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1457 Vol 43#5 Art 02.Indd 1457 The Canadian Mineralogist Vol. 43, pp. 1457-1468 (2005) WILUITE FROM ARICCIA, LATIUM, ITALY: OCCURRENCE AND CRYSTAL STRUCTURE FABIO BELLATRECCIA Dipartimento di Scienze della Terra, Università di Roma “La Sapienza”, Piazzale Aldo Moro 5, I–00185 Roma, Italy, and Dipartimento di Scienze Geologiche, Università Roma Tre, Largo S. Leonardo Murialdo 1, I–00146 Roma, Italy FERNANDO CÁMARA AND LUISA OTTOLINI CNR – Istituto di Geoscienze e Georisorse, Sede di Pavia, via Ferrata 1, I–27100 Pavia, Italy GIANCARLO DELLA VENTURA§, GIANNANTONIO CIBIN AND ANNIBALE MOTTANA Dipartimento di Scienze Geologiche, Università Roma Tre, Largo S. Leonardo Murialdo 1, I–00146 Roma, Italy ABSTRACT We report a new occurrence of the rare mineral wiluite, the B-rich equivalent of vesuvianite, from Ariccia, Alban Hills volcano, Rome, Italy. The specimen studied was found in the collection of the Museum of Mineralogy of the University of Rome (label MMUR22496/482). Wiluite from Ariccia was sampled at the Parco Chigi quarry, within the phreatomagmatic unit emitted by the Albano maar known locally as “Peperino di Marino”. It occurs as dark brown to black euhedral, well-formed prismatic crystals, up to 1.0 cm in length and 0.5 cm across. Optical observations show a weak pleochroism and an imperfect extinction. The mineral is uniaxial (+) with ␻ 1.722(2) and ␧ 1.727(2). It is tetragonal P4/nnc, a 15.716(2), c 11.704(2) Å, V 2890.8(7) Å3. The crystal-chemical formula, obtained by combining EMP, SIMS and XREF data and calculated on the basis of 18 Si atoms, is: X Y(1) 3+ Y(2) 3+ Y(3) 3+ T(1) (Ca18.72Mg0.15Sr0.02La0.05Ce0.04Nd0.01) (Fe 0.36Mg0.26Ti0.27Mn0.11) (Al3.67Fe 0.19Mg0.14) (Al3.29Fe 1.36Mg3.35) (B2.18 T(2) Z O(11) [O(10)+O(12)] Al0.02Be0.02H0.47Ⅺ1.31) (B0.68H0.32) Si18O68 (F1.21O6.79) O2.68. The micro OH-stretching FTIR spectrum consists of a defi ned triplet of broad bands at 3639, 3573 and 3488 cm–1, respectively, and a very broad, composite absorption at 3300 cm–1. All bands are strongly polarized, with maximum absorption for E // c and minimum absorption for E ֊ c. The integrated –1 –2 –1 molar absorption coeffi cient for wiluite is ␧i = 90.000 ± 1500 l mol cm . In the 1600–1100 cm region, absorptions due to both [3]B–O and [4]B–O bonds are observed. The Mg and Al K-edge X-ray-absorption spectra are consistent with the presence of two octahedral coordination sites for both atoms, as determined by XREF, with the addition of a third, highly unusual, fi ve-fold pyramidal site for the divalent cation. Keywords: wiluite, vesuvianite, electron-microprobe data, secondary-ion mass spectrometry, infrared spectroscopy, single-crystal X-ray diffraction, boron, Ariccia, Italy. SOMMAIRE Nous décrivons un nouvel exemple de la wiluite, espèce rare, l’analogue riche en bore de la vésuvianite, provenant d’Ariccia, volcan des collines albanes, à Rome, en Italie. L’échantillon a été trouvé dans la collection du Musée de Minéralogie de l’Uni- versité de Rome (numéro MMUR22496/482). Cet échantillon provient de la carrière de Parco Chigi, de l’unité phréatomagma- tique émise par le maar de Albano, appelée localement “Peperino di Marino”. La wiluite y est présente en cristaux prismatiques idiomorphes bruns foncés à noirs, atteignant 1.0 cm de long et 0.5 cm de diamètre. Les observations optiques révèlent un faible pléochroïsme et une extinction imparfaite. Le minéral est uniaxe (+), avec ␻ 1.722(2) et ␧ 1.727(2). Il est tétragonal P4/nnc, a 15.716(2), c 11.704(2) Å, V 2890.8(7) Å3. La formule cristallochimique, obtenue à la lumière des données obtenues avec une microsonde électronique, une microsonde ionique et par diffraction X sur monocristal, et recalculées sur une base de 18 atomes X Y(1) 3+ Y(2) 3+ Y(3) 3+ de Si, serait: (Ca18.72Mg0.15Sr0.02La0.05Ce0.04Nd0.01) (Fe 0.36Mg0.26Ti0.27Mn0.11) (Al3.67Fe 0.19Mg0.14) (Al3.29Fe 1.36M T(1) T(2) Z O(11) [O(10)+O(12)] g3.35) (B2.18Al0.02Be0.02H0.47Ⅺ1.31) (B0.68H0.32) Si18O68 (F1.21O6.79) O2.68. La microspectrométrie infrarouge de la zone d’étirement de OH avec transformation de Fourier révèle un trio de bandes fl oues, à 3639, 3573 et 3488 cm–1, respec- tivement, et une absorption composite très fl oue à 3300 cm–1. Toutes ces bandes sont fortement polarisées, avec une absorption maximum pour E // c et une absorption minimum pour E ֊ c. Le coeffi cient d’absorption molaire intégré de la wiluite ␧i serait 90.000 ± 1500 l mol–1 cm–2. Des absorptions dues aux liaisons [3]B–O et [4]B–O sont présentes entre 1600 et 1100 cm–1. Les § E-mail address: [email protected] 1458 THE CANADIAN MINERALOGIST spectres d’absorption des rayons X émis par Mg et Al concordent avec la présence de deux sites à coordinence octaèdrique pour chaque atome, tel qu’indiqué par affi nement