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HEPHAISTOSITE, Tipb2cls, a NEW THALLIUM MINERAL SPECIES from LA FOSSA CRATER, VULCANO, AEOLIAN ISLANDS, ITALY

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HEPHAISTOSITE, Tipb2cls, a NEW THALLIUM MINERAL SPECIES from LA FOSSA CRATER, VULCANO, AEOLIAN ISLANDS, ITALY 701 The Canadian Mineralogist Vol. 46, pp. 701-708 (2008) DOl: 1O.3749/canmin.46.3.701 HEPHAISTOSITE, TIPb2Cls, A NEW THALLIUM MINERAL SPECIES FROM LA FOSSA CRATER, VULCANO, AEOLIAN ISLANDS, ITALY ITALO CAMPOSTRINI, FRANCESCO DEMARTIN§ AND CARLO MARIA GRAMACCIOLI Dipartimento di Chimiea Strutturale e Stereoehimiea Inorganiea, Universita degli Studi di Milano, via Venezian 21,1-20133 Milano, Italy PAOLO ORLANDI Dipartimento di Scien;e della Terra, Universita degli Studi di Pisa, Via S. Maria 53, 1-56126 Pisa, Italy ABSTRACT Hephaistosite, TIPb2CIs, a newly discovered species of thallium lead chloride, was found in a high-temperature fumarole (~400°C) at the rim of La Fossa crater, Vulcano Island, Aeolian archipelago, Sicily, Italy. The mineral occurs as aggregates of pale yellow-green crystals tabular on {01O} up to 0.1 mm in length on fragments of altered pyroclastic breccia, in association with bismuthinite (Bi2S3), cotunnite (PbCh), challacolloite (KPb2CIs) and pseudocotunnite (K2PbCI4). The mineral is mono- clinic, space group P21/e. Cell parameters refined from powder-diffraction data are: a 8.9477(6), b 7.9218(7), e 12.4955(5) A, 13 90.092(4t, V 885.70(7) A3, with Z = 4. The strongest six reflections in the X-ray powder-diffraction data [d (in A)(l)(hkl)] are: 3.696(100)(013),3.971(83)(020), 2.109(45)(402,215), 2.569(42)(204),1.848(41)(142,026), and 2.851(38)(213). Crystals of hephaistosite show the forms {01O}, {101}, {110}, {100}, {001}, and {011}. Chemical analyses obtained by EDS microprobe gave, on average, in wt.%, TI23.78, K 0.01, Pb 51.78, CI21.40, Br 1.34, F 0.17, for a total of98.48, corresponding to an empirical formula (based on 8 apfu) of Tl094Pb201(CI48SBr014Fo07)1506. Hephaistosite is isostructural with challacolloite; intermediate members of the series between the two species occur in the same fumarole. The calculated density for the synthetic compound (TIPb2CIs) is 5.932 g/cm", The mean index ofrefraction n, obtained from a natural sample using Brewster angle measurement, is 2.0(1). The structure was refined using two different crystals, with TI:K atom ratios of 86:14 and 64:36; the final R index is 0.028 and 0.038, respectively. The mineral, approved by the IMA Commission on New Minerals, Nomenclature and Classifica- tion (No. 2006--043), is named in honor of the ancient Greek god of fire, Hephaistos (Hephaestus, H¢>CUUTO<;),whoseworkshops were alleged to be located at Vulcano. Keywords: hephaistosite, new mineral species, crystal structure, challacolloite, thallium minerals, Vulcano island, Italy. SOMMAIRE Nous avons rcccmment decouvert la hephaistosite, TIPb2CIs, nouvelle cspcce de chlorure de thallium et de plomb, dans une fumerolle de haute temperature (~400°C) en bordure du cratere La Fossa, sur I'He de Vulcano, dans I' archipel Aeolien, partie de la Sicile, en Italie. Le mineral se prcscnte en agregats de cristaux jaune-vert pale, tabulaires sur {01O}, jusqu'a 0.1 mm de long, sur des fragments de breche pyroclastique alteree; lui sont associes bismuthinite (Bi2S3), cotunnite (PbCh), challacolloite (KPb2CIs) et pseudocotunnite (K2PbCI4). Le mineral est monoclinique, groupe spatial P21/e. Les parametres reticulaires, affincs it partir du spectre de diffraction sur poudre, sont: a 8.9477(6), b 7.9218(7), e 12.4955(5) A, 13 90.092(4t, V 885.70(7) A3, avec Z = 4. Les six raies les plus intenses de ce spectre [d (en A)(l)(hkl)] sont: 3.696(100)(013),3.971(83)(020),2.109(45)(402,215), 2.569(42)(204),1.848(41)(142,026), et 2.851(38)(213). Les cristaux de hephaistosite montrent les formes {01O}, {101}, {110}, {100}, {001}, et {011}. Les analyses chimiques effcctuccs avec une microsonde clcctroniquc en dispersion d'energie ont donne, en moyenne, en pourcentages pondcraux, TI23.78, K 0.01, Pb 51.78, CI21.40, Br 1.34, F 0.17, pour un total de 98.48, ce qui correspond it une formule empirique fondee sur huit atomes par formule unitaire de Tlo.94Pb2.01(CI4.8SBro.14Fo.07)lS.06.La hephaistosite est isostructurale avec la challacolloite; des membres intermediaires de la serie entre les deux poles coexistent dans la merne fumerolle. La densitc calculee de I'analogue synthctique (TIPb2CIs) est 5.932 g/cm", L'indice de refraction n moyen d'un echantillon naturel, obtenu en mesurant I'angle de Brewster, est 2.0(1). Nous avons affine la structure de deux cristaux, de composition en terme de rapports atomiques TI:K de 86:14 et 64:36, jusqu'a un residu R de 0.028 et 0.038, respectivement. Le mineral a ete approuvc par la Commission sur les Nouveaux Mineraux, Nomenclature et Classification de I'IMA (no. 2006--043); son nom est inspire du dieu du feu, en mythologie grecque, Hephaistos (Hephaestus, H¢>CUUTO<;),dontles ateliers, semble-t-il, ctaient situcs it Vulcano. (Traduit par la Redaction) Mots-cles: