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Camaronesite, [Fe3+(H2O)2(PO3OH)]2(SO4)·1–2H2O, a new phosphate-sulfate from the Camarones Valley, Chile, structurally related to taranakite

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, CA 90007, USA
S. J. Mills
Affiliation:
Geosciences, Museum Victoria, GPO Box 666, Melbourne 3001, Australia
B. P. Nash
Affiliation:
Department of Geology and Geophysics, University of Utah, Salt Lake City, Utah 84112, USA
R. M. Housley
Affiliation:
Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, California 91125, USA
G. R. Rossman
Affiliation:
Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, California 91125, USA
M. Dini
Affiliation:
Pasaje San Agustin 4045, La Serena, Chile
*

Abstract

Camaronesite (IMA 2012-094), [Fe3+(H2O)2(PO3OH)]2(SO4)·1–2H2O, is a new mineral from near the village of Cuya in the Camarones Valley, Arica Province, Chile. The mineral is a low-temperature, secondary mineral occurring in a sulfate assemblage with anhydrite, botryogen, chalcanthite, copiapite, halotrichite, hexahydrite, hydroniumjarosite, pyrite, römerite, rozenite and szomolnokite. Lavender-coloured crystals up to several mm across form dense intergrowths. More rarely crystals occur as drusy aggregates of tablets up to 0.5 mm in diameter and 0.02 mm thick. Tablets are flattened on {001} and exhibit the forms {001}, {104}, {015} and {018}. The mineral is transparent with white streak and vitreous lustre. The Mohs hardness is 2½, the tenacity is brittle and the fracture is irregular, conchoidal and stepped. Camaronesite has one perfect cleavage on {001}. The measured and calculated densities are 2.43(1) and 2.383 g/cm3, respectively. The mineral is optically uniaxial (+) with ω = 1.612(1) and ε = 1.621(1) (white light). The pleochroism is O (pale lavender) > E (colourless). Electron-microprobe analyses provided Fe2O331.84, P2O529.22, SO315.74, H2O 23.94 (based on O analyses), total 100.74 wt.%. The empirical formula (based on 2 P a.p.f.u.) is: Fe1.94(PO3OH)2(S0.96O4)(H2O)4·1.46H2O. The mineral is slowly soluble in concentrated HCl and extremely slowly soluble in concentrated H2SO4. Camaronesite is trigonal, R32, with cell parameters:a = 9.0833(5), c = 42.944(3) Å, V = 3068.5(3) Å3 and Z = 9. The eight strongest lines in the X-ray powder diffraction pattern are [dobs Å (I)(hkl)]: 7.74(45)(101), 7.415(100)(012), 4.545(72)(110), 4.426(26)(018), 3.862(32)(021,202,116), 3.298(93)(027,119), 3.179(25)(208) and 2.818(25)(1·1·12,125). In the structure of camaronesite (R1 = 2.28% for 1138 Fo > 4σF), three types of Fe octahedra are linked by corner sharing with (PO3OH) tetrahedra to form polyhedral layers perpendicular to c with composition [Fe3+(H2O)2(PO3OH)]. Two such layers are joined through SO4 tetrahedra (in two half-occupied orientations) to form thick slabs of composition [Fe3+(H2O)2(PO3OH)]2(SO4). Between the slabs are partially occupied H2O groups. The only linkages between the slabs are hydrogen bonds. The most distinctive component in the structure consists of two Fe octahedra linked to one another by three PO4 tetrahedra yielding an [Fe2(PO4)3] unit. This unit is also the key component in the sodium super-ionic conductor (NASICON) structure and has been referred to as the lantern unit. The polyhedral layers in the structure of camaronesite are similar to those in the structure of taranakite. The Raman spectrum exhibits peaks consistent with sulfate, phosphate, water and OH groups.

