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6, a New Mineral Isotructural with Claringbullite: Description and Crystal Structure

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6, a New Mineral Isotructural with Claringbullite: Description and Crystal Structure Mineralogical Magazine, December 2014, Vol. 78(7), pp. 1755–1762 Barlowite, Cu4FBr(OH)6, a new mineral isotructural with claringbullite: description and crystal structure 1,2, 3 2 PETER ELLIOTT *, MARK A. COOPER AND ALLAN PRING 1 School of Earth and Environmental Sciences, The University of Adelaide, Adelaide, South Australia 5005, Australia 2 South Australian Museum, North Terrace, Adelaide, South Australia 5000, Australia 3 Department of Geological Sciences, University of Manitoba, Winnipeg, Manitoba R3T 2N2, Canada [Received 22 April 2014; Accepted 22 June 2014; Associate Editor: G. D. Gatta] ABSTRACT The new mineral species barlowite, ideally Cu4FBr(OH)6, has been found at the Great Australia mine, Cloncurry, Queensland, Australia. It is the Br and F analogue of claringbullite. Barlowite forms thin blue, platy, hexagonal crystals up to 0.5 mm wide in a cuprite-quartz-goethite matrix associated with gerhardtite and brochantite. Crystals are transparent to translucent with a vitreous lustre. The streak is sky blue. The Mohs hardness is 2À2.5. The tenacity is brittle, the fracture is irregular and there is one perfect cleavage on {001}. Density could not be measured; the mineral sinks in the heaviest liquid available, diluted Clerici solution (D &3.8 g/cm3). The density calculated from the empirical formula is 4.21 g/cm3. Crystals are readily soluble in cold dilute HCl. The mineral is optically non-pleochroic and uniaxial (À). The following optical constants measured in white light vary slightly suggesting a small variation in the proportions of F, Cl and Br: o 1.840(4)À1.845(4) and e 1.833(4)À1.840(4). The empirical formula, calculated on the basis of 18 oxygen atoms and H2Ocalculatedtoachieve8anions and charge balance, is Cu4.00F1.11Br0.95Cl0.09(OH)5.85. Barlowite is hexagonal, space group P63/mmc, a = 6.6786(2), c = 9.2744(3) A˚ , V = 358.251(19) A˚ 3, Z = 2. The five strongest lines in the powder X-ray diffraction pattern are [d(A˚ )(I)(hkl)]: 5.790(100)(010); 2.889(40)(020); 2.707(55)(112); 2.452(40)(022); 1.668(30)(220). KEYWORDS: barlowite, new mineral species, copper bromide fluoride, crystal structure, Great Australia mine. Introduction donated the type specimen to the South DURING the late 1980s and the 1990s, specimens Australian Museum in 1990. Barlowite is containing a suite of unusual Cu minerals, isostructural with claringbullite (Fejer et al., including buttgenbachite, claringbullite, connel- 1977; Burns et al., 1995b) and is the second lite, cornetite, gerhardtite and nantokite (Wallace new species described from the deposit after and Pring, 1990; Day and Beyer, 1995; Sharpe cloncurryite (Colchester et al., 2007). The Great and Williams 1999; Hibbs et al., 2003) were Australia mine, is one of several hundred mines collected from the dumps of the Great Australia within the mineral-rich, 60,000 square kilometre mine, located 2 km south of Cloncurry, northwest Mt. IsaÀCloncurry province. Major copper and Queensland, Australia.Barlowitehasbeen lead-zinc-silver, and smaller gold, uranium and identified on several specimens collected in the cobalt mineralization is hosted in Early-to- late 1980s by Ron and Betty Wallace, who Middle Proterozoic rocks. It was the first of several copper deposits discovered in north western Queensland in the late 1860s by Ernest * E-mail: [email protected] Henry, a pastoralist who travelled to the region in DOI: 10.1180/minmag.2014.078.7.17 search of land suitable for cattle production # 2014 The Mineralogical Society PETER ELLIOTT ET AL. (Hardy, 1984). The mine was worked intermit- Physical and optical properties tently until closure in 1919, producing 100,000 tonnes of ore (Carter et al., 1961). It was Barlowite occurs in cavities in a cuprite-quartz- reopened and worked by open pit mining goethite matrix as thin, blue, hexagonal crystals, between 1995 and 1999 by the Cloncurry flattened on {001} and as aggregates of platy Mining Company NL. Barlowite is named in crystals up to 3 mm across. Individual crystals are honour of William Barlow (1845À1934), English up to 0.5 mm across and 0.3 mm thick. The only amateur geologist and crystallographer. Barlow form observed is {0001}. Associated minerals are was one of three workers who independently crystals of blue gerhardtite and greenish-blue enumerated the 230 space groups in 3 dimen- brochantite. The streak is sky blue. Crystals are sions, the other two being E.S. Fedorov and A.M. transparent to translucent with a vitreous lustre. Scho¨nflies. Barlow also proposed several crystal The