Hostname: page-component-78c5997874-j824f Total loading time: 0 Render date: 2024-11-13T12:51:38.277Z Has data issue: false hasContentIssue false
  • English
  • Français

The crystal structure of ammoniojarosite, (NH4)Fe3(SO4)W(OH)6 and the crystal chemistry of the ammoniojarosite–hydronium jarosite solid-solution series

Published online by Cambridge University Press:  05 July 2018

L. C. Basciano  and
R. C. Peterson
L. C. Basciano*
Affiliation:
Department of Geological Sciences and Geological Engineering, Queen’s University, Kingston, Ontario, Canada, K7L 3N6
R. C. Peterson
Affiliation:
Department of Geological Sciences and Geological Engineering, Queen’s University, Kingston, Ontario, Canada, K7L 3N6
*
E-mail: basciano@students.geol.queensu.ca
Get access Rights & Permissions [Opens in a new window]

Abstract

The atomic structure of ammoniojarosite,[(NH4)Fe3(SO4)2(OH)6], a = 7.3177(3) Å, c = 17.534(1) Å, space group Rm, Z = 3, has been solved using single-crystal X-ray diffraction (XRD) to wR 3.64% and R 1.4%. The atomic coordinates of the hydrogen atoms of the NH4 group were located and it was found that the ammonium group has two different orientations with equal probability. Hydronium commonly substitutes into jarosite group mineral structures and samples in the ammoniojarosite–hydronium jarosite solid-solution series were synthesized and analysed using powder XRD and Rietveld refinement. Changes in unit-cell dimensions and bond lengths are noted across the solidsolution series. The end-member ammoniojarosite synthesized in this study has no hydronium substitution in the A site and the unit-cell dimensions determined have a smaller a dimension and larger c dimension than previous studies. Two natural ammoniojarosite samples were analysed and shown to have similar unit-cell dimensions to the synthetic samples. Short-wave infrared and Fourier transform infrared spectra were collected for samples from the NH4–H3O jarosite solid-solution series and the differences between the end-members were significant. Both are useful tools for determining NH4 content in jarosite group minerals.

Keywords

ammoniojarositeammoniojarosite–hydronium jarosite solid-solution seriescrystal synthesisIR spectroscopySWIRcrystal structureXRDRietveld refinement
Type
Research Article
Information
Mineralogical Magazine , Volume 71 , Issue 4 , August 2007 , pp. 427 - 441
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2007

