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A contribution to the crystal chemistry of the voltaite group: solid solutions, Mössbauer and infrared spectra, and anomalous anisotropy

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Abstract

Voltaite is a mineral of fumaroles, solfatares, coal-fire gas vents, and acid-mine drainage systems. The nominal composition is K2Fe5 2+Fe3 3+Al(SO4)12·18H2O and the nominal symmetry is cubic, \(Fd\overline{3}c\). The tetragonal (I41/acd) superstructure of voltaite is known as the mineral pertlikite. In this study, we investigated 22 synthetic voltaite samples in which Fe2+ was partially or completely replaced by Mg, Zn, Mn, or Cd, by single-crystal and powder X-ray diffraction (both in-house and synchrotron). Two samples contained NH4 + instead of K+. The structure of voltaite is based on a framework defined by kröhnkite-like heteropolyhedral chains which host both M3+ and M2+ in octahedral coordination. Unit cell dimensions of the end-members scale almost linearly with the size of M2+. In the Fe2+-Mg-Zn solid solutions, the Fe2+-Mg and Fe2+-Zn solutions are linear (ideal) in terms of their lattice-parameter variations. The Mg-Zn solid solution, however, is strongly non-ideal. A detailed analysis of the topology of the chains showed that this behavior originates in expansion and contraction of individual M2+-O bonds within the chains. In the Mg-Zn solid solution, some of the M2+-O bonds expand while none contract. In the other solid solutions, expansion of some M2+-O bonds is always compensated by contraction of the other ones. Parts of the nominally cubic crystals are optically anisotropic and their symmetry is found to be tetragonal by single crystal X-ray diffraction measurements. The coexistence of cubic and tetragonal sectors within a single crystal without any detectable difference in their chemical composition is difficult to explain in terms of growth of such composite crystals. Mössbauer and infrared spectra collected on our synthetic crystals conform with previously published data.

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References

  • Allen FM, Buseck PR (1988) XRD, FTIR, and TEM studies of optically anisotropic grossular garnets. Am Mineral 73:568–584

    Google Scholar 

  • Beveridge D, Day P (1979) Charge transfer in mixed valence solids. Part 9. Preparation, characterization, and optical spectroscopy of the mixed valence mineral voltaite [aluminum pentairon(II) triiron(III) dipotassiumdodecasulfate 18-hydrate] and its solid solutions with cadmium(II). J Chem Soc Dalton Trans 4:648–653

    Article  Google Scholar 

  • Brugger J, Bonin M, Schenk KJ, Miesser N, Berlepsch P, Ragu A (1999) Description and crystal structure of nabiasite, BaMn9[(V, As)O4]6(OH)2, a new mineral from the Central Pyrénées (France). Eur J Mineral 11:879–890

    Google Scholar 

  • Buerger MJ, Dollase WA, Garaycochea-Wittke I (1967) The structure and composition of the mineral pharmacosiderite. Z Kristallogr 125:92–108

    Article  Google Scholar 

  • Dahlman B (1952) The crystal structure of kroehnkite, CuNa2(SO4)2(H2O)2 and brandtite, MnCa2(AsO4)2(H2O)2. Ark Mineral Geol 1:339–366

    Google Scholar 

  • Ertl A, Dyar MD, Hughes JH, Brandstatter F, Gunter ME, Prem M, Peterson RC (2008) Pertlikite, a new tetragonal Mg-rich member of the voltaite group from Madeni Zakh, Iran. Can Mineral 46:661–669

    Article  Google Scholar 

  • Fleck M, Kolitsch U, Hertweck B (2002) Natural and synthetic compounds with kröhnkite-type chains: review and classification. Z Kristallogr 217:435–443

    Article  Google Scholar 

  • Gieré R, Blackford M, Smith KL, Williams CT, Kirk C (2007) Metal sulfates in PM emissions from a coal-fired power plant. Goldschmidt conference abstracts, A322

