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Alcaparrosaite, K3Ti4+Fe3+(SO4)4O(H2O)2, a new hydrophobic Ti4+ sulfate from Alcaparrosa, Chile

Published online by Cambridge University Press:  05 July 2018

A. R. Kampf*
Affiliation:
Mineral Sciences Department, Natural History Museum of Los Angeles County, 900 Exposition Boulevard, Los Angeles, California 90007, USA
S. J. Mills
Affiliation:
Geosciences, Museum Victoria, GPO Box 666, Melbourne 3001, Victoria, Australia
R. M. Housley
Affiliation:
Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, California 91125, USA
P. A. Williams
Affiliation:
School of Natural Sciences, University of Western Sydney, Locked Bag 1797, Penrith, New South Wales 2751, Australia
M. Dini
Affiliation:
Pasaje San Agustin 4045, La Serena, Chile
*

Abstract

Alcaparrosaite, ideally K3Ti4+Fe3+(SO4)4O(H2O)2, is a new mineral from the Alcaparrosa mine, Cerritos Bayos, El Loa Province, Antofagasta, Chile (IMA2011-024). The mineral occurs on and intergrown with coquimbite, and is also associated with ferrinatrite, krausite, pertlikite, pyrite, tamarugite and voltaite. It is a relatively early phase which forms during the oxidation of pyritic masses under increasingly arid conditions. Alcaparrosaite crystallizes from hyperacidic solutions in a chemical environment that is consistent with its association with coquimbite. It occurs as pale yellow blades and tapering prisms up to 4 mm in length, flattened on {010} and elongated along [100]. The observed crystal forms are {010}, {110}, {1.13.0} and {021}. The mineral is transparent and has a white streak, vitreous lustre, Mohs hardness of about 4, brittle tenacity, conchoidal fracture and no cleavage. The measured and calculated densities are 2.80(3) and 2.807 g cm–3, respectively. It is optically biaxial (+) with α = 1.643(1), β = 1.655(1), γ = 1.680(1) (white light), 2Vmeas = 70(2)° and 2Vcalc = 70.3°. The mineral exhibits strong parallel dispersion, r < v. The optical orientation is X = b; Y^c = 27° in the obtuse angle β. No pleochroism was observed. Electron-microprobe analyses (average of 4) provided: Na2O 0.32, K2O 20.44, Fe2O3 11.58, TiO2 11.77, P2O50.55, SO347.52, H2O 5.79 (calc); total 97.97 wt.%. The empirical formula (based on 19 O) is (K2.89Na0.07)Σ2.96Ti0.984+Fe0.973+(S0.99P0.01O4)4O0.72(OH)0.28(H2O)2. The mineral is hydrophobic, insoluble in cold and hot water, very slowly soluble in acids and decomposes slowly in bases. Alcaparrosaite is monoclinic, C2/c, with the cell parameters a = 7.55943(14), b = 16.7923(3), c = 12.1783(9) Å, β = 94.076(7)°, V = 1542.01(12) Å3 and Z = 4. The eight strongest lines in the X-ray powder diffraction pattern [dobs in A ˚ (Irel) (hkl)] are 6.907 (41) (021,110); 3.628 (34) (023,13); 3.320 (32) (02); 3.096 (100) (202,33,150); 3.000 (40) (51); 2.704 (38) (23,152); 1.9283 (30) (55); 1.8406 (31) (53,06). In the structure of alcaparrosaite (R1 = 2.57% for 1725 Fo > 4σF), Ti4+ and Fe3+, in roughly equal amounts, occupy the same octahedrally coordinated site. Octahedra are linked into dimers by corner sharing. The SO4 tetrahedra link the dimers into chains parallel to [001] and link the chains into undulating sheets parallel to {010}. The sheets link via 10- and 11-coordinated K atoms in the interlayer region. The structure shares some features with that of goldichite.

