Spectroscopic studies of synthetic and natural ringwoodite, γ-(Mg, Fe)2SiO4

Autor: Richard Wirth, Monika Koch-Müller, Ansgar Greshake, Dieter Rhede, Michail N. Taran, Irmgard Abs-Wurmbach
Rok vydání: 2008
Předmět:
Zdroj: Physics and Chemistry of Minerals
ISSN: 1432-2021
0342-1791
DOI: 10.1007/s00269-008-0271-1
Popis: Synthetic ringwoodite γ-(Mg1−x Fe x )2SiO4 of 0.4 ≤ x ≤ 1.0 compositions and variously colored micro-grains of natural ringwoodite in shock metamorphism veins of thin sections of two S6-type chondrites were studied by means of microprobe analysis, TEM and optical absorption spectroscopy. Three synthetic samples were studied in addition with Mossbauer spectroscopy. The Mossbauer spectra consist of two doublets caused by VIFe2+ and VIFe3+, with IS and QS parameters close to those established elsewhere (e.g., O’Neill et al. in Am Mineral 78:456–460, 1993). The Fe3+/Fetotal ratio evaluated by curve resolution of the spectra, ranges from 0.04 to 0.1. Optical absorption spectra of all synthetic samples studied are qualitatively very similar as they are directly related to the iron content. They differ mostly in the intensity of the observed absorption features. The spectra consist of a very strong high-energy absorption edge and a series of absorption bands of different width and intensity. The three strongest and broadest absorptions of them are attributed to splitting of electronic spin-allowed 5 T 2g → 5 E g transitions of VIFe2+ and intervalence charge-transfer (IVCT) transition between ferrous and ferric ions in adjacent octahedral sites of the ringwoodite structure. The spin-allowed bands at ca. 8,000 and 11,500 cm−1 weakly depend on temperature, whilst the Fe2+/Fe3+ IVCT band at ~16,400 cm−1 displays very strong temperature dependence: i.e., with increasing temperature it decreases and practically disappears at about 497 K, a behavior typical for bands of this type. With increasing pressure the absorption edge shifts to lower energies while the spin-allowed bands shift to higher energy and strongly decreases in intensity. The IVCT band also strongly weakens and vanishes at about 9 GPa. We assigned this effect to pressure-induced reduction of Fe3+ in ringwoodite. By analogy with synthetic samples three broad bands in spectra of natural (meteoritic) blue ringwoodite are assigned to electronic spin-allowed transitions of VIFe2+ (the bands at ~8,600 and ~12,700 cm−1) and Fe2+/Fe3+ IVCT transition (~18,100 cm−1), respectively. Spectra of colorless ringwoodite of the same composition consist of a single broad band at ca. 12,000 cm−1. It is assumed that such ringwoodite grains are inverse (Fe, Mg)2SiO4-spinels and that the single band is caused by the split spin-allowed 5 E → 5 T 2 transition of IVFe2+. Ringwoodite of intermediate color variations between dark-blue and colorless are assumed to be partly inversed ringwoodite. No glassy material between the grain boundaries in the natural colored ringwoodite aggregates was found in our samples and disprove the cause of the coloration to be due to light scattering effect (Lingemann and Stoffler in Lunar Planet Sci 29(1308), 1998).
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