Kra´Snoite, the Fluorophosphate Analogue of Perhamite, from the Huber Open Pit, Czech Republic and the Silver Coin Mine, Nevada, USA
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Mineralogical Magazine, June 2012, Vol. 76(3), pp. 625–634 Kra´snoite, the fluorophosphate analogue of perhamite, from the Huber open pit, Czech Republic and the Silver Coin mine, Nevada, USA 1, 2 3 4 5 6 7 S. J. MILLS *, J. SEJKORA ,A.R.KAMPF ,I.E.GREY ,T.J.BASTOW ,N.A.BALL ,P.M.ADAMS , 8 6 M. RAUDSEPP AND M. A. COOPER 1 Geosciences, Museum Victoria, GPO Box 666, Melbourne 3001, Australia 2 Department of Mineralogy and Petrology, National Museum Prague, Vaclavske´na´m. 68, CZ-115 79 Praha 1, Czech Republic 3 Mineral Sciences Department, Natural History Museum of Los Angeles County, 900 Exposition Boulevard, Los Angeles, California 90007, USA 4 CSIRO Process Science and Engineering, Box 312, Clayton South, Victoria 3169, Australia 5 CSIRO Materials Science and Engineering, Private Bag 33, Rosebank MDC, Clayton, Victoria 3169, Australia 6 Department of Geological Sciences, University of Manitoba, Winnipeg, Manitoba R3T 2N2, Canada 7 126 South Helberta Avenue, #2, Redondo Beach, California 90277, USA 8 Department of Earth and Ocean Sciences, University of British Columbia, Vancouver, British Columbia V6T 1Z4, Canada [Received 11 January 2012; Accepted 22 March 2012; Associate Editor: Giancarlo Della Ventura] ABSTRACT Kra´snoite is a new mineral (IMA2011-040) from the Huber open pit, Kra´sno ore district, Czech Republic and the Silver Coin mine, Nevada, USA. Kra´snoite is the fluorophosphate analogue of perhamite. Kra´snoite occurs as compact to finely crystalline aggregates, balls and rosette-like clusters up to 1 mm across. Individual crystals are platy, show a hexagonal outline and can reach 0.1 mm on edge at Kra´sno and 0.4 mm at Silver Coin. At both localities, kra´snoite occurs very late in phosphate- rich paragenetic sequences. Kra´snoite crystals are partly transparent with a typically pearly lustre, but canalsoappeargreasy(Kra´sno) or dull (Silver Coin). The streak is white and the hardness is 5 on the Mohs scale. Crystals are brittle, have an irregular fracture, one imperfect cleavage on {001} and are not fluorescent under SW and LW ultraviolet light. Penetration twinning \ {001} is common. The density for both Kra´sno and Silver Coin material is 2.48(4) g cmÀ3, measured by the sink–float method in an aqueous solution of sodium polytungstate. The calculated density is 2.476 g cmÀ3 (Kra´sno). Kra´snoite crystals are uniaxial (+), with o =1.548(2)ande = 1.549(2) (Kra´sno) and o =1.541(1)ande = 1.543(1) (Silver Coin). The simplified formula of kra´snoite is: Ca3Al7.7Si3P4O23.5(OH)12.1F2·8H2O. Kra´snoite is trigonal, space group P3¯m1, with a = 6.9956(4), c = 20.200(2) A˚ , V = 856.09(9) A˚ 3 and Z = 3. Raman and infrared spectroscopy, coupled with magic-angle spinning nuclear magnetic resonance (MAS–NMR) spectrometry, confirmed the presence of PO3F, PO4,SiO4,H2O and OH in the crystal structure of kra´snoite. KEYWORDS: kra´snoite, perhamite, new mineral, Kra´sno ore district, Czech Republic, Silver Coin mine, USA, NMR, fluorophosphate. Introduction DURING investigations of supergene F-rich phos- * E-mail: [email protected] phate assemblages by two different research DOI: 10.1180/minmag.2012.076.3.13 groups, one working on the occurrence at the # 2012 The Mineralogical Society S. J. MILLS ET AL. abandoned Huber open pit, Kra´sno ore district, coloured fluorapatite in cavities in a quartz gangue Czech Republic, and the other on that at the Silver (Sejkora et al., 2006a). Coin mine, Nevada, USA, a number of rare and Kra´snoite belongs to the last stage of supergene unusual minerals have been discovered. mineralisation at the Huber open pit, where it Collaboration between the groups has already forms from the breakdown of fluorapatite, triplite yielded the new mineral iangreyite, Ca2Al7(PO4)2 and isokite in the presence of acidic ground- (PO3OH)2(OH,F)15·8H2O (IMA2009-087; Mills waters. The kra´snoiteÀfluorapatite intergrowths et al., 2011). Both groups had also previously are similar to the perhamiteÀfluorapatite inter- noted the new mineral reported herein. Sejkora et growths found in South Australian phosphate al. (2006a) first reported 13 EMPA analyses, with deposits (e.g. Mills, 2003; Dunn and Appleman, powder X-ray diffraction data, on unnamed 1977), and this suggests that both kra´snoite and mineral UNK1 from Kra´sno, which they perhamite may form under the same conditions. described as a possible F-analogue of perhamite. The same phase was also noted at the Silver Coin Silver Coin mine, during the investigations which led to the description of meurigite-Na (Kampf et al., 2009). Kra´snoite occurs at the Silver Coin mine The mineral is named in honour of the district (SW sec. 1 and SE sec. 2, T35N, R41E), where it was first