Type
Research Article
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2013

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References

Anantharamulu, N., Koteswara Rao, K.K., Rambabu, G., Kumar, B.V., Radha, V. and Vithal, M. (2011) A wide-ranging review on Nasicon type materials. Journal of Materials Science, 46, 28212837.CrossRefGoogle Scholar
Bayliss, P., Kolitsch, U., Nickel, E.H. and Pring, A. (2010) Alunite supergroup: recommended nomenclature. Mineralogical Magazine, 74, 919927.CrossRefGoogle Scholar
Beukes, G.J., Schoch, A.E., Van der Westhuizen, W.A., Bok, L.D.C. and de Bruiyn, H. (1984) Hotsonite, a new hydrated aluminum-phosphate-sulfate from Pofadder, South Africa. American Mineralogist, 69, 979983.Google 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
Colombo, F., Rius, J., Pannunzio-Miner, E.V., Pedregosa, J.C., Camí, G.E. and Carbonio, R.E. (2011) Ab initio sanjuanite crystal structure solution from laboratory powder diffraction data, complemented by FTIR spectroscopy and DT-TG analyses. The Canadian Mineralogist, 49, 835847.CrossRefGoogle Scholar
de Bruiyn, H., Beukes, G.J., van der Westhuizen, W.A. and Tordiffe, E.A.W. (1989) Unit cell dimensions of the hydrated aluminium phosphate-sulphate minerals sanjuanite, kribergite, and hotsonite. Mineralogical Magazine, 53, 385386.CrossRefGoogle Scholar
Dick, S., Goßner, U., Weiß, A., Robl, C., Großmann, G., Ohms, G. and Zeiske, T. (1998) Taranakite – the mineral with the longest crystallographic axis. lnorganica Chimica Acta, 269, 4757.CrossRefGoogle Scholar
Downs, R.T. (2006) The RRUFF Project: an integrated study of the chemistry, crystallography, Raman and infrared spectroscopy of minerals. In Program and abstracts of the 19th General Meeting of the International Mineralogical Association in Kobe, Japan. O0313.Google Scholar
Fang, J.H. and Robinson, P.D. (1970) Crystal structures and mineral chemistry of hydrated ferric sulfates. I. the crystal structure of coquimbite. American Mineralogist, 55, 15341540.Google Scholar
Goodenough, J.B., Hong, H.Y.-P. and Kafalas, J.A. (1976) Fast Na+ ion transport in skeleton structures. Materials Research Bulletin, 11, 203220.CrossRefGoogle Scholar
Hagman, L.-O. and Kierkegaard, P. (1968) The crystal structure of NaMe2 IV(PO4)3; MeIV = Ge,, Ti, Zr. Acta Chemica Scandinavica, 22, 18221832.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 Signifcance. Reviews in Mineralogy, 40. Mineralogical Society of America, Washington, D.C.Google Scholar
Higashi, T. (2001) ABSCOR. RigakuCorporation, Tokyo.Google Scholar
Hong, H.Y.-P. (1976) Crystal structures and crystal chemistry in the system Na1+xZr2SixP3–xO12. Materials Research Bulletin, 11, 173182.CrossRefGoogle Scholar
Mandarino, J.A. (2007) The Gladstone–Dale compatibility of minerals and its use in selecting mineral species for further study. The Canadian Mineralogist, 45, 13071324.CrossRefGoogle Scholar
Martini, J. (1978) Sasaite, a new phosphate mineral from West Driefontein Cave, Transvaal, South Africa. Mineralogical Magazine, 42, 401404.CrossRefGoogle Scholar
Masquelier, C., Wurm, C., Rodriguez-Carvajal, J., Gaubicher, J. and Nazar, L. (2000) A Powder neutron diffraction investigation of the two rhombohedral NASICON analogues: g-Na3Fe2(PO4)3 and Li3Fe2(PO4)3 . Chemistry of Materials, 12, 525532.CrossRefGoogle Scholar
Mills, S.J., Hatert, F., Nickel, E.H. and Ferraris, G. (2009) The standardisation of mineral group hierarchies: application to recent nomenclature proposals. European Journal of Mineralogy, 21, 10731080.CrossRefGoogle Scholar
Mills, S.J., Kampf, A.R., Dini, M. and Molina, A. (2012) Die weltbesten Destinezit-Kristalle und andere seltene Sulfate von Mejillones, Chile. Mineralien- Welt, 23, 7381.Google Scholar
Mills, S.J., Ma, C. and Birch, W.D. (2011) A contribution to understanding the complex nature of peisleyite. Mineralogical Magazine, 75, 27332737.CrossRefGoogle Scholar
Moore, P.B. and Araki, T. (1979) Crystal structure of synthetic (NH4)H8Fe3+ 3 (PO4)6·6H2O. American Mineralogist, 64, 578592.Google Scholar
Nakamoto, K. (1978) Infrared and Raman Spectra of Inorganic and Coordination Compounds, 3rd Edition. Wiley Interscience, New York.Google Scholar
Nash, W.P. (1992) Analysis of oxygen with the electron microprobe: applications to hydrous glass and minerals. American Mineralogist, 77, 453457.Google Scholar
Peacor, D.R., Rouse, R.C., Coskren, T.D. and Essene, E.J. (1999) Dest i nezi t e ("diadochite ") , Fe2(PO4)(SO4)(OH)·6(H2O): its crystal structure and role as a soil mineral at Alum Cave Bluff, Tennessee. Clays and Clay Minerals, 47, 111.CrossRefGoogle Scholar
Pouchou, J.-L. and Pichoir, F. (1991) Quantitative analysis of homogeneous or stratified microvolumes applying the model "PAP." Pp. 3174. in: Electron Probe Quantitation (K.F.J. Heinrich and D.E. Newbury, editors). Plenum Press, New York.CrossRefGoogle Scholar
Robinson, P.D. and Fang, J.H. (1971) Crystal structures and mineral chemistry of hydrated ferric sulfates. I. the crystal structure of paracoquimbite. American Mineralogist, 55, 15671572.Google Scholar
Rossman, G.R. (1976) The optical spectroscopic comparison of the ferric iron tetrameric clusters in amarantite and leucophosphite. American Mineralogist, 61, 933938.Google Scholar
Salas, R.O. (1964) Breve informe de una visita realizada a los cateos de sulfato de hierro, en la zona de Cuya, Quebrada de Camarones, Arica. Instituto de Investigaciones Geológicas, Arica.Google Scholar
Salas, R.O. (1965) Informe preliminar de la Mina Minerva, Quebrada de Camarones, departamento de Arica. Instituto de Investigaciones Geológicas, Arica.Google Scholar
Sheldrick, G.M. (2008) A short history of SHELX. Acta Crystallographica, A64, 112122.CrossRefGoogle Scholar
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