201. In situ simultaneous Fe K-edge XAS spectroscopy and resistivity measurements of riebeckite: Implications for anomalous electrical conductivity in subduction zones.
- Author
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Della Ventura, Giancarlo, Galdenzi, Federico, Marcelli, Augusto, Cibin, Giannantonio, Oberti, Roberta, Hawthorne, Frank C., Bernardini, Simone, and Mihailova, Boriana
- Subjects
ELECTRIC conductivity ,SUBDUCTION zones ,X-ray absorption spectra ,OCEANIC crust ,OXIDATION states ,X-ray absorption near edge structure - Abstract
In this paper, we address two key features of the behaviour of Fe-rich amphibole at high temperatures: (1) the Fe
2+ → Fe3+ + e− exchange within the crystal bulk, and (2) the consequent rise in electrical conductivity. Cycling heating-cooling experiments were done in situ up to 542 °C (815 K) at beamline B11 of the Diamond Synchrotron Laboratory (UK). X-ray absorption spectra at the Fe K-edge and electrical resistivity were measured simultaneously on a single crystal of riebeckite with a composition very close to the ideal formulaA □B Na 2C (Fe2+ 3 Fe3+ 2)T Si 8 O 22W (OH) 2. The Fe3+ /Fe tot ratio was monitored via analysis of the pre-edge feature in the XANES spectra. Our data show slight oscillations of the oxidation state of Fe with temperature cycling up to around 400 °C (673 K), followed by a substantial gradual increase in Fe2+ → Fe3+ oxidation that starts at ~450 °C (~723 K) and is completed at ~525 °C (~798 K). The conductivity (σ) measured along the crystallographic c-axis oscillates strongly with cycling temperature allowing us to conclude that it is intrinsically related to the electron hopping induced by thermal treatment. The activation-energy derived from the σ(T) trend is E a = 74.4 ± 0.6 kJ/mol (0.77 ± 0.01 eV), in agreement with small-polaron conduction. This study provides direct and robust support of the conduction mechanisms in Fe-amphibole previously inferred from indirect methods. Given that riebeckite is a significant component in the glaucophanitic amphiboles common in blueschists associated with subducted oceanic crust, our data provide a link between atomic-scale processes and Earth-scale anomalous conductivity observed via geophysical measurements. [Display omitted] [ABSTRACT FROM AUTHOR]- Published
- 2024
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