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Manganese incorporation in synthetic hercynite

Published online by Cambridge University Press:  02 January 2018

G. D. Bromiley*
Affiliation:
School of GeoSciences, Grant Institute, University of Edinburgh, King’s Buildings, Edinburgh EH9 3JW, UK Centre for Science at Extreme Conditions, Erskine Williamson Building, University of Edinburgh, King’s Buildings, Edinburgh EH9 3JZ, UK
G. D. Gatta
Affiliation:
Dipartimento di Scienze della Terra, Università degli Studi Milano, Via Botticelli 23, I-20133 Milano, Italy CNR - Istituto di Cristallografia, Sede di Bari, Via G. Amendola 122/o, I-70126 Bari, Italy
T. Stokes
Affiliation:
School of GeoSciences, Grant Institute, University of Edinburgh, King’s Buildings, Edinburgh EH9 3JW, UK

Abstract

Manganese incorporation in synthetic hercynite, and partitioning between hercynite and silicate melt synthesized at 1.0 GPa, 1250°C, and at an fO2 buffered by Fe–FeO, has been studied by X-ray absorption spectroscopy and single-crystal X-ray structure refinement. Spectra indicate the presence of both Mn2+ and Mn3+ (and possibly also Mn4+) in synthetic hercynite and partitioning of Mn2+ into the melt phase, and Mn3+ into hercynite, respectively, under run conditions. X-ray refinement is consistent with partial disorder of Fe and Al across tetrahedral and octahedral sites. A higher than expected degree of Fe-Al disorder in the Mn-bearing hercynite can be explained by preferential incorporation of Mn2+ onto the tetrahedral site, and indicates that Fe-Al disorder in pure, stoichiometric hercynite cannot necessarily be used to determine closure temperatures in natural spinel. However, partitioning of Mn2+ and Mn3+ between melt and hercynite suggests that Mn incorporation in hercynite could be used as a measure of fO2 conditions in magmas during spinel crystallization.

