Éditeur(s) : HAL CCSD Springer Verlag (Germany) Springer Verlag
Résumé : International audience
We have investigated the partitioning of Fe3+ between orthopyroxene (Opx) and garnet (Grt) in well-equilibrated mantle xenoliths using Mössbauer spectroscopy. The samples cover a wide range of P–T conditions (2.1–6.6 GPa, 690–1,412 °C) and geothermal gradients, and are thus representative for Earth’s upper mantle in both on-craton and off-craton continental settings. Garnet has Fe3+/Fetot ratios of 0.03–0.13 and Fe2O3 contents of 0.24–1.00 wt%. Orthopyroxene has, on average, lower Fe3+/Fetot ratios (0.01–0.09) and Fe2O3 contents (0.05–0.63 wt%). In low-pressure, high-temperature samples, however, Opx is systematically richer in Fe2O3 than the coexisting Grt. The Fe3+ Opx/Grt partition coefficient (DOpx/GrtFe3+) shows no obvious relationship with temperature, but increases with decreasing pressure and with increasing NaOpx. The observed Opx/Grt Fe3+ systematics imply that the Opx–Grt Fe–Mg exchange thermometer is not robust against redox changes if total Fe is treated as Fe2+. An approximate evaluation of errors on T estimates due to redox effects predicts negligible deviations for strongly reduced conditions (<65 °C), but potentially large deviations (> to ≫100 °C) for strongly oxidized conditions, especially at very high pressure and when both P and T are calculated by iteration.
ISSN: 0010-7999

hal-01121606
https://hal.archives-ouvertes.fr/hal-01121606
DOI : 10.1007/s00410-014-1101-8

Éditeur(s) : HAL CCSD Mineralogical Society of America
Résumé : International audience
Wadsleyites with various iron contents were synthesized at ~12-14 GPa and 1400 °C under oxidizing and hydrous conditions in coexistence with enstatite. The samples were studied using micro-X-ray absorption near edge structure (XANES) and micro-Mössbauer spectroscopy to determine the ferric iron contents in polyphasic samples and secondary ion mass spectrometry (SIMS) to determine the water concentrations. XANES and Mössbauer analyses show that ferric iron content increases with increasing total iron content, and reaches a maximum of ~30% Fe3+/Fetotal. Two XANES results were cross-checked by Mössbauer analysis and both methods are in reasonable agreement. The use of Fourier transform infrared spectroscopy reveals a new protonation scheme in wadsleyite, with a significant proportion of protons associated with the high-frequency band at 3611 cm−1 and a new band located at 3500 cm−1. The intensity of these two bands is higher for Fe3+-rich wadsleyite. SIMS analyses show that water contents in wadsleyite vary from 4500 to 9400 ppm H2O by weight. Pyroxene water contents range from 790 to 1600 ppm wt H2O. The concentration of water in both phases decreases with increasing iron content. The partition coefficient of water between wadsleyite and pyroxene varies between 5 and 9 and increases with increasing Fe-number of wadsleyite [i.e., XFe/(XFe + XMg) × 100 ratio]. The divalent cation concentrations (i.e., Mg2+ + Fe2+), the Si as well as the H content in wadsleyite decrease with increasing Fe3+ content, indicating an incorporation mechanism via substitution into the metal (Me = Mg2+ and Fe2+) and Si sites with a ratio of 5/3 for (Fe3++H+):Me and of 5/1 for (Fe3++H+):Si, similarly as in the dry system. Thus, coupled substitution of Fe3+ and H+ does not affect the incorporation mechanism of Fe3+, but does affect the location of H+, which is partly incorporated at tetrahedral edges forming [FeSi′-(OH)o*]X neutral defects substituting for Si. In this model 25% of the ferric iron occupies the tetrahedral sites.
ISSN: 0003-004X

hal-00758071
https://hal.archives-ouvertes.fr/hal-00758071
DOI : 10.2138/am.2012.3869