High-temperature vesuvianite: crystal chemistry and surface considerations |
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Authors: | Chiara Elmi Maria Franca Brigatti Luca Pasquali Monica Montecchi Angela Laurora Daniele Malferrari Stefano Nannarone |
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Institution: | 1.Dipartimento di Scienze della Terra,Università di Modena e Reggio Emilia,Modena,Italy;2.Dipartimento di Ingegneria dei Materiali e dell’Ambiente,Università di Modena e Reggio Emilia,Modena,Italy;3.IOM INFM-CNR Area Science Park,Basovizza,Italy |
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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 Fe0.1142+ Fe1.3753+ 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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