966) Anwendungen der Schwingungsspektroskopie in der anorganischen Chemie, Springer Berlin

Števko M, Sejkora J, Bačík P (2011) Mineralogy and origin of supergene mineralization at the Farbište ore occurrence near Poniky, central Slovakia. J Geosci 56: 273-298

Terente LMR, Cabal CL, Claverol MG (2006): Los registros mineros para sustancias metálicas en Asturias. Trabajos de Geología 26: 19-55

VVAA (1994) Revista de Minerales y Yacimientos de España. Bocamina, Grupo Mineralogista de Madrid 0: 50

Wells AF (1986) Structural inorganic chemistry. Clarendon Press Oxford

Williams SA (1982) Theisite, a new mineral from Colorado, Mineral Mag 46: 49-50

Yvon K, Jeitschko W, Parthé E (1977) Lazy Pulverix, a computer program for calculation X-ray and neutron diffraction powder patterns. J Appl Cryst 10: 73-74

Zhao X, Mei D, Xu J, Wu Y (2016) ASb2(SO4)2(PO4) (A=H3O+, K, Rb): Layred structure containing ordered sulfate and phosphate anions. Zeits Allgem Anorg Chem 642: 343-349