Type
Research Article
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2015

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References

Agilent Technologies (2012) Xcalibur CCD system, Crysalis software system. Oxford Diffraction Ltd, Yarnton, Oxfordshire, UK.Google Scholar
Andreozzi, G.B., Lucchesi, S., Skogby, H. and Della Giusta, A. (2001) Compositional dependence of cation distribution in some synthetic (Mg,Zn) (Al,Fe3+)2O4 spinels. European Journal of Mineralogy, 13, 391402.CrossRefGoogle Scholar
Andreozzi, G.B. and Lucchesi, S. (2002) Intersite distribution of Fe2+ and Mg in the spinel (sensu stricto)-hercynite series by single-crystal X-ray diffraction. American Mineralogist, 87, 11131120.CrossRefGoogle Scholar
Anthony, J.W., Bideaux, R.A., Bladh, K.W. and Nichols, M.C. (1997) Handbook of Mineralogy Vol . III : Halides , Hydroxides , Oxides. Mineralogical Society of America, Chantilly, Virginia, USA. Beard, J.S. and Tracy, R.J. (2002) Spinels and other oxides in Mn-rich rocks from the Hutter mine, Pittsylvania county, Virginia, USA: Implications for miscibility and solvus relations among jacobsite, galaxite, and magnetite. American Mineralogist, 87, 690698.Google Scholar
Bosi, F., Hålenius, U., Andreozzi, G.B., Skogby, H. and Lucchesi, S. (2007) Structural refinement and crystal chemistry of Mn-doped spinel: A case for tetrahedrally coordinated Mn3+ in an oxygen-based structure. American Mineralogist, 92, 2733.CrossRefGoogle Scholar
Bromiley, G., Keppler, H., McCammon, C., Bromiley, F. and Jacobsen, S. (2004) Hydrogen solubility and speciation in natural, gem-quality Cr-diopside. American Mineralogist, 89, 941949.CrossRefGoogle Scholar
Bromiley, G.D., Nestola, F., Redfern, S.A.T. and Zhang, M. (2010) Water incorporation in synthetic and natural MgAl 2O4 spinel. Geochimica et Cosmochimica Acta, 74, 705718.CrossRefGoogle Scholar
Carbonin, S., Russo, U. and Della Giusta, A. (1996) Cation distribution in some natural spinels from Xray diffraction and Mössbauer spectroscopy. Mineralogical Magazine, 60, 355368.CrossRefGoogle Scholar
Guillemet-Fritsch, S., Navrotsky, A., Tailhades, P., Coradin, H. and Wang, M. (2005) Thermo-chemistry of iron manganese oxide spinels. Journal of Solid State Chemistry, 178, 106113.CrossRefGoogle Scholar
Hålenius, U., Skogby, H. and Andreozzi, G.B. (2002) Influence of cation distribution on the optical absorption spectra of Fe3+-bearing spinel s.s.-hercynite crystals: Evidence for electron transitions in FeVI(2+)-FeVI(3+) clusters. Physics and Chemistry of Minerals, 29, 319330.Google Scholar
Harrison, R.J., Redfern, S.A.T. and O’Neill, H.S.C. (1998) The temperature dependence of the cation distribution in synthetic hercynite (FeAl2O4) from in-situ neutron structure refinements. American Mineralogist, 83, 10921099.CrossRefGoogle Scholar
Hill, R.J. (1984) X-ray-powder diffraction profile refinement of synthetic hercynite. American Mineralogist, 69, 937942.Google Scholar
Johnson, H.P. and Jensen, S.D. (1974) High-temperature oxidation of magnetite to maghemite. Transactions-American Geophysical Union, 55, 233233.Google Scholar
Kohn, S.C., Charnock, J.M., Henderson, C.M.B. and Greaves, G.N. (1990) The structural environments of trace-elements in dry and hydrous silicate-glasses – a manganese and strontium K-edge X-ray absorption spectroscopic study. Contributions to Mineralogy and Petrology, 105, 359368.CrossRefGoogle Scholar
Larson, A.C. (1967) Inclusion of secondary extinction in least-squares calculations. Acta Crystallographica, 23, 664665.CrossRefGoogle Scholar
Larsson, L., Oneill, H.S. and Annersten, H. (1994) Crystal-chemistry of synthetic hercynite (FeAl2O4) from XRD structural refinements and Mössbauer spectroscopy. European Journal of Mineralogy, 6, 3951.CrossRefGoogle Scholar
Lavina, B., Princivalle, F. and Della Giusta, A. (2005) Controlled time-temperature oxidation reaction in a synthetic Mg-hercynite. Physics and Chemistry of Minerals, 32, 8388.CrossRefGoogle Scholar
Lavina, B., Cesare, B., Alvarez-Valero, A.M., Uchida, H., Downs, R.T., Koneva, A. and Dera, P. (2009) Closure temperatures of intracrystalline ordering in anatectic and metamorphic hercynite, Fe2+Al2O4. American Mineralogist, 94, 657665.CrossRefGoogle Scholar
