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In situ high-temperature X-ray diffraction and spectroscopic study of fibroferrite, FeOH(SO4)·5H2O

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Abstract

The thermal dehydration process of fibroferrite, FeOH(SO4)·5H2O, a secondary iron-bearing hydrous sulfate, was investigated by in situ high-temperature synchrotron X-ray powder diffraction (HT-XRPD), in situ high-temperature Fourier transform infrared spectroscopy (HT-FTIR) and thermal analysis (TGA-DTA) combined with evolved gas mass spectrometry. The data analysis allowed the determination of the stability fields and the reaction paths for this mineral as well as characterization of its high-temperature products. Five main endothermic peaks are observed in the DTA curve collected from room T up to 800 °C. Mass spectrometry of gases evolved during thermogravimetric analysis confirms that the first four mass loss steps are due to water emission, while the fifth is due to a dehydroxylation process; the final step is due to the decomposition of the remaining sulfate ion. The temperature behavior of the different phases occurring during the heating process was analyzed, and the induced structural changes are discussed. In particular, the crystal structure of a new phase, FeOH(SO4)·4H2O, appearing at about 80 °C due to release of one interstitial H2O molecule, was solved by ab initio real-space and reciprocal-space methods. This study contributes to further understanding of the dehydration mechanism and thermal stability of secondary sulfate minerals.

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Acknowledgments

This work was supported by the Grants from the Italian Ministry of University and Research (PRIN 2010–2011). We thank two reviewers, S. Krivovichev and H. Effenberger, for their constructive comments, which helped us to improve the clarity of the manuscript.

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Authors and Affiliations

  1. Dipartimento di Scienze della Terra e Geoambientali, Università di Bari, via Orabona, 4, 70125, Bari, Italy

    Gennaro Ventruti, Maria Lacalamita & Emanuela Schingaro

  2. Dipartimento Scienze Geologiche, Università di Roma Tre, Largo S. Leonardo Murialdo 1, 00146, Rome, Italy

    Giancarlo Della Ventura & Umberto Susta

  3. Istituto di Cristallografia – CNR, Via G. Amendola, 122/O, 70126, Bari, Italy

    Nicola Corriero

  4. Dipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Modena e Reggio Emilia, Via Campi 103, 41125, Modena, Italy

    Daniele Malferrari & Alessandro F. Gualtieri

Authors
  1. Gennaro Ventruti
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  2. Giancarlo Della Ventura
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  3. Nicola Corriero
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  4. Daniele Malferrari
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  5. Alessandro F. Gualtieri
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  6. Umberto Susta
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  7. Maria Lacalamita
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  8. Emanuela Schingaro
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Correspondence to Gennaro Ventruti.

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Ventruti, G., Ventura, G.D., Corriero, N. et al. In situ high-temperature X-ray diffraction and spectroscopic study of fibroferrite, FeOH(SO4)·5H2O. Phys Chem Minerals 43, 587–595 (2016). https://doi.org/10.1007/s00269-016-0819-4

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  • DOI: https://doi.org/10.1007/s00269-016-0819-4

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