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OH incorporation in nearly pure MgAl2O4 natural and synthetic spinels |
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| Authors: | Davide Lenaz Henrik Skogby Francesco Princivalle |
| Institution: | a Dipartimento di Scienze della Terra, via Weiss 8, I-34127 Trieste, Italy b Department of Mineralogy, Swedish Museum of Natural History, Box 50007, SE-10405 Stockholm, Sweden c Dipartimento di Geoscienze, Corso Garibaldi 37, I-35137 Padova, Italy |
| Abstract: | Four nearly pure MgAl2O4 spinels, of both natural and synthetic occurrence, have been studied by means of X-ray single crystal diffraction and FTIR spectroscopy in order to detect their potential OH content. Absorption bands that can be assigned to OH incorporated in the spinel structure were only observed in spectra of a non-stoichiometric synthetic sample. The absorption intensity of two bands occurring at 3350 and 3548 cm−1 indicate an OH content of 90 ppm H2O. Based on correlations of OH vibrational frequencies and O-H?O distances, the observed absorption bands correspond to O-H?O distances of 2.77 and 2.99 Å, respectively, which is close to the values obtained by the structure refinements for VIO-Ounsh (2.825 Å) and IVO-O (3.001 Å). This indicates that one probable local position for hydrogen incorporation is the oxygens coordinating a vacant tetrahedral site. The present spectra demonstrate that the detection limit for OH in Fe-free spinels is in the range 10-20 ppm H2O. However, at appreciable Fe2+ levels, the detection of OH bands becomes hampered due to overlap with strong absorption bands caused by electronic d-d transitions in Fe2+ in the tetrahedral position. |
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