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Iron speciation using electron microprobe techniques: application to glassy melt pockets within a spinel lherzolite xenolith

Published online by Cambridge University Press:  05 July 2018

M. Fialin ,
C. Wagner  and
M.-L. Pascal
M. Fialin*
Affiliation:
Centre de Microanalyse Camparis, UPMC Univ Paris 06, IPGP, CNRS-UMR 7094, F-75005, Paris, France
C. Wagner
Affiliation:
UPMC Univ Paris 06, UMR 7193, ISTeP, F-75005, Paris, France CNRS, UMR 7193, ISTeP, F-75005, Paris, France
M.-L. Pascal
Affiliation:
UPMC Univ Paris 06, UMR 7193, ISTeP, F-75005, Paris, France CNRS, UMR 7193, ISTeP, F-75005, Paris, France
*
*E-mail: [email protected]
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Abstract

A quantitative determination of Fe3+/ΣFe ratios using the electron microprobe is presented for glasses. The measurements are based on the shift of the Fe-Lα peak position between Fe3+ and Fe2+, resulting from differences in self-absorption. We present new calibration curves for glasses with Fe contents as low as 2 wt.% Fe.

This method was used for glasses from a metasomatized spinel Iherzolite (Massif Central, France) in which highly vesicular glass associated with secondary minerals occurs in reaction pockets around corroded Cr-spinels. The glass was found to be oxidized homogeneously with Fe3+/ΣFe ≈ 0.70 (measured with an uncertainty of ±0.06), in contrast with the value of ∼0.15 that would correspond to the former melt under fo2 conditions inferred from secondary minerals. The glass oxidation probably results from the dissociation of the melt-water content under degassing, prior to local hematite depositions (spinel rims and crack fillings).

Keywords

iron speciationelectron microprobeoxidationmantle-xenolith glasses
Type
CNMNC Newsletter 8
Information
Mineralogical Magazine , Volume 75 , Issue 2 , April 2011 , pp. 347 - 362
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2011