Mohs hardness is 2À2.5. The tenacity is structures in the 1880s, that were later validated brittle, the fracture is irregular and there is one by X-ray crystallography, including the sodium perfect cleavage on {001}. Density could not be chloride, cesium chloride, nickel arsenide, measured; the mineral sinks in the heaviest liquid sphalerite and wurtzite structures (Pope, 1935; available, diluted Clerici solution Pauling, 1994). The type specimen of barlowite is (D &3.8 g/cm3). The density calculated from lodged in the collection of South Australian the empirical formula is 4.21 g/cm3. Crystals are Museum (registration number G17449). readily soluble in cold dilute HCl. The mineral is optically non-pleochroic and uniaxial (À). The refractive indices measured in white light vary Occurrence slightly suggesting a small variation in the The geological province known as the Mt Isa proportions of F, Cl and Br: o 1.840(4)À inlier comprises a north-northwesterly trending 1.845(4) and e 1.833(4)À1.840(4). The range in belt of Precambrian rocks, ~500 km long and with the observed refractive indices is consistent with an average width of 120 km (Blake, 1987). It the range in content of Br, F and Cl from the consists of Proterozoic sediments and igneous microprobe analysis of two grains of the mineral. rocks associated with multiple rifting and granite A Gladstone-Dale calculation, using an nmean emplacement events between 1900 and 1600 Ma. value of 1.839 from the measured range of The host rocks for the Great Australia lode are refractive indices and the calculated density Lower Proterozoic basaltic meta-andesites, doler- from the empirical formula, gives a compatibility ites and interbedded metasediments of the Toole index of 0.001, which is regarded as superior Creek Volcanics. Vein-replacement style miner- (Mandarino, 1981). alization occurs within a major splay of the NÀS trending Cloncurry fault and is considered to be of magmatic origin, related to the intrusion of the Williams/Naraku batholith (Cannell and Davidson, 1998). Primary mineralization TABLE 1. Compositional data for barlowite. comprises Co-bearing pyrite and chalcopyrite within a gangue mineral assemblage of dolo- Constituent Wt.% Range Standard mite-calcite-quartz-actinolite-albite-magnetite. A deviation zone of supergene enrichment is dominated by abundant malachite, chrysocolla, cuprite, chalco- CuO 70.08 68.65–70.93 0.78 cite and native copper. The assemblage of F 4.64 3.96À5.03 0.25 secondary copper minerals, which are mostly Cl 0.73 0.59À1.04 0.12 found lining cavities in cuprite-rich rocks, have Br 16.79 16.1À17.43 0.39 formed by oxidation of primary Cu mineralization H2O* 11.59 (copper, chalcopyrite, cuprite) under low-temp- O=F À1.95 erature conditions. The overall sequence of O=Cl À0.16 O=Br À1.68 crystallization probably represents a change from acid to more alkaline conditions, with Total 100.04 claringbullite and barlowite being among the last minerals to form (Williams, 1990; Day and Number of analysis = 20. Beyer 1995). * Calculated to obtain charge balance. 1756 BARLOWITE, Cu4FBr(OH)6, A NEW MINERAL FIG. 1. Fourier transform IR spectrum of powdered barlowite. Chemical analysis Powder X-ray diffraction data Chemical analyses (Table 1) were performed in Powder X-ray diffraction data (Table 2) were wavelength-dispersive spectroscopic (WDS) obtained with a 100 mm Guinier-Ha¨gg camera mode on a Cameca SX51 electron microprobe. Data reduction was performed using the f(rZ) method of Pouchou and Pichoir (1985). The TABLE 2. Powder X-ray diffraction data for barlowite. operating voltage was 20 kV, the beam current was 20 nA and the beam size 5 mm. The following ˚ ˚ standards were used: CuKa (chalcopyrite), FKa Iobs dobs (A) Icalc dcalc (A) hkl (fluorite), ClKa (tugtupite), BrKa (thallium bromide). An energy-dispersion spectrum indi- 100 5.790 100 5.786 0 1 0 cated the absence of elements with an atomic 5 4.915 5 4.909 0 1 1 number greater than 8 other than those reported 2 3.618 0 1 2 15 3.338 13 3.340 1 1 0 here. The empirical formula, calculated on the 40 2.889 46 2.893 0 2 0 basis of 18 oxygen atoms and H2O calculated to 15 2.759 19 2.762 0 2 1 achieve 8 anions and charge balance, is 2 2.726 0 1 3 Cu4.00F1.11Br0.95Cl0.09(OH)5.85. 55 2.707 62 2.710 1 1 2 40 2.452 49 2.454 0 2 2 5 2.316 8 2.318 0 0 4 Infrared spectroscopy 5 2.184 12 2.187 1 2 0 An infrared (IR) absorption spectrum of barlowite 5 2.148 10 2.152 0 1 4 was obtained using a Nicolet 5700 FTIR spectro- 9 2.128 1 2 1 5 2.112 0 2 3 meter equipped with a Nicolet Continuum IR 1 1.978 1 2 2 microscope and a diamond anvil cell. A crystal 1 1.929 0 3 0 aggregate was crushed in the diamond cell and a 7 1.905 1 1 4 À1 spectrum recorded in the range 4000 to 650 cm 8 1.888 0 3 1 (Fig.
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