discovered, the Kra´sno ore Valmy, Nevada, USA, as part of a rich secondary district, and because it was found to be more phosphate assemblage (e.g. Thomssen and Wise, abundant at this occurrence than at the Silver Coin 2004), which formed on phosphatic argillite wall mine. In addition, we were able to obtain more rocks of the abandoned Pb-Zn-Ag mine. and higher quality data from the material from Kra´snoite occurs very late in a paragenetic Kra´sno. Both, however, are considered type sequence that includes (in approximate order localities. The mineral and name have been from early to late) quartz, baryte, fluorapatite, approved by the IMA-CNMNC (IMA2011-040). goethite, rockbridgeite, cacoxenite, alunite, The cotype material is housed in the collections of wardite, turquoise/chalcosiderite, leucophosphite, the Department of Mineralogy and Petrology, lipscombite/zinclipscombite, kidwellite, strengite/ National Museum Prague, catalogue number P1P variscite, iangreyite, kra´snoite, meurigite-Na and 2/2011 (Kra´sno) and in the collections of Mineral jarosite (minerals separated by slashes exhibit Sciences Department, Natural History Museum of variations in chemistry between the two species). Los Angeles County catalogue numbers 62372 At the Silver Coin mine, kra´snoite is likely to and 62373 (Silver Coin). have formed under acidic conditions mainly from the breakdown of primary fluorapatite found within the phosphatic argillite. Occurrence and paragenesis Kra´ sno Physical and optical properties Samples of kra´snoite were found at the abandoned Huber open pit (50º07’21.28’’ N, 12º47’59.15’’ E), Kra´ sno Kra´sno ore district near Hornı´ Slavkov, Kra´snoite occurs as compact to finely crystalline Slavkovsky´ les mountains, western Bohemia, aggregates, generally about 0.1 mm across, which Czech Republic (Sejkora et al., 2006a). Kra´snoite are further intergrown, forming millimetre-size occurs in strongly altered areas (Sejkora et al., clusters (Fig. 1). The crystals are platy, have a 2006b), which range in size from 1 cm to 10 cm hexagonal outline and can reach 0.1 mm on edge across. Accumulations of kra´snoite up to 3.5 cm (Fig. 2); isolated crystals have not been found. across are present; however, the mineral is always The form {001} is prominent and crystals are intergrown with white to pale yellow supergene bounded by faces of the {100} form. Kra´snoite fluorapatite. Fluorine-rich crandallite, whitish crys- varies in colour from snow white (most common) tals of kolbeckite, and whitish earthy aggregates of to pale yellowish white and white with a greenish younger generation of isokite are also found with tint. Crystals are partly transparent with a pearly some specimens of kra´snoite. Two different to greasy lustre, have a white streak and an mineral assemblages commonly host kra´snoite: estimated hardness of 5 on the Mohs scale. (1) plimerite (Sejkora et al., 2011), kolbeckite, Crystals are brittle, have an irregular fracture, pharmacosiderite and minerals of the chalcosi- one imperfect cleavage on {001}, and are not derite–turqouise series; and (2) fluellite and milky- fluorescent under SW and LW ultraviolet light. 626 KRA´ SNOITE for all the data from Kra´sno is 0.005, which is classed as superior. Silver Coin At Silver Coin, kra´snoite forms as off-white coloured balls and rosette-like clusters up to about 1 mm across. Within these clusters, hexagonal plates may reach 0.4 mm in diameter, but are exceedingly thin (41 mm thick) and always intergrown. The crystals have a dull to pearly lustre. The density, measured as described above, is 2.48(4) g cmÀ3.Theindicesof refraction, measured in white light, o = 1.541(1) and e = 1.543(1), are slightly lower than those FIG. 1. Pearly aggregates of kra´snoite from Kra´sno, obtained for the Kra´sno sample. Czech Republic. The field of view is 4.5 mm. Chemical composition Penetration twinning \ {001} is common. The Chemical analyses (60) on kra´snoite from Kra´sno density, measured by the sinkÀfloat method in an were carried out using an electron microprobe in aqueous solution of sodium polytungstate, is wavelength-dispersive spectrometry (WDS) mode 2.48(4) g cmÀ3. The calculated density is (Table 1) at 15 kV, 4 nA with a 10 mmbeam 2.476 g cmÀ3, based on the empirical formula diameter. The elements Sb, V, Co, Ni, U and Bi and refined unit cell, and is in excellent agreement were sought, but not detected. Peak counting times with the measured density. were 20 s for the major elements and 30 to 60 s for Kra´snoite crystals are uniaxial (+), with o = the minor and trace elements. The presence of H2O 1.548(2) and e = 1.549(2), measured at 589 nm. and OH was confirmed by Raman and infrared Kra´snoite crystals are not pleochroic. The spectroscopy (see below). The empirical formula, GladstoneÀDale compatibility index calculated based on (Al + Fe) + (Si + P + Ti) + (P + As) = 14.70, FIG.