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  • 1
    ISSN: 1476-4687
    Quelle: Nature Archives 1869 - 2009
    Thema: Biologie , Chemie und Pharmazie , Medizin , Allgemeine Naturwissenschaft , Physik
    Notizen: [Auszug] The oxidation state recorded by rocks from the Earth's upper mantle can be calculated from measurements of the distribution of Fe3+ and Fe2+ between the constituent minerals. The capacity for minerals to incorporate Fe3+ may also ...
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 2
    Digitale Medien
    Digitale Medien
    [s.l.] : Macmillan Magazines Ltd.
    Nature 387 (1997), S. 694-696 
    ISSN: 1476-4687
    Quelle: Nature Archives 1869 - 2009
    Thema: Biologie , Chemie und Pharmazie , Medizin , Allgemeine Naturwissenschaft , Physik
    Notizen: [Auszug] The lower mantle constitutes more than half the Earth's interior by volume, and is believed to consist predominantly of (Mg,Fe)SiO3 perovskite with up to approximately 20% (Mg,Fe)O. In the system FeO–MgO–SiO2, iron partitions preferentially into (Mg,Fe)O ...
    Materialart: Digitale Medien
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  • 3
    Digitale Medien
    Digitale Medien
    Springer
    Physics and chemistry of minerals 23 (1996), S. 94-98 
    ISSN: 1432-2021
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Geologie und Paläontologie , Physik
    Notizen: Abstract Majorite of bulk composition Mg0.86Fe0.15SiO3 was synthesized at 19 GPa and 1900 °C at an oxygen fugacity close to the Re/ReO2 buffer. Optical absorption spectra of polycrystalline samples were measured from 4000 to 25000cm−1. The following features were observed: (1) Three bands at 4554, 6005 and 8093 cm−1 due to the 5Eg → 5T2g transition of Fe2+ in a distorted dodecahedral site. (2) A band at 9340 cm−1 due to the transition 5T2g → 5Eg of octahedral Fe2+. (3) A band at 22784 cm−1 resulting from Fe3+, probably in an octahedral site (6A1g → 4A1g, 4Eg). (4) A very intense system of Fe2+ → Fe3+ intervalence charge transfer bands which can be modelled by two Gaussian components centered at 16542 and 20128 cm−1. The existence of two components in the charge transfer spectrum could be related to the fact that the tetragonal majorite structure may contain Fe3+ in two different octahedral sites. The crystal field splitting Δ of Fe2+ in dodecahedral coordination is 5717 cm−1. If a splitting of the ground state in the order of 1000 cm−1 is assumed, this yields a crystal field stabilization energy (CFSE) of 3930 cm−1, comparable to the CFSE of Fe2+ in pyrope-rich garnet. However, the splitting of 5T2g is significantly higher than in pyrope. This would be consistent with Fe2+ preferentially occupying the more distorted one of the two dodecahedral sites in the majorite structure. For octahedral Fe2+, Δ= 9340 cm−1 and CFSE=3736 cm−1, assuming negligible splitting of the ground state.
    Materialart: Digitale Medien
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  • 4
    Digitale Medien
    Digitale Medien
    Springer
    Physics and chemistry of minerals 17 (1991), S. 636-641 
    ISSN: 1432-2021
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Geologie und Paläontologie , Physik
    Notizen: Abstract To investigate the equation of state of α-MnS at high pressure and the possibility of a phase transition, the compression curve was measured at 298 K from 0 to 21 GPa using powder x-ray diffraction with a diamond anvil cell. The compression data are fit to a thirdorder Birch-Murnaghan equation of state, with parameters K 0 = 72(2) GPa and K′ 0 = 4.2(13). To compare present results with previous work, the data sets from three previous investigations (Clendenen and Drickamer 1966; Wakabayashi et al. 1968; Kraft and Greuling 1988) are refit to a Birch-Murnaghan equation of state. In the low pressure region (P 〈 10 GPa), the results of Clendenen and Drickamer (1966) agree with the present data; however the results of Wakbayashi et al. (1968) differ by more than 10%. A greater discrepancy between the present and previous results occurs above 10 GPa. Kraft and Greuling (1988) reported a structure transition at 7 GPa, and Clendenen and Drickamer (1966) observed a structure distortion at approximately 10 GPa; the present data show no evidence of either transition, and are well fit by a single equation of state from 0 to 21 GPa. Nonhydrostatic stress is discussed as one possibility for the discrepancy.
    Materialart: Digitale Medien
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  • 5
    ISSN: 1432-0967
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Geologie und Paläontologie
    Notizen: Abstract Although the electron microprobe has become the standard microanalytical tool in modern geosciences, conventional electron microprobe analysis does not allow determination of the valence states of elements such as Fe. The correct classification of minerals and interpretation of reaction microfabrics and grain zonation require high-quality information on ferric/ferrous ratios on a scale of micrometers. The flank method developed by Höfer et al. (1994, Eur J Mineral 6:407–418) has revived new interest in electron-induced X-ray-spectroscopy to resolve oxidation states in minerals with high spatial resolution. We have recharacterized well-documented sodic amphiboles of the glaucophane–ferroglaucophane–riebeckite–magnesioriebeckite series by electron probe microanalysis and combined the microanalytical data with ferric/ferrous ratios from Mössbauer spectroscopy, Li data from bulk ICP-AES analysis and H2O data from bulk Karl–Fischer titration. The combination of microanalysis and high-quality analysis on the bulk materials results in a data set that allows comparison of model-based stoichiometric calculations and the calibration of the high-resolution flank method. The calibration obtained allows ferric/ferrous ratios to be determined within an error of ±5%. We have found it necessary to apply an empirical correction for absorption phenomena. The advantages of the method must be weighed against the complex calibration procedures necessary and thus the flank method will probably not find use as a routine method. However, in cases where high-resolution data in terms of valence state are needed, the flank method will provide useful data on ferric/ferrous ratios down to minimum FeOtotal content of 6–8 wt%.