  • Gossner B, Arm M (1930) Chemische und röntgenographische Untersuchung an Stoffen und Kristallen von komplexer Bauart. Z Kristallogr 72:202–236

    Google Scholar 

  • Gossner B, Bäuerlein T (1933) Optical anomalies: voltaite-like sulfates. NJb Min Geol Pal 66A:1–40

    Google Scholar 

  • Gossner B, Besslein J (1934) Hydrated sulfates of three metals. Centr Mineral Geol 1934A:358–364

    Google Scholar 

  • Gossner B, Drexler K (1933) Structural and molecular units of sulfates of the voltaite type. Centr Mineral Geol 1933A:83–91

    Google Scholar 

  • Gossner B, Fell E (1932) Sulfates of the voltaite type. Ber Deutsch Chem Ges 65B:393–395

    Google Scholar 

  • Griffen DT, Ribbe PH (1979) Distortions in the tetrahedral oxyanions of crystalline substances. Neues Jahrb Miner Abh 137:54–73

    Google Scholar 

  • Hawthorne FC, Krivovichev SV, Burns PC (2000) The crystal chemistry of sulfate minerals. Rev Mineral Geochem 40:1–112

    Article  Google Scholar 

  • Hermon E, Haddad R, Simkin D, Brandao DE, Muir WB (1976) Magnetic properties and the distribution of iron ions in voltaites. Can J Phys 54:1149–1156

    Article  Google Scholar 

  • Hertweck B, Libowitzky E (2002) Vibrational spectroscopy of phase transitions in leonite-type minerals. Eur J Mineral 14:1009–1017. doi:10.1127/0935-1221/2002/0014-1009

    Article  Google Scholar 

  • Jambor JL, Nordstrom DK, Alpers CN (2000) Metal-sulfate salts from sulfide mineral oxidation. Rev Mineral Geochem 40:303–350. doi:10.2138/rmg.2000.40.6

    Article  Google Scholar 

  • Long GJ, Longworth G, Day P, Beveridge D (1980) A Mössbauer-effect study of the electronic and magnetic properties of voltaite, a mixed-valence. Mineral Inorg Chem 19:821–829

    Article  Google Scholar 

  • Majzlan J, Alpers CN, Bender Koch C, McCleskey RB, Myneni SCB, Neil JM (2011) Vibrational, X-ray absorption, and Mössbauer spectra of sulfate minerals from the weathered massive sulfide deposit at Iron Mountain, California. Chem Geol 284:296–305

    Article  Google Scholar 

  • Marquez-Zavalia MF, Lomniczi de Upton I, Galliski MA (2001) Krausite in fumaroles from Santa Barbara mine, northwestern Argentina. Neues Jb Miner Monat 8:378–384

    Google Scholar 

  • Mereiter K (1972) Die Kristallstruktur des Voltaits, K2Fe5 2+Fe3 3+Al[SO4]12∙18H2O. Tschermaks Min Petr Mitt 18:185–202

    Article  Google Scholar 

  • Mookherjee M, Redfern SAT, Zhang M, Harlov DE (2002) Orientational order–disorder of ND4 +/NH4 +in synthetic ND4 +/NH4 +- phlogopite: a low-temperature infrared study. Eur J Mineral 14:1033–1039

    Article  Google Scholar 

  • Nordstrom DK, Alpers CN (1999) Negative pH, efflorescent mineralogy, and consequences for environmental restoration at the Iron Mountain. Proc Natl Acad Sci USA 96:3455–3462

    Article  Google Scholar 

  • Peterson RC, Valyashko E, Wang R (2009) The atomic structure of (H3O)Fe3+(SO4)2 and rhomboclase, (H5O2)Fe3+(SO4)2·2H2O. Can Mineral 47:625–634

    Article  Google Scholar 

  • Rammelsberg CF (1860) Handbuch der Mineralchemie. Verlag von Wilhelm Engelman, Leipzig

