The crystal chemistry of birefringent natural uvarovites. Part IV. OH defect incorporation mechanisms in non-cubic garnets derived from polarized IR spectroscopy

Author(s)
Michael Andrut, Manfred Wildner, Anton Beran
Abstract

The anisotropic OH stretching vibrational behavior of three birefringent garnet crystals with compositions close to the uvarovite-grossular binary from the locality Saranov (Ural Mountains, Russia) are investigated in detail by polarized IR microspectroscopy. These garnet samples exhibit low but significantly different water contents (Sar-899 <Sar-w2 <Sar-k12 <0.5 wt.% H2O). The IR polarization behavior in the OH stretching vibrational region of samples Sar-899, Sar-k12, and Sar-w2 complies with orthorhombic, monoclinic, and triclinic crystal symmetry, respectively. The corresponding spectra consist of 14 discernible, partly superimposing absorption bands between 3680 and 3470 cm-1, which are assigned to structurally incorporated hydroxyl groups. According to the individual pleochroic behavior of ten clearly non-isotropic bands, six different pleochroic patterns, i.e. four band doublets and two single bands are distinguished. For the band doublets at 3559/3540 cm-1, 3572/3565 cm-1, and 3595/3588 cm-1, as well as for the single 3618 cm-1 band, models for a structural OH incorporation based on the classical (O4H4) hydrogarnet substitution are proposed. In contrast, for the band doublet at 3652/3602 cm-1 and the single band at 3640 cm-1, OH defect incorporation is explained assuming the presence of vacancies on octahedral or dodecahedral cation positions, leading to [SiO3(OH)] tetrahedral groups. It is concluded that in garnets with low water contents the [SiO3(OH)] substitution plays an essential role as OH defect incorporation mechanism.

Organisation(s)
Department of Mineralogy and Crystallography
External organisation(s)
University of Vienna
Journal
European Journal of Mineralogy: an international journal of mineralogy, geochemistry and related sciences
Volume
14
Pages
1019-1026
No. of pages
8
ISSN
0935-1221
DOI
https://doi.org/10.1127/0935-1221/2002/0014-1019
Publication date
2002
Peer reviewed
Yes
Austrian Fields of Science 2012
1051 Geology, Mineralogy
Portal url
https://ucrisportal.univie.ac.at/en/publications/5ec1d68c-dc8d-4389-80d8-23d8cf4b2573