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References

Amthauer, G. (1996) Ligand field theoryand inter- and intracrystalline cation distribution of transition elements in minerals and related inorganic compounds. Physics and Chemistry of Minerals, 23, 276-283.CrossRefGoogle Scholar
Amundsen, H.E.F. and Neumann, E.-R. (1992) Redox control during mantle/melt interaction. Geochimica et Cosmochimica Acta, 56, 2405-2416.CrossRefGoogle Scholar
Ballhaus, C. (1993) Redox states of lithospheric and asthenospheric upper mantle. Contributions to Mineralogy and Petrology, 114, 331-348.CrossRefGoogle Scholar
Ballhaus, C., Berry, R.F. and Green, D.H. (1991) High pressure experimental calibration of the olivineorthopyroxene-spinel oxygen barometer: implication for the oxidation state of the mantle. Contributions to Mineralogy and Petrology, 107, 27-40.CrossRefGoogle Scholar
Bingham, P.A., Parker, J.M., Searle, T.M. and Smith, I. (2007) Local structure and medium range ordering of tetrahedrallycoordinated Fe3+ ions in alkali-alkaline earth-silica glasses. Journal of Non-Crystalline Solids, 353, 2479-2494.CrossRefGoogle Scholar
Botcharnikov, R.E., Koepke, J., Holtz, F., McCammon, C. and Wilke, M. (2005) The effect of water activity on the oxidation and structural state of Fe in a ferrobasaltic melt. Geochimica et Cosmochimica Acta, 69(21), 5071-5085.CrossRefGoogle Scholar
Brandon, A.D. and Draper, D.S. (1996) Constraints on the origin of the oxidation state of mantle overlying subduction zones: An example from Simcoe, Washington, USA. Geochimica et Cosmochimica Acta, 60, 1739-1749.CrossRefGoogle Scholar
Canil, D. and O’Neill, H.S.C. (1996) Distribution of ferric iron in some upper mantle assemblages. Journal of Petrology, 37, 609-635.CrossRefGoogle Scholar
Canil, D., O’Neill, H.St.C., Pearson, D.G., Rudnik, R.L., McDonough, W.F. and Carswell, D.A. (1994) Ferric iron in peridotites and mantle oxidation state. Earth and Planetary Science Letters, 123, 205-220.CrossRefGoogle Scholar
Coltorti, M., Beccaluva, L., Bonadiman, C., Salvini, L. and Siena, F. (2000) Glasses in mantle xenoliths as geochemical indicators of metasomatic agents. Earth and Planetary Science Letters, 183, 303-320.CrossRefGoogle Scholar
Cook, G.B. and Cooper, R.F. (2000) Iron concentration and the physical processes of dynamic oxidation in an alkaline earth aluminosilicate glass. American Mineralogist, 85, 397-406.CrossRefGoogle Scholar
Cook, G.B., Cooper, R.F. and Wu, T. (1990) Chemical diffusion and crystalline nucleation during oxidation of ferrous iron-bearing magnesium aluminosilicate glass. Journal of Non-Crystalline Solids, 120, 207-222.CrossRefGoogle Scholar
Cooper, R.F., Fanselow, J.B., Weber, J.K.R., Merkley, D.R. and Poker, D.B. (1996) Dynamics of oxidation of a Fe2+-bearing aluminosilicate (basaltic) melt. Science, 274, 1173-1176.CrossRefGoogle ScholarPubMed
Creighton, S., Stachel, T., Matveev, S., Höfer, H., McCammon, C. and Luth, R.W. (2009) Oxidation of the Kaapvaal lithospheric mantle driven bymetasomatism. Contributions to Mineralogy and Petrology, 157, 491-504.CrossRefGoogle Scholar
Farges, F., Lefrère, Y., Rossano, S., Berthereau, A., Calas, G. and Brown, G.E. (2004) The effect of redox state on the local structural environment of iron in silicate glasses: a molecular dynamics, combined XAFS spectroscopy, bond valence study. Journal of Non-Crystalline Solids, 344, 176-188.CrossRefGoogle Scholar
Fialin, M., Wagner, C., Métrich, N., Humler, E., Galoisy, L. and Bézos, A. (2001) Fe3+/SFe vs. Fe-La peak energyfor minerals and glasses: recent advances with the electron microprobe. American Mineralogist, 86, 456-465.CrossRefGoogle Scholar
Fialin, M., Bézos, A., Wagner, C., Magnien, V. and Humler, E. (2004) Quantitative electron microprobe analysis of Fe3+/SFe: Basic concepts and experimental protocol for glasses. American Mineralogist, 89, 654-662.CrossRefGoogle Scholar
Foley, S.E. (2010) A reappraisal of redox melting in the earth's mantle as a function of tectonic setting and time. Journal of Petrology, doi:10.1093/petrology/ egq061.CrossRefGoogle Scholar
Galoisy, L., Calas, G. and Arrio, M.A. (2001) Highresolution XANES spectra of iron in minerals and glasses: structural informations from the pre-edge region. Chemical Geology, 174, 307-319.CrossRefGoogle Scholar
Garvie, L.A.J. and Buseck, P.R. (1998) Ratios of ferrous to ferric iron from nanometre-sized areas in minerals. Nature, 396, 667-670.CrossRefGoogle Scholar