hephaistosite, nouvelle cspcce minerale, structure cristalline, challacolloite, mincraux de thallium, He de Vulcano, Italie. E-mail address:[email protected] 702 THE CANADIAN MINERALOGIST INTRODUCTION the ancient Greek god of fire, Hephaistos (Hephaestus, H<\JaLCTTO<;),whose workshops were alleged to be The island of Vulcano, part of the Aeolian Archi- located at Vulcano. The holotype is deposited (No. pelago, is situated in proximity of the northern coast of 2006-2) in the Reference Collection of Dipartimento Sicily. Its notably interesting geological features have di Chimica Strutturale e Stereochimica Inorganica of long been known. Mercalli & Silvestri (1890) described Universita degli Studi di Milano. the last series of explosive eruptions, which took place from 1888 to 1890. More recent documents on the OCCURRENCE, CHEMICAL DATA geology of Vulcano were published by Sicardi (1973), AND PHYSICAL PROPERTIES Barberi et al. (1974), Keller (1980), and Frazzetta et al. (1983). In 2006, the presence of a new thallium-lead chlo- In recent years, a substantial set of important works ride was noticed by one of us (I.e.) on fragments of concerning this island have been published in the altered pyroclastic breccia collected in a high-temper- fields of volcanology and geochemistry. A detailed ature fumarole (~400°C) at the rim of the crater, using survey of the fumarole field was performed by Harris an EDS-equipped electron microprobe. The mineral & Maciejewski (2000). A semiquantitative estimate of forms aggregates of pale yellow-green crystals tabular fluxes oftrace elements in these fumaroles was provided on {01O}, up to 0.1 mm in length. It is associated with by Cheynet et al. (2000), and a chemical mapping of bismuthinite (Bi2S3), cotunnite (PbC12), challacolloite the fumarolic field has been published by Aiuppa et al. (KPb2Cls) and pseudocotunnite (K2PbC4). (2005, and references therein). Such a renewed interest Quantitative analyses performed using a JEOL JSM was stimulated by a notable increase in fumarolic 5500 LV scanning electron microscope equipped with flow-rates and temperatures, which started in 1987 and an IXRF EDS 2000 microprobe (20 kV, 10-11A, 2 p.m reached a maximum in 1993. beam diameter) showed Tl, Pb, and Cl to be the main Turning our attention to the most relevant mineral- constituents, with minor amounts of Br, K and F; the ogical works, important contributions are due to Alfonso mean analytical results for a specimen close to the Cossa, who described the occurrence of the new species Tl-end member are reported in Table 1. An electron- hieratite, K2SiF6 (Cossa 1881-1882, 1882, 1884). Years microprobe analysis in wavelength-dispersion mode later, additional new fluorides were also observed, was also attempted, but the results were poor owing to such as barberiite, NH4BF4 (Garavelli & Vurro 1994), volatilization of the sample under the electron beam. The demartinite, a hexagonal (6mm) polymorph of K2SiF6 empirical formula (based on eight atoms per formula (Gramaccioli & Campostrini 2007), and a most inter- unit) is Tlo.94Pb2.00(C14.8SBro.14Fo.07hs.06,leading to a esting hexafluorosilicate-tetrafluoroborate, knasibfite, simplified formula: Tll'b-Ck, which ideally requires: K3Na4[SiF6b[BF4] (Demartin et al. 2008). Tl 25.67, Pb 52.06, Cl 22.27 wt.%. In both EDS and The same fumaroles are the type locality for the WDS scans, traces of K were detected also, but no Rb lead-bismuth sulfosalt cannizzarite, Pb4SBis4S127 or Cs. The nature of the analyzed sample was confirmed (Zambonini et al. 1924), which occurs together with by the practical identity of the X-ray powder-diffraction bismuthinite (Bi2S3) and galenobismutite (PbBi2S4), pattern with that of the synthetic pure compound pointing out the importance of bismuth minerals in this Tl l'b-Cl-, of monoclinic P21/C symmetry, which is environment. In more recent times, and in connection near that of the isostructural potassium salt KPb2Cls or with the increased activity of the fumaroles, there has challacolloite (Table 2, and see below). However, the been a renewed interest in the rare minerals occurring existence of a series of more potassium-rich samples at La Fossa crater, leading to the discovery of native in the same environment is suggested by the results of gold and tellurium (Fulignati & Sbrana 1998). In addi- a series of preliminary EDS-microprobe analyses and tion, a number of Bi-bearing sulfosalts (e.g., lillianite, Pb3Bi2S6, and kirkiite, Pb1OBi3As3S19:see, for instance, Pinto 2005) have also been discovered, even including TABLE 1 new species such as mozgovaite, PbBi4(S,Seh, and CHEMICAL COMPOSITION OF HEPHAISTOSITE vurroite, Pb2oSn2(Bi,Ash2Ss4C16 (Vurro et al. 1999, Constituent Ideal wt.% Range Standard Microprobe Garavelli et al. 2005, and references therein), pointing formula deviation standard to an analogy with high-sulfidation epithermal ore deposits. Furthermore, interesting chlorides, such TI 25.67 2378 23.03-2420 0.1 Synthetic TIBr K 0.01 0.00-002 0.1 Synthetic KF as lafossaite, TlCl (Roberts et al.
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