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ANSTO Publications Online >
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Please use this identifier to cite or link to this item:
http://apo.ansto.gov.au/dspace/handle/10238/2884
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| Title: | XANES calibration for determining the oxidation state of iron in mantle garnet. |
| Authors: | Berry, AJ Yaxley, GM Woodland, AB Foran, GJ |
| Keywords: | Garnets Iron Valence Oxygen Absorption X-Ray Spectra |
| Issue Date: | 1-Nov-2010 |
| Publisher: | Elsevier |
| Citation: | Berry, A. J., Yaxley, G. M., Woodland, A. B., & Foran, G. J. (2010). XANES calibration for determining the oxidation state of iron in mantle garnet. Chemical Geology, 278(1-2), 31-37. |
| Abstract: | Iron K-edge X-ray absorption near edge structure (XANES) spectra were recorded for synthetic garnets of the almandine–skiagite (Fe3Al2Si3O12–Fe3Fe2Si3O12), andradite–skiagite (Ca3Fe2Si3O12–Fe3Fe2Si3O12), Fe–knorringite–skiagite (Fe3Cr2Si3O12–Fe3Fe2Si3O12), and andradite–grossular (Ca3Fe2Si3O12–Ca3Al2Si3O12) solid solutions. Fe3+/ΣFe varied systematically in these samples from 0 to 1. The variation in the energy and intensity of spectral features as a function of Fe3+/ΣFe was investigated to identify correlations that could be used to determine Fe3+/ΣFe of unknowns. The pre-edge energy, which is commonly used for quantification, was found to be relatively insensitive for garnet, particularly at low values of Fe3+/ΣFe. The best correlation was for the absorption edge energy, which may provide an accurate and precise method for determining Fe3+/ΣFe of garnets in metapelitic rocks. The resulting calibration curve, however, significantly and non-systematically overestimates the Fe3+/ΣFe value of mantle garnets (from xenoliths and megacrysts) for which Fe3+/ΣFe had been determined previously by Mössbauer spectroscopy. This is probably a result of differences in composition between the synthetic and natural garnets. For the mantle garnets, Fe3+/ΣFe is strongly correlated with the intensity ratio of post-edge features at 7138.4 and 7161.7 eV. The deviation of the Mössbauer results from a linear fit is less than 0.01 (1 σ). This suggests a new method for determining Fe3+/ΣFe from XANES spectra that does not require precise energy calibration or spectral fitting. The accuracy and precision for mantle garnets (within the compositional range studied: 0.75 ≤ Mg/(Mg + Fe) ≤ 0.86, 3.7–6.3 wt.% CaO, and 0.3–7.4 wt.% Cr2O3) is comparable to those of Mössbauer spectrosopy, however, XANES spectra can be acquired in ~ 15 min, allowing large numbers of samples to be analysed or the distribution of Fe3+/ΣFe to be mapped with micron spatial resolution. © 2010, Elsevier Ltd. |
| URI: | http://dx.doi.org/10.1016/j.chemgeo.2010.08.019 http://apo.ansto.gov.au/dspace/handle/10238/2884 |
| ISSN: | 0009-2541 |
| Appears in Collections: | Journal Articles |
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