    Book  Google Scholar 

  • Rondeau B, Fritsch E, Guiraud M, Chalain JP, Notari F (2004) Three historical ‘asteriated’ hydrogen-rich diamonds: growth history and sector-dependent impurity incorporation. Diam Relat Mater 13:1658–1673

    Article  Google Scholar 

  • Shannon RD (1976) Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallogr A32:751–767

    Google Scholar 

  • Sheldrick G (2008) A short history of SHELX. Acta Crystallogr A64:112–122

    Google Scholar 

  • Shigley JE, Fritsch E, Stockton CM, Koivula JI, Fryer CW, Kane RE (2005a) The gemological properties of the Sumitomo gem-quality synthetic yellow diamonds. In: Shigley JE (ed) Synthetic diamonds. Gems & Gemology in Review 30–45

  • Shigley JE, Fritsch E, Stockton CM, Koivula JI, Fryer CW, Kane RE, Hargett DR, Welch CW, (2005b) The gemological properties of the De Beers gem-quality synthetic diamonds. In: Shigley JE (ed) Synthetic diamonds. Gems & Gemology in Review 46–64

  • Shtukenberg AG (2005) Metastability of atomic ordering in lead-strontium nitrate solid solutions. J Solid State Chem 178:2608–2612

    Article  Google Scholar 

  • Shtukenberg AG, Popov DY, Punin YO (2005) Growth ordering and anomalous birefringence in ugrandite garnets. Mineral Mag 69:537–550

    Article  Google Scholar 

  • Stracher GB, Prakash A, Schroeder P, McCormack J, Zhang X, Van Dijk P, Blake D (2005) New mineral occurrences and mineralization processes: Wuda coal-fire gas vents of Inner Mongolia. Am Mineral 90:1729–1739

    Article  Google Scholar 

  • Welbourn CM, Cooper M, Spear PM (2005) De Beers natural versus synthetic diamond verification instruments. In: Shigley JE (ed) Synthetic diamonds. Gems & Gemology in Review 139–151

  • Wildner M, Andrut M (2001) The crystal chemistry of birefringent natural uvarovites: Part II. Single-crystal X-ray structures. Am Mineral 86:1231–1251

    Google Scholar 

  • Zavalia MFM, Galliski MA (1995) Goldichite of fumarolic origin from the Santa Barbara mine, Jujuy, northwestern Argentina. Can Mineral 33:1059–1062

    Google Scholar 

  • Zemann J (1948) Formel und Strukturtyp des Pharmakosiderits. Tschermaks Min Petr Mitt 1:1–13

    Article  Google Scholar 

Download references

Acknowledgments

We are grateful to two anonymous reviewers for their constructive criticism. We thank D. Merten (Institute of Geosciences, Friedrich-Schiller-Universität Jena) for the ICP-OES analyses, H. Görls (Institute for Inorganic and Analytical Chemistry, Friedrich-Schiller-Universität Jena) for the single-crystal XRD data, G. Sentis (Institute of Pharmacy, Friedrich-Schiller-Universität Jena) for the infrared spectra, and B. Kreher-Hartmann (Institute of Geosciences, Friedrich-Schiller-Universität Jena) for the macrophotographs of the voltaite crystals. We acknowledge the ANKA Angströmquelle Karlsruhe for the provision of the beamtime at the PDIFF and SCD beamlines.

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Correspondence to Juraj Majzlan.

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Editorial handling: T. Armbruster

Dedicated to Prof. Josef Zemann on the occasion of his 90th birthday

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Majzlan, J., Schlicht, H., Wierzbicka-Wieczorek, M. et al. A contribution to the crystal chemistry of the voltaite group: solid solutions, Mössbauer and infrared spectra, and anomalous anisotropy. Miner Petrol 107, 221–233 (2013). https://doi.org/10.1007/s00710-012-0254-2

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