Accurate determination of ferric iron in garnets by bulk Mössbauer spectroscopy and synchrotron micro-XANES
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M. Darby Dyar
Abstract
Measurements of Fe3+/ΣFe in geological materials have been intractable because of lack of access to appropriate facilities, the time-consuming nature of most analyses, and the lack of precision and reproducibility in most techniques. Accurate use of bulk Mössbauer spectroscopy is limited by largely unconstrained recoilless fraction (f), which is used to convert spectral peak area ratios into valid estimates of species concentrations and is unique to different mineral groups and compositions. Use of petrographic-scale synchrotron micro-XANES has been handicapped by the lack of a consistent model to relate spectral features to Fe3+/ΣFe. This paper addresses these two deficiencies, focusing specifically on a set of garnet group minerals. Variable-temperature Mössbauer spectra of the Fe2+-bearing almandine and Fe3+-bearing andradite end-members are used to characterize f in garnets, allowing Fe3+/ΣFe to be measured accurately. Mössbauer spectra of 19 garnets with varying composition were acquired and fit, producing a set of garnet-specific standards for Fe3+ analyses. High-resolution XANES data were then acquired from these and 15 additional previously studied samples to create a calibration suite representing a broad range of Fe3+ and garnet composition. Several previously proposed techniques for using simple linear regression methods to predict Fe3+/ΣFe were evaluated, along with the multivariate analysis technique of partial least-squares regression (PLS). Results show that PLS analysis of the entire XANES spectral region yields the most accurate predictions of Fe3+ in garnets with both robustness and generalizability. Together, these two techniques present reliable choices for bulk and microanalysis of garnet group minerals.
© 2015 by Walter de Gruyter Berlin/Boston
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Artikel in diesem Heft
- MSA Roebling medal lecture. Mineralogy, petrology, U-Pb geochronology, and geologic evolution of the Dabie-Sulu classic ultrahigh-pressure metamorphic terrane, East-Central China
- Brittle-ductile microfabrics in naturally deformed zircon: Deformation mechanisms and consequences for U-Pb dating
- In situ hot-stage AFM study of the dissolution of the barite (001) surface in water at 30–55 °C
- A multi-domain gem-grade Brazilian apatite
- High-temperature structural behaviors of anhydrous wadsleyite and forsterite
- Rates and mechanism of Y, REE, and Cr diffusion in garnet
- EPR discrimination of microcrystalline calcite geomaterials
- Crystal chemistry of Bi- and Mn-bearing vesuvianite from Långban, Sweden
- Cation ordering in Pb2+-bearing, Mn3+-rich pargasite from Långban, Sweden
- Long-term solid-phase fate of co-precipitated U(VI)-Fe(III) following biological iron reduction by Thermoanaerobacter
- The sulfur speciation in S-bearing minerals: New constraints by a combination of electron microprobe analysis and DFT calculations with special reference to sodalite-group minerals
- Simultaneous sound velocity and density measurements of NaCl at high temperatures and pressures: Application as a primary pressure standard
- The temperature and compositional dependence of disordering in Fe-bearing dolomites
- Quantifying crystallization and devitrification of rhyolites by means of X-ray diffraction and electron microprobe analysis
- Reactions of strontium anorthite with H2O+CaCl2 fluids at 500 °C and high pressure: Kinetic information from in situ synchrotron-radiation XRF analyses of the fluid
- Solubility of xenotime in a 2 M HCl aqueous fluid from 1.2 to 2.6 GPa and 300 to 500 °C
- Elastic and anelastic anomalies due to spin-state transitions in orthorhombic perovskite from isoelectronic behavior of Co3+ and Fe2+
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- Re-investigation of the crystal structure of enstatite under high-pressure conditions
- Second-order P6̄c2-P31c transition and structural crystallography of the cyclosilicate benitoite, BaTiSi3O9, at high pressure
- High-pressure structural studies of eskolaite by means of single-crystal X-ray diffraction
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- Krasheninnikovite, KNa2CaMg(SO4)3F, a new mineral from the Tolbachik volcano, Kamchatka, Russia
- Crystal structure of pseudojohannite, with a revised formula, Cu3(OH)2[(UO2)4O4(SO4)2](H2O)12
- Letter. A natural photoelectrochemical cell for water splitting: Implications for early Earth and Mars
- Letter. In situ observation of the breakdown of magnetite (Fe3O4) to Fe4O5 and hematite at high pressures and temperatures
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