Ghiorso, M.S. and Sack, R.O. (1995) Chemical Mass Transfer in Magmatic Processes. IV. A revised and internally consistent thermodynamic model for the interpolation and extrapolation of liquid-solid equilibria in magmatic systems at elevated temperatures and pressures. Contributions to Mineralogy and Petrology, 119, 197-212.CrossRefGoogle Scholar
Giuli, G., Pratesi, G., Cipriani, C. and Paris, E. (2002) Iron local structure in tektites and impact glasses by extended X-rayabsorption fine structure and highresolution X-rayabsorption near-edge structure spectroscopy. Geochimica et Cosmochimica Acta, 66, 4347-4353.CrossRefGoogle Scholar
Gudmundsson, G. and Wood, B.J. (1995) Experimental tests of garnet peridotite oxygen barometry. Contributions to Mineralogy and Petrology, 19, 56-67.CrossRefGoogle Scholar
Haggerty, S.E. (1976) Oxidation of opaque mineral assemblages in basalts. Pp. 1–100 in: Oxide Minerals (Rumble, D. III, editor). Reviews in Mineralogy, 3, Mineralogical Societyof America, Washington, D.C.Google Scholar
Helz, R.T. and Thornber, C.R. (1987) Geothermometry of Kilauea Iki Lava Lake, Hawaii. Bulletin of Volcanology, 49, 651-668.CrossRefGoogle Scholar
Höfer, H.E. and Brey, G.P. (2007) The iron oxidation state of garnet byelectron microprobe: Its determination with the flank method combined with majorelement analysis. American Mineralogist, 92, 873-885.CrossRefGoogle Scholar
Höfer, H.E. and Woodland, A.B. (2003) Iron oxidation state of mantle minerals determined from the L emission spectra bythe electron microprobe. In: 8th International Kimberlite Conference, Long Abstract, 4 pp.Google Scholar
Höfer, H.E., Brey, G.P., Schulz-Dobrick, B. and Oberhänsli, R. (1994) The determination of the oxidation state of iron bythe electron microprobe. European Journal of Mineralogy, 6, 407-418.CrossRefGoogle Scholar
Höfer, H.E., Weinbruch, S., McCammon, C.A. and Brey, G.P. (2000) Comparison of two electron probe microanalysis techniques to determine ferric iron in synthetic wüstite samples. European Journal of Mineralogy, 12, 63-71.CrossRefGoogle Scholar
Holloway, J.R. (2004) Redox reactions in seafloor basalt: possible insights into silicic hydrothermal systems. Chemical Geology, 210, 225-230.CrossRefGoogle Scholar
Jackson, W.E., Farges, F., Yeager, M., Mabrouk, P.A., Rossano, S., Waychunas, G.A., Solomon, E.I. and Gordon, E.B. Jr. (2005) Multi-spectroscopic studyof Fe (II) in silicate glasses: Implications for the coordination environment of Fe(II) in silicate melts. Geochimica et Cosmochimica Acta, 69, 4315-4332.CrossRefGoogle Scholar
Luth, R.W. and Canil, D. (1993) Ferric iron in mantlederived pyroxenes and a new oxybarometer for the mantle. Contributions to Mineralogy and Petrology, 113, 236-248.CrossRefGoogle Scholar
Malchukova, A., Boizot, B., Petite, G. and Ghaleb, D. (2009) Irradiation effects in oxide glasses doped with transition and rare-earth elements. The European Physical Journal Applied Physics, 45, 10701, 1-10.Google Scholar
McCammon, C.A. and Kopylova, M.G. (2004) A redox profile of the Slave mantle and oxygen fugacity control in the cratonic mantle. Contributions to Mineralogy and Petrology, 148, 55-68.CrossRefGoogle Scholar
McCammon, C.A., Chaskar, V. and Richards, G.G. (1991) A technique for spatiallyresolved Mössbauer spectroscopya pplied to quenched metallurgical slags. Measurement Science and Technology, 2, 657-662.CrossRefGoogle Scholar
McCammon, C.A., Griffin, W.L., Shee, S.H. and O’Neill, H.S.C. (2001) Oxidation during metasomatism in ultramafic xenoliths from the Wesselton kimberlite, South Africa: implications for the survival of diamond. Contributions to Mineralogy and Petrology, 141, 287-296.CrossRefGoogle Scholar
McGuire, A., Dyar, M. and Nelson, J. (1991) Metasomatic oxidation of upper mantle peridotite. Contributions to Mineralogy and Petrology, 109, 252-254.CrossRefGoogle Scholar
Métrich, N., Susini, J., Foy, E., Farges, F., Massare, D., Sylla, L., Lequien, S. and Bonnin-Mosbah, M. (2006) Redox state of iron in peralkaline rhyolitic glass/melt: X-raya bsorption micro-spectroscopy experiments at high temperature. Chemical Geology, 231, 350-363.CrossRefGoogle Scholar
Minitti, M.E., Mustard, J.F., and Rutherford, J.R. (2002) Effects of glass content and oxidation on the spectra of SNC-like basalts: Application to Mars remote sensing. Journal of Geophysical Research, 107, E5, 5030, 6-1. 6–11.Google Scholar
Morgan VI, G.B. and London, D. (1996) Optimizing the electron microprobe analysis of hydrous alkali aluminosilicate glasses. American Mineralogist, 81, 1176-1185.CrossRefGoogle Scholar
