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High-temperature vesuvianite: crystal chemistry and surface considerations

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Abstract

A multi-methodical approach has been applied for characterizing the bulk and surface crystal chemical features of a high-temperature vesuvianite crystal from skarns of Mount Somma-Vesuvius Volcano (Naples, Italy). Vesuvianite belongs to the space group P4/nnc with unit cell parameters a = 15.633(1) Å, c = 11.834(1) Å and chemical formula (Ca18.858 Na0.028 Ba0.004 K0.006 Sr0.005 □0.098)19.000 (Al8.813 Ti0.037 Mg2.954 Mn0.008 Fe 2+0.114 Fe 3+1.375 Cr0.008 B0.202)13.511 Si18.000(O0.261 F0.940 OH7.799)9.000. Structure refinement, which converges at R = 0.0328, demonstrates a strong positional disorder down the fourfold axes, indicating that the Y1 site is split into two positions (Y1A and Y1B) alternatively occupied. However, because of X4 proximity to Y1B and Y1A, X4 cannot be occupied if Y1B or Y1A are. Overall Y1 occupancy (Y1A + Y1B) reaches approximately 0.5, as common in vesuvianite and occupancy of Y1B site is extremely limited. Moreover, T1 position, limitedly occupied, accommodates the excess of cations generally related to Y position. A small quantity (0.202 apfu) of boron is sited at the T2 site that, like T1, is poorly occupied. The determination of the amount of each element on the (100) vesuvianite surface, obtained through X-ray photoelectron spectroscopy high-resolution spectra in the region of the Si2p, Al2p, Mg1s, and Ca2p core levels, evidences that a greater amount of aluminum and a smaller amount of calcium characterize the surface with respect to the bulk. Although both of these features require further investigation, we may consider the Al increase can be related to preferential orientation of Al-rich sites on the (100) plane. Furthermore, the surface structure of vesuvianite suggests that Al, Ca, and Mg cations maintain coordination features at the surface similar to the bulk. Silica, however, while presenting fourfold coordination, shows also a [1]-fold small coordinated component at binding energy 99.85 eV, due to broken Si–O bonds at the surface. The presence of eight- and nine-coordinated Ca cations is suggested by a large XPS feature resulting from the merging of Ca2p3/2 and Ca2p1/2 peaks at 348.45 and 352.05 eV, respectively.

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Acknowledgments

Our research is supported by Italian Ministero dell’Istruzione Università e Ricerca (MIUR) under project PRIN 2008. XAS spectra were collected at ELETTRA Synchrotron at Trieste. We would also kindly thank Dr. Federico Spizzo (Laboratory of Mössbauer spectroscopy, Università di Ferrara) for precious help in the analysis and interpretation of Mössbauer spectrum and Dr. Daniela Manzini (Centro Interdipartimentale Grandi Strumenti (CIGS), Università di Modena e Reggio Emilia) for her valuable support in the use of LA-ICP-MA. We thank Catherine McCammon and L.A. Groat for their critical readings of the manuscript, helpful corrections and additions to its contents.

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Authors and Affiliations

  1. Dipartimento di Scienze della Terra, Università di Modena e Reggio Emilia, Largo S. Eufemia 19, 41121, Modena, Italy

    Chiara Elmi, Maria Franca Brigatti, Angela Laurora & Daniele Malferrari

  2. Dipartimento di Ingegneria dei Materiali e dell’Ambiente, Università di Modena e Reggio Emilia, Via Vignolese 905, 41125, Modena, Italy

    Luca Pasquali, Monica Montecchi & Stefano Nannarone

  3. IOM INFM-CNR Area Science Park, Building MM, S.S. 14, Km 163.5, 34012, Basovizza, TS, Italy

    Luca Pasquali, Monica Montecchi & Stefano Nannarone

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  1. Chiara Elmi
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  2. Maria Franca Brigatti
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  3. Luca Pasquali
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  4. Monica Montecchi
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  5. Angela Laurora
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Correspondence to Maria Franca Brigatti.

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Elmi, C., Brigatti, M.F., Pasquali, L. et al. High-temperature vesuvianite: crystal chemistry and surface considerations. Phys Chem Minerals 38, 459–468 (2011). https://doi.org/10.1007/s00269-011-0419-2

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