A systematic study of OH in hydrous wadsleyite from polarized FTIR spectroscopy and single-crystal X-ray diffraction: Oxygen sites for hydrogen storage in Earthʼs interior
-
Steven D. Jacobsen
,
Sylvie Demouchy
Abstract
The incorporation of hydrogen into wadsleyite (β-Mg2SiO4) was investigated using polarized FTIR spectroscopy and X-ray diffraction on oriented single crystals. The experiments were carried out with a new suite of samples containing between ~100 and ~10 000 ppm H2O by weight (wt ppm), encompassing the H-contents most relevant to Earth's potentially hydrous mantle transition zone. Attempts to synthesize anhydrous wadsleyite resulted in water contents of no less than ~50 wt ppm H2O. An empirical relation between the b/a axial ratio against estimated wt ppm concentrations of H2O in wadsleyite (CH2O) was determined: (b/a) = 2.008(1) + 1.25(3) × 10-6 · CH2O
Polarized infrared absorption spectra were measured in the three orthogonal sections perpendicular to the major axes of the optical indicatrix ellipsoid and are used in concert with results from new structure refinements to place constraints on the main absorbers in the structure. All of the main bands in the O-H stretching region of the FTIR can be explained by protonation of O1, the anomalous non-silicate oxygen site. We assign the band at 3614 cm-1 to a bent hydrogen bond O1···O1 (2.887 Å) along the M3 edge in the a-c plane. The band at 3581 cm-1 is assigned to a bent hydrogen bond on O1···O3 (3.016 Å) of the M3 edge in the b-c plane. The absorption bands at 3360, 3326, and 3317 cm-1 are best explained by hydrogen bonds on O1···O4 (3.092 Å) and O1···O4 (2.795 Å) along the M3 and M2 edges with possible splitting of one band due to vacancy ordering, but we cannot rule out contributions from three other (O1···O3) edges. The broad absorption feature at 3000 cm-1 is unambiguously assigned to the O4···O4 (2.720 Å) tetrahedral edge of the Si2O7 group pointing along the [100] vector. On hydration to ~1 wt% H2O, M-site vacancies are observed exclusively at M3. A systematic shortening of several (interpreted) hydrogen bonded O···O M-site edges is attributed to reduced O-O repulsive forces on protonation in the vicinity of an M-site vacancy.
© 2015 by Walter de Gruyter Berlin/Boston
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Articles in the same Issue
- Contact metamorphism of the White Mountain Peak metavolcanic complex, eastern California
- Structure and luminescence characteristics of quartz from pegmatites
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- The influence of OH in coesite on the kinetics of the coesite-quartz phase transition
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- Relationships between SEM-cathodoluminescence response and trace-element composition of hydrothermal vein quartz
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- Biotic and abiotic products of Mn(II) oxidation by spores of the marine Bacillus sp. strain SG-1
- The Mn, Mg-intracrystalline exchange reaction in donpeacorite (Mn0.54Ca0.03Mg1.43Si2O6) and its relation to the fractionation behavior of Mn in Fe, Mg-orthopyroxene
- Crystal structures of chalcostibite (CuSbS2) and emplectite (CuBiS2): Structural relationship of stereochemical activity between chalcostibite and emplectite
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- Relict coesite exsolution in omphacite from Western Tianshan eclogites, China
- Hyperfine electric field gradients and local distortion environments of octahedrally coordinated Fe2+
- A synchrotron Mössbauer spectroscopy study of (Mg,Fe)SiO3 perovskite up to 120 GPa
- Temporal stability and pressure calibration of barium carbonate and talc/pyrex pressure media in a piston-cylinder apparatus
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