Type
Research Article
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2012

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References

Appleby, M.P. and Wilkes, S.H. (1922) The system ferric oxide-sulphuric acid-water. Journal of the Chemical Society, 121, 337348.CrossRefGoogle Scholar
Baes, C.F. Jr and Mesmer, R.E. (1976) The Hydrolysis of Cations. Wiley and Sons, New York.Google Scholar
Bandy, M.C. (1938) Mineralogy of three sulfate deposits of northern Chile. American Mineralogist, 23, 669760.Google Scholar
Baskerville, W.H. and Cameron, F.K. (1935) Ferric oxide and aqueous sulfuric acid at 25°C. Journal of Physical Chemistry, 39, 769779.CrossRefGoogle Scholar
Brown, I.D. and Altermatt, D. (1985) Bond-valence parameters from a systematic analysis of the inorganic crystal structure database. Acta Crystallographica, B41, 244247.CrossRefGoogle Scholar
Burla, M.C, Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G.L., De Caro, L., Giacovazzo, C, Polidori, G. and Spagna, R. (2005) SIR2004: an improved tool for crystal structure determination and refinement. Journal of Applied Crystallography, 38, 381388.CrossRefGoogle Scholar
Cameron, F.K. and Robinson, C. (1907) Ferric sulfates. Journal of Physical Chemistry, 11, 641650.CrossRefGoogle Scholar
Cox, J.D., Wagman, D.D. and Medvedev, V.A. (1989) CODATA Key Values for Thermodynamics. Hemisphere Publishing Corporation, New York.Google Scholar
Gatehouse, B.M., Platts, S.N and Williams, T.B. (1993) Structure of anhydrous titanyl sulfate, titanyl sulfate monohydrate and prediction of a new structure. Acta Crystallographica, B49, 428435.CrossRefGoogle Scholar
Graeber, E.J. and Rosenzweig, A. (1971) The crystal structures of yavapaiite, KFe(SO4)2, and goldichite, KFe(SO4)2–4H2O. American Mineralogist, 56, 19171933 Google Scholar
Grzmil, B.U., Grela, D. and Kic, B. (2008) Hydrolysis of titanium sulphate compounds. Chemical Papers, 62, 1825.CrossRefGoogle Scholar
Hawthorne, F.C., Krivovichev, S.V. and Burns, P.C. (2000) The crystal chemistry of sulfate minerals. Pp. 1112 in: Sulfate Minerals—Crystallography, Geochemistry, and Environmental Significance. Reviews in Mineralogy & Geochemistry, 40. Mineralogical Society of America, Washington D.C.CrossRefGoogle Scholar
Hemingway, B.S., Seal, R.R and Chou, I.-M. (2002) Thermodynamic data for modelling acid mine drainage problems: compilation and estimation of data for selected soluble iron-sulfate minerals. United States Geological Survey Open-File Report, 02161.Google Scholar
Mackey, T.S. (1974) Acid leaching of ilmenite into synthetic rutile. Industrial and Engineering Chemistry Product Research and Development, 13, 917.CrossRefGoogle Scholar
Majzlan, J., Navrotsky, A., McCleskey, RB. and Alpers, C.N. (2006) Thermodynamic properties and crystal structure refinement of ferricopiapite, coquimbite, rhomboclase and Fe2(SO4)3(H2O)5. European Journal of Mineralogy, 18, 175186.CrossRefGoogle Scholar
Mandarino, J.A. (1981) The Gladstone-Dale relation-ship: part IV. The compatibility concept and its application. The Canadian Mineralogist, 19, 441450.Google Scholar
Merwin, H.E. and Posnjak, E. (1937) Sulfate incrustations in the Copper Queen mine, Bisbee, Arizona. American Mineralogist, 22, 567571.Google Scholar
Posnjak, E. and Merwin, H.E. (1922) The system, Fe2O3—SO3—H2O. Journal of the American Chemical Society, 44, 19651994.CrossRefGoogle Scholar
Robertson, E.B. and Dunford, H.B. (1964) The state of the proton in aqueous sulfuric acid. Journal of the American Chemical Society, 86, 50805089.CrossRefGoogle Scholar
Sheldrick, GM. (2008) A short history of SHELX. Acta Crystallographica, A64, 112122.CrossRefGoogle Scholar
Szilagyi, I., Konigsberger, E. and May, P.M. (2009a) Spectroscopic characterization of weak interactions in acidic titanyl sulfate solutions for production of titanium dioxide precipitates. Inorganic Chemistry, 48, 22002204.CrossRefGoogle Scholar
Szilagyi, I., Konigsberger, E. and May, P.M. (2009b) Characterization of chemical speciation of titanyl sulfate-iron(II) sulfate solutions. Journal of the Chemical Society, Dalton Transactions, 2009, 77177724.CrossRefGoogle Scholar
Ungemach, P. (1935) Sur certains mineraux sulfates du Chili. Bulletin de la Societe franqaise de Mineralogie, 58, 97221.Google Scholar
Wirth, F. and Bakke, B. (1914) Untersuchung iiber Ferrisulfate. Darstellung und Eigenschaften der verschiedenen normalen, basischen und sauren Ferrisulfate. Loslichkeits-und Stabilitatsverhalt-nisse in Wasser und Schwefelsaure. Kristallisationsgang. Zeitschrift fur anorganische Chemie, 87, 1346.CrossRefGoogle Scholar
Wood, RM. and Palenik, G.J. (1999) Bond valence sums in coordination chemistry using ne. R0 values. Potassium—oxygen complexes. Inorganic Chemistry, 38, 10311034.Google Scholar