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

Altaner, S.P., Fitzpatrick, J.J., Krohn, M.D., Bethke, P.M., Hayba, D.O., Goss, J.A. and Brown, Z.A. (1988) Ammonium in alunites. American Mineralogist, 73, 145–152.Google Scholar
Balzar, D. (1999) Voigt–function model in diffraction line–broadening analysis. International Union of Crystallography Monographs on Crystallography, 10, 94–126.Google Scholar
Basciano, L.C. and Peterson, R.C. (2007) Jarosite–hydronium jarosite solid–solution series with full iron occupancy: mineralogy and crystal chemistry. American Mineralogist, 92, 1464–1473.CrossRefGoogle Scholar
Baur, W.H. (1972) Prediction of hydrogen bonds and hydrogen atom positions in crystalline solids. Acta Crystallographica, B28, 1456–1465.Google Scholar
Bishop, J.L. and Murad, E. (2005) The visible and infrared spectral properties of jarosite and alunite. American Mineralogist, 90, 1100–1107.CrossRefGoogle Scholar
Brophy, G.P., Scott, E.S. and Snellgrove, R.A. (1962) Sulfate studies II: Solid–solution between alunite and jarosite. American Mineralogist, 22, 773–784.Google Scholar
Bruker, A.X.S. (2000) Crystal structure analysis package, SHELXTL (Version 6.14), SAINT (Version 7.23A). Bruker AXS Inc., Madison, WI.Google Scholar
Cheary, R.W. and Coelho, A.A. (1998) Axial divergence in a conventional X–ray powder diffractometer I. Theoretical foundations. Journal of Applied Crystallography, 31, 851–861.Google Scholar
Coelho, A.A. (2004) TOPAS–Academic. http://members.optusnet.com.au/~alancoelho.Google Scholar
Dowty, E. (2003) ATOMS version 6.0. Shape Software, Kingsport, Tennessee.Google Scholar
Drouet, C. and Navrotsky, A. (2003) Synthesis, characterization, and thermochemistry of K–Na–H3O jarosites. Geochimica et Cosmochimica Acta, 11, 2063–2076.Google Scholar
Drouet, C., Pass, K.L., Baron, D., Draucker, S. and Navrotsky, A. (2004) Thermochemistry of jarositealunite and natrojarosite–natroalunite solid–solutions. Geochimica et Cosmochimica Acta, 68, 2197–2205.CrossRefGoogle Scholar
Dutrizac, J.E. and Kaiman, S. (1976) Synthesis and properties of jarosite–type compounds. The Canadian Mineralogist, 14, 151–158.Google Scholar
Dutrizac, J.E. and Jambor, J.L. (2000) Jarosites and their application in hydrometallurgy. Pp. 405–452 in: Sulfate Minerals–Crystallography, Geochemistry, and Environmental Significance (Alpers, C.N., Jambor, J.L. and Nordstrom, D.K., editors). Reviews in Mineralogy and Geochemistry, 40. Mineralogical Society of America, Washington D.C. Google Scholar
Frost, R.L., Wills, R., Martens, W. and Weier, M. (2005) NIR spectroscopy of jarosites. Spectrochimica Acta, A62, 869–874.Google Scholar
Frost, R.L., Wills, R., Kloprogge, J.T. and Martens, W. (2006) Thermal decomposition of ammonium jarosite (NH4)Fe3(SO4)2(OH)6 . Journal of Thermal Analysis and Calorimetry, 84, 489–496.CrossRefGoogle Scholar
Glynn, P. (2000) Solid–solution solubilities and thermodynamics: Sulfates, carbonates, and halides. Pp. 481–511 in: Sulfate Minerals: Crystallography, Geochemistry, and Environmental Significance (Alpers, C.N., Jambor, J.L. and Nordstrom, D.K., editors). Reviews in Mineralogy and Geochemistry, 40. Mineralogical Society of America, Chantilly, Virginia.Google Scholar
Hendricks, S.B. (1937) The crystal structure of alunite and the jarosites. American Mineralogist, 22, 773–784.Google Scholar
Hill, R.J. and Flack, H.D. (1987) The use of the Durbin– Watson d statistic in Rietveld analysis. Journal of Applied Crystallography, 20, 356–361.CrossRefGoogle Scholar
Hölzer, G., Fritsch, M., Deutsch, M., Härtwig, J. and Förster, E. (1997) Kα1,2 and Kβ1,3 X–ray emission lines of the 3d transition metals. Physical Review, A56, 4554–4568.Google Scholar
Khan, A.A. and Baur, W.H. (1972) Salt hydrates: VIII. The crystal structures of sodium ammonium orthochromate dehydrate and magnesium diammonium bis (hydrogen orthophosphate) tetrahydrate and a discussion of the ammonium ion. Acta Crystallographica, B28, 683–693.Google Scholar
Kubisz, J. (1970) Studies on synthetic alkali–hydronium jarosites. I. Synthesis of jarosite and natrojarosite. Mineralogia Polonica, 1, 47–57.Google Scholar
Majzlan, J., Stevens, R., Boerio–Goates, J., Woodfield, B.F., Navr otsky, A., Burns, P.C., Craw ford, M.K. and Amos, T.G. (2004) Thermodynamic properties, low – temperature heat–capacity anomalies, and singlecrystal X–ray refinement of hydronium jarosite, (H3O)Fe3(SO4)2(OH)6 . Physics and Chemistry of Minerals, 31, 518–531.CrossRefGoogle Scholar
Musić, S., Popović, S., Orehovec, Z. and Czako–Nagy, I. (1993) Properties of precipitates formed by hydrolysis of Fe3+ ions in NH4Fe(SO4)2 solutions. Journal of Colloid and Interface Science, 160, 479–482.CrossRefGoogle Scholar
Odem, J.K., Hauff, P.L. and Farrow, R.A. (1982) A new occurrence of ammoniojarosite in Buffalo, Wyoming. The Canadian Mineralogist, 20, 91–95.Google Scholar
Ripmeester, J.A., R atcliff, C.I., Du trizac, J. E. and Jambor, J.L. (1986) Hydronium ion in the alunitejarosite group. The Canadian Mineralogist, 24, 435–447.Google Scholar
Ristić, M., Musić, S. and Orehovec, Z. (2005) Thermal decomposition of synthetic ammonium jarosite. Journal of Molecular Structure, 744–747, 295–300.Google Scholar
Salinas, E., Roca, A., Crue lls, M., Patino, F. and Córdoba, D.A. (2001) Characterization of alkaline decomposition–cyanidation kinetics of industrial ammonium jarositein NaOH media. Hydrometallurgy, 60, 237–246.CrossRefGoogle Scholar
Scott, K.M. (1987) Solid–solution in, and classification of, gossan–derived members of the alunite–jarosite family, northwest Queensland, Australia. American Mineralogist, 72, 178–187.Google Scholar
Shannon, E.V. (1927) Ammoniojarosite, a new mineral of the jarosite group from Utah. American Mineralogist, 12, 424–426.Google Scholar
Shannon, E.V. (1929) Tschermigite, ammoniojarosite, epsomite, celestite, and paligorskite from southern Utah. U.S. National Museum Proceedings, 74, 1–13.Google Scholar
Smith, W.L. and Lampert, J.E. (1973) Crystal data for ammoniojarosite NH4Fe3(OH)6(SO4)2 . Journal of Applied Crystallography, 6, 490–491.CrossRefGoogle Scholar
Stoffregen, R.E. (1993) Stability relations of jarosite and natrojarosite at 150–250ºC. Geochimica et Cosmochimica Acta, 57, 2417–2429.CrossRefGoogle Scholar
Stoffregen, R.E. and Alpers, C.N. (1987) Woodhouseite and svanbergite in hydrothermal ore deposits: Products of apatite destruction during advanced argillic alteration. The Canadian Mineralogist, 25, 201–211.Google Scholar
Young, R.A. (1993) Introduction to the Rietveld method. Pp. 1–38 in: The Rietveld Method (Young, R.A., editor). Oxford Science Publications, UK.Google Scholar