de la structure, et aussi la présence d’un troisième site très inhabituel à coordinence cinq, pyramidal, pour le cation bivalent. (Traduit par la Rédaction) Mots-clés: wiluite, vésuvianite, microsonde électronique, microsonde ionique, spectroscopie infrarouge, diffraction X sur mono- cristal, bore, Ariccia, Italie. INTRODUCTION of Rome “La Sapienza” (label MMUR 22496/482, hereafter 26FB). It was collected at the ignimbrite quarry Wiluite, Ca19(Al,Mg,Fe,Ti)13(B,Al,Ⅺ)5Si18O68 of Parco Chigi, Ariccia community, Rome, Latium. The (O,OH)10, is the B-rich analogue of vesuvianite, phreatomagmatic unit in which wiluite occurs, locally recently characterized from a sample of Wilui River, known as “Peperino di Marino”, erupted about 23,000 Sakha Republic, Russian Federation, and found within years ago from the polygenetic Lake Albano maar, part serpentinite associated with grossular and serpentine- of the Alban Hills volcano in central Italy (Giordano group minerals. Although it has been known for some et al. 2002). In Latium, vesuvianite typically occurs in time that vesuvianite commonly contains boron and that skarn-type ejecta (Bellatreccia 2003), which are frag- vesuvianite from the Wilui region, in particular, contains ments of the metasomatized carbonate-rich wallrock. signifi cant amounts of boron (indeed, the name wiluite Wiluite from Parco Chigi is found scattered within the had been in use in the literature for samples from there pyroclastic deposit; as such, it is unclear whether it for a long time), the species had never been formally originated from disaggregated metasomatic xenoliths defi ned until the work of Groat et al. (1998). As shown or by magmatic crystallization. by Groat et al. (1994) vesuvianite can incorporate up Wiluite occurs as well-formed, euhedral, prismatic to 4 wt% B2O3, the boron substitutes for H, according crystals (Fig. 1), with a maximum dimension of 1.0 to the BMgH–2Al–1 exchange vector. Boron is distri- cm along c and 0.5 cm across. All crystals show a buted over two sites of the vesuvianite structure: T(1), well-defi ned morphology, with a short prismatic habit; where it replaces two H1 hydrogen atoms and adopts they consist of tetragonal {100} and {110} prisms tetrahedral coordination, and T(2), where it replaces one doubly terminated by ditetragonal {101} pyramids H2 hydrogen atom and adopts triangular coordination cut at the apex by the {001} pinacoid. They are dark (Groat et al. 1994, 1996). brown to black in hand specimen. In thin section, the During a systematic crystal-chemical study of vesu- mineral is colorless to light yellowish green, very vianite-group minerals (Bellatreccia 2003) collected weakly pleochroic. There is a strong optical sector- in the tephra scattered within the Plio-Pleistocene zoning, from cross-hatched domains to fi ne lamellar volcanic region of Latium, Italy, we found that most of zones; under crossed polarizers, the extinction is never the samples studied contain signifi cant boron, and one perfect. The indices of refraction were measured on a sample in particular has B >> 0.25 atoms per formula single polished surface of more than 1 mm2 using a unit (apfu), thus allowing it to be classifi ed as wiluite. jeweller’s refractometer in monochromatic light (590 Wiluite is a very rare mineral and has been so far nm), with an accuracy of about 0.002 (Hurlbut 1984). reported only from three localities in the world (Groat Wiluite from Ariccia is uniaxial (+), with ␻ 1.722(2) et al. 1998): 1) Wilui River, Sakha Republic, Russian and ␧ 1.727(2). Vesuvianite is an optically negative Federation, 2) Templeton Township, Quebec, Canada, mineral (Deer et al. 1982); however, B-rich vesuvianite and 3) Bill Waley mine, Tulare County, California, (and wiluite) are invariably positive (Groat et al. 1992, USA. Here, we report on the crystal-chemical study of 1998). Borovikova et al. (2003) recently revised the wiluite from Ariccia, Latium, Italy, a new occurrence. optical characteristics of a large number of samples We emphasize that the high B content of vesuvianite- and concluded that, among the B-rich (low- and high- group minerals from Alban Hills, and from the Ariccia symmetry) vesuvianite samples, those containing [3]B quarry in particular, had previously been noted (A. are negative, whereas those containing [4]B are positive. Taddeucci, pers. commun.); however, the data were Owing to the mixed occupancy of the T sites, the actual never published. distribution of boron between sites and the coordination of B are not easy to obtain directly with X-ray methods. OCCURRENCE, PHYSICAL This information, however, is provided, at least qualita- AND OPTICAL PROPERTIES tively, by IR spectroscopy in the B–O stretching region (1200–1000 cm–1).
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