Lenaz, D., Skogby, H., Princivalle, F. and Hålenius, U. (2004) Structural changes and valence states in the MgCr2O4-FeCr2O4 solid solution series. Physics and Chemistry of Minerals, 31, 633642.CrossRefGoogle Scholar
Lenaz, D., Skogby, H., Princivalle, F. and Hålenius, U. (2006) The MgCr2O4-MgFe2O4 solid solution series: Effects of octahedrally coordinated Fe3+ on T-O bond lengths. Physics and Chemistry of Minerals, 33, 465474.CrossRefGoogle Scholar
Liang, X.L., Zhong, Y.H., Tan, W., Zhu, J.X., Yuan, P., He, H.P. and Jiang, Z. (2013) The influence of substituting metals (Ti, V, Cr, Mn, Co and Ni) on the thermal stability of magnetite. Journal of Thermal Analysis and Calorimetry, 111, 13171324.CrossRefGoogle Scholar
Lotgering, F.K. (1964) Semiconduction + cation valencies in manganese ferrites. Journal of Physics and Chemistry of Solids, 25, 95103.CrossRefGoogle Scholar
Lucchesi, S., Russo, U. and DellaGiusta, A. (1997) Crystal chemistry and cation distribution in some Mn-rich natural and synthetic spinels. European Journal of Mineralogy, 9, 3142.CrossRefGoogle Scholar
Manceau, A., Marcus, M.A. and Grangeon, S. (2012) Determination of Mn valence states in mixed-valent manganates by xanes spectroscopy. American Mineralogist, 97, 816827.CrossRefGoogle Scholar
Miles, A.J., Graham, C.M., Hawkesworth, C.J., Gillespie, M.R., Hinton, R.W. and Edinburgh Ion Microprobe Facilty (2013) Evidence for distinct stages of magma history recorded by the compositions of accessory apatite and zircon. Contributions to Mineralogy and Petrology, 166, 119.CrossRefGoogle Scholar
Myers, J. and Eugster, H.P. (1983) The system Fe-Si-O: oxygen buffer calibrations to 1,500K. Contributions to Mineralogy and Petrology, 82, 7590.CrossRefGoogle Scholar
O’Neill, H.S.C. and Navrotsky, A. (1983) Simple spinels-crystallographic parameters, cation radii, lattice energies, and cation distribution. American Mineralogist, 68, 181194.Google Scholar
Ravel, B. and Newville, M. (2005) ATHENA, ARTEMIS, HEPHAESTUS: Data analysis for X-ray absorption spectroscopy using IFEFFIT. Journal of Synchrotron Radiation, 12, 537541.CrossRefGoogle ScholarPubMed
Raye, U., Anthony, E.Y., Stern, R.J., Kimura, J.I., Ren, M.H., Qing, C. and Tani, K. (2011) Composition of the mantle lithosphere beneath south-central Laurentia: Evidence from peridotite xenoliths, Knippa, Texas. Geosphere, 7, 710723.CrossRefGoogle Scholar
Redfern, S., Harrison, R., O’Neill, H.S.C. and Wood, D. (1999) Thermodynamics and kinetics of cation ordering in MgAl2O4 spinel up to 1600ºC from in situ neutron diffraction. American Mineralogist, 84, 299310.CrossRefGoogle Scholar
Righter, K., Sutton, S.R., Newville, M., Lei, L., Schwandt, C.S., Uchida, H., Lavina, B. and Downs, R.T. (2006) An experimental study of the oxidation state of vanadium in spinel and basaltic melt with implications for the origin of planetary basalt. American Mineralogist, 91, 16431656.CrossRefGoogle Scholar
Schollenbruch, K., Woodland, A.B. and Frost, D.J. (2010) The stability of hercynite at high pressures and temperatures. Physics and Chemistry of Minerals, 37, 137143.CrossRefGoogle Scholar
Sheldrick, G. (1997) SHELX-97-a program for crystal structure refinement. University of Gottingen, Germany. Turnock, A.C. and Eugster, H.P. (1962) Fe-Al oxides-phase relationships below 1,000ºC. Journal of Petrology, 3, 533565.Google Scholar
Waerenborgh, J.C., Figueiredo, M.O., Cabral, J.M.P. and Pereira, L.C.J. (1994) Powder XRD structure refinements and Fe-57 Mössbauer-effect study of synthetic Zn1-xFexAl2O4 (0<x41) spinels annealed at different temperatures. Physics and Chemistry of Minerals, 21, 460468.CrossRefGoogle Scholar
Wilson, A.J.C. and Prince, E. (Editors) (1999) International Tables for X-ray Crystallography, Volume C: Mathematical, Physical and Chemical Tables (2nd Edition). Kluwer Academic, Dordrecht, The Netherlands. Woodland, A.B. and Wood, B.J. (1990) The breakdown of hercynite at low fO2 . American Mineralogist, 75, 13421348.Google Scholar