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Determination of manganese valence states in (Mn3+, Mn4+) minerals by electron energy-loss spectroscopy

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Published/Copyright: April 2, 2015
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American Mineralogist
From the journal American Mineralogist Volume 95 Issue 11-12

Abstract

Various manganese valence quantification methods using manganese L2,3 and oxygen K electron energy loss near-edge spectra (ELNES) were applied to determine the relative portions of individual valence state in a mixed (Mn3+, Mn4+) valence system. Multiple linear least-squares (MLLS) fitting of Mn L2,3 ELNES using reference spectra and Gaussian peak fitting of Mn L3 edge are newly developed and the feasibility of these methods was tested on a set of cryptomelane minerals with different valence states. The selection of appropriate standards is crucial to the success of the MLLS method. The O K-edge structures for manganese oxides can provide valuable guidance in the selection of appropriate reference spectra for quantitative determination of Mn valence state. Gaussian peak fitting, however, failed to determine the Mn valence for (Mn3+, Mn4+) minerals due to the small separation between the primary L3 peaks from Mn4+ and Mn3+ valence. As to the methods based on calibration curves, the energy difference between Mn L3 and oxygen K, i.e., ΔE (L3-O K) vs. valence, is the most valence-sensitive method in the range of Mn3+ and Mn4+ and yields good agreement with the actual values.

Keywords: EELS; valence determination; manganese oxides; cryptomelane
Received: 2009-12-3
Accepted: 2010-5-25
Published Online: 2015-4-2
Published in Print: 2010-11-1

© 2015 by Walter de Gruyter Berlin/Boston

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https://doi.org/10.2138/am.2010.3468
Keywords for this article
EELS; valence determination; manganese oxides; cryptomelane

Articles in the same Issue

  1. Characterization of cation environments in polycrystalline forsterite by 25Mg MAS, MQMAS, and QCPMG NMR
  2. Structure of nanocrystalline phyllomanganates produced by freshwater fungi
  3. First-principles study on variation of lattice parameters of mullite Al4+2xSi2–2xO10–x (x = 0.125, 0.250, 0.375)
  4. Natrolite may not be a “soda-stone” anymore: Structural study of fully K-, Rb-, and Cs-exchanged natrolite
  5. Metal retention, mineralogy, and design considerations of a mature permeable reactive barrier (PRB) for acidic mine water drainage in Northumberland, U.K.
  6. A relationship between d104 value and composition in the calcite-disordered dolomite solid-solution series
  7. XRD, micro-XANES, EMPA, and SIMS investigation on phlogopite single crystals from Mt. Vulture (Italy)
  8. Volume behavior of the 10 Å phase at high pressures and temperatures, with implications for H2O content
  9. Interfacial tension between immiscible liquids in the system K2O-FeO-Fe2O3-Al2O3-SiO2 and implications for the kinetics of silicate melt unmixing
  10. H2O and the dehydroxylation of phyllosilicates: An infrared spectroscopic study
  11. Effects of intermediate range structure on the 29Si NMR chemical shifts of framework silicates: Results for analcime
  12. High-temperature Mössbauer spectroscopy: A probe for the relaxation time of Fe species in silicate melts and glasses
  13. The thermal equation of state of FeTiO3 ilmenite based on in situ X-ray diffraction at high pressures and temperatures
  14. OH species, U ions, and CO/CO2 in thermally annealed metamict zircon (ZrSiO4)
  15. Crystallographic and chemical constraints on the nature of the proustite–pyrargyrite solid-solution series
  16. Accurate μRaman characterization of reaction products at the surface of (bio)oxidized pyrite
  17. Determination of manganese valence states in (Mn3+, Mn4+) minerals by electron energy-loss spectroscopy
  18. AFM study of the epitaxial growth of brushite (CaHPO4·2H2O) on gypsum cleavage surfaces
  19. Compressibility of protoamphibole: A high-pressure single-crystal diffraction study of protomangano-ferro-anthophyllite
  20. Crystal structure of hydrous wadsleyite with 2.8% H2O and compressibility to 60 GPa
  21. Dehydration and rehydration processes in gmelinite: An in situ X-ray single-crystal study
  22. Characteristics of emission centers in alkali feldspar: A new approach by using cathodoluminescence spectral deconvolution
  23. Mechanism of metamorphic zircon growth in a granulite-facies quartzite, Adirondack Highlands, Grenville Province, New York
  24. Speciation and mixing behavior of silica-saturated aqueous fluid at high temperature and pressure
  25. A critical comment on Thy et al. (2009b): Liquidus temperatures of the Skaergaard magma
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