    Materialart: Digitale Medien
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  • 6
    Digitale Medien
    Digitale Medien
    Springer
    Hyperfine interactions 92 (1994), S. 1235-1239 
    ISSN: 1572-9540
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Physik
    Notizen: Abstract Mössbauer spectra of absorbers with diameters smaller than 500 μm can be recorded using a high specific activity Mössbauer source. The spectrum quality as defined by the signal/noise ratio has been calculated for57Fe experiments as a function of absorber composition, thickness and diameter for both conventional and high specific activity source configurations. Results are in excellent agreement with experimental data for sodium nitroprusside, and demonstrate that high quality Mössbauer spectra can be collected for absorbers with diameters smaller than 500 μm if electronic absorption is low.
    Materialart: Digitale Medien
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  • 7
    Digitale Medien
    Digitale Medien
    Springer
    Hyperfine interactions 94 (1994), S. 1989-1993 
    ISSN: 1572-9540
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Physik
    Notizen: Abstract Mössbauer spectra were recorded at 80 and 4.2 K for Fe x O (x〉 0.95) samples that had been synthesized at 1000
    Materialart: Digitale Medien
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  • 8
    ISSN: 1572-9540
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Physik
    Notizen: Abstract The milliprobe technique has expanded the number of potential applications of Mössbauer spectroscopy, including the study of single crystals. Recent work has reported determination of the electric field gradient and mean-squared displacement tensors in hedenbergite, a member of the pyroxene mineral group. Results are used to assess Mössbauer data collected from clinopyroxene single crystals that occur as inclusions in diamond.
    Materialart: Digitale Medien
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  • 9
    Digitale Medien
    Digitale Medien
    Springer
    Hyperfine interactions 93 (1994), S. 1511-1514 
    ISSN: 1572-9540
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Physik
    Notizen: Abstract An in situ study of cubanite (CuFe2S3) was performed using energy dispersive X-ray diffraction and Mössbauer spectroscopy in a diamond anvil cell at room temperature and pressures up to 5 GPa. Mössbauer spectra of orthorhombic cubanite show a single iron site with a hyperfine magnetic field that is relatively insentive to pressure, and a centre shift which decreases with pressure at a rate consistent with no significant changes in bonding. Above 3 GPa, however, a nonmagnetic component appears that can be fitted to a single asymmetric quadrupole doublet with a centre shift corresponding to valence between Fe2+ and Fe3+. This is consistent with X-ray diffraction data that show an accompanying transition from the orthorhombic structure to the NiAs structure, where localised electron transfer could occur across pairs of face-shared octahedra or extended electron delocalisation could occur along sheets of face- and edge-shared octahedra.
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  • 10
    Digitale Medien
    Digitale Medien
    Springer
    Hyperfine interactions 90 (1994), S. 89-105 
    ISSN: 1572-9540
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Physik
    Notizen: Abstract New phases formed at high pressure and temperature can be successfully quenched to ambient conditions if the kinetics of the back transformation are slow. One important application of this technique is to mineral physics — the combination of microscopic measurements of the structural, physical and chemical properties of high-pressure minerals measured in the laboratory with macroscopic geophysical and geochemical data to produce a unified description of the Earth's interior. The dominant high-pressure phases inferred to be present in the Earth's mantle have been synthesised using a multi-anvil press to correlate structural and chemical information obtained from Mössbauer data with bulk geophysical and geochemical data to determine properties of the mantle, such as the oxidation state. Results from experiments on the major transition zone minerals β−(Mg, Fe)2SiO4, (Mg, Fe)SiO3 garnet and γ−(Mg, Fe)2SiO4 spinel include the discovery of significant Fe3+ in these phases synthesised in equilibrium with metallic iron and excess silica, implying that the oxygen fugacity (fO2) of the transition zone must be substantially lower than the upper mantlefO2. Mössbauer spectra of the lower mantle phase (Mg, Fe)SiO3 perovskite show that Fe2+ occupies the large distorted site almost exclusively, and that significant Fe3+ is present at the minimum fO2 stability limit. Low temperature spectra indicate a phase transition possibly corresponding to a distortion of the perovskite structure. Mössbauer spectra of FexO quenched from high pressure indicate that the Fe3+ content of samples in equilibrium with metallic iron is small, implying that the minimum amount of Fe3+ in the lower mantle (Mg, Fe)O at lower mantle conditions is also small. Mössbauer spectra from samples of (Mg, Fe)O synthesised at different temperatures andfO2 conditions show that the Fe3+ content can be reliably measured, and that it varies significantly withfO2. Implications of these results to properties of the Earth's interior are discussed.
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