Mysen, B.O. and Toplis, M.J. (2007) Structural behavior of Al3+ in peralkaline, metaluminous, and peraluminous silicate melts and glasses at ambient pressure. American Mineralogist, 92, 933-946.CrossRefGoogle Scholar
Olivier, F.Y., Boizot, B., Ghaleb, D. and Petite, G. (2005) Raman and EPR studies of b-irradiated oxide glasses: The effect of iron concentration. Journal of Non-Crystalline Solids, 351, 1061-1066.CrossRefGoogle Scholar
Parkinson, I.J. and Arculus, R.J. (1999) The redox state of subduction zones: insights from arc-peridotites. Chemical Geology, 160, 409-423.CrossRefGoogle Scholar
Petit, P.E., Farges, F., Wilke, M. and Solé, V.A. (2001) Determination of the iron oxidation state in Earth materials using XANES pre-edge information. Journal of Synchrotron Radiation, 8, 952-954.CrossRefGoogle Scholar
Putirka, K.D. (2008) Thermometers and barometers for volcanic systems. Pp. 61–120 in: Minerals, Inclusions and Volcanic Processes (Putirka, K.D. and Tepley, F.J., III, editors). Reviews in Mineralogy and Geochemistry, 69, Mineralogical Societyof America, Chantilly, Virginia, and the Geochemical Society, St. Louis, Missouri, USA.CrossRefGoogle Scholar
Roeder, P.L. and Emslie, R.F. (1970) Olivine-liquid equilibrium. Contributions to Mineralogy and Petrology, 29, 275-289.CrossRefGoogle Scholar
Rossano, S., Behrens, H. and Wilke, M. (2008) Advanced analyses of 57Fe Mössbauer data of alumino-silicate glasses. Physics and Chemistry of Minerals, 35, 77-93.CrossRefGoogle Scholar
Rossano, S., Jean-Soro, L., Boizot, B., Farges, F., van Hullebusch, E., Labanowski, J., Gouzin, L., Combes, R., Linares, J., Swarbrick, C. and Harfouche, M. (2009) Oxidation state variation under b-irradiation in an iron-bearing soda lime glass system. Journal of Physics: Conference Series, 190, 012194.1–012194.4.CrossRefGoogle Scholar
Rowe, M.C., Kent, A.J.R. and Nielsen, R.L. (2009) Subduction influence on oxygen fugacity and trace and volatile elements in basalts across the Cascade Volcanic Arc. Journal of Petrology, 50, 61-91.CrossRefGoogle Scholar
Shaw, C.S.J. and Dingwell, D.B. (2008) Experimental peridotite-melt reaction at one atmosphere: a textural and chemical study. Contributions to Mineralogy and Petrology, 155, 199-214.CrossRefGoogle Scholar
Van Aken, P.A., Liebscher, B. and Styrsa, V.J. (1998) Quantitative determination of iron oxidation states in minerals using Fe L2,3-edge electron energy-loss near-edge structure spectroscopy. Physics and Chemistry of Minerals, 25, 323-327.CrossRefGoogle Scholar
Van Aken, P.A., Styrsa, V.J., Liebscher, B., Woodland, A.B. and Redhammer, G.J. (1999) Microanalysis of Fe3+/SFe in oxide and silicate minerals byinvestigation of electron energy-loss near-edge structures (ELNES) at the M2,3 edge. Physics and Chemistry of Minerals, 26, 584-590.CrossRefGoogle Scholar
Wagner, C. and Deloule, E. (2007) Behaviour of Li and its isotopes during metasomatism of French Massif central lherzolites. Geochimica et Cosmochimica Acta, 71, 4279-4296.CrossRefGoogle Scholar
Weigel, C., Cormier, L., Calas, G., Galoisy, L. and Bowron, D.T. (2008) Intermediate-range order in the silicate network glasses NaFexAl1–xSi2O6 (x = 0, 0.5, 0.8, 1): a neutron diffraction and empirical potential structure refinement modeling investigation. Physical Review B, 78, 064202–1.–064202–11.CrossRefGoogle Scholar
Wilke, M., Farges, F., Petit, P.M., Brown, G.E. Jr. and Martin, F. (2001) Oxidation state and coordination of Fe in minerals: An Fe K-XANES spectroscopic study. American Mineralogist, 86, 714-730.CrossRefGoogle Scholar
Wood, B.J. and Virgo, D. (1989) Upper mantle oxidation state: Ferric iron contents of lherzolite spinels by 57Fe Mössbauer spectroscopyand resultant oxygen fugacities. Geochimica and Cosmochimica Acta, 53, 1277-1291.CrossRefGoogle Scholar
Wood, B.J., Bryndzia, L.T. and Johnson, K.E. (1990) Mantle oxidation state and its relationship to tectonic environment and fluid speciation. Science, 248, 337-345.CrossRefGoogle ScholarPubMed
Woodland, A.B. and Koch, M. (2003) Variation in oxygen fugacity with depth in the upper mantle beneath the Kaapvaal craton, Southern Africa. Earth and Planetary Science Letters, 214, 295-310.CrossRefGoogle Scholar
Woodland, A.B., Kornprobst, J., McPherson, E., Bodinier, J.-L. and Menzies, M.A. (1996) Metasomatic interactions in the lithospheric mantle: petrologic evidence from the Lherz massif, French Pyrenees. Chemical Geology, 134, 83-112.CrossRefGoogle Scholar