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Investigation of cation ordering in triclinic sodium birnessite via 23Na MAS NMR spectroscopy

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Published/Copyright: April 2, 2015
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American Mineralogist
From the journal American Mineralogist Volume 97 Issue 5-6

Abstract

Birnessite is a widespread, naturally occurring layered manganese oxide that exerts significant influence over the geochemical cycling of environmentally relevant cations due to its high-interlayer adsorption capacity. Triclinic sodium birnessite was used as a synthetic analog to gain a better understanding of the nature of cation adsorption in this important phyllomanganate. Drawing from previous work correlating observed 23Na NMR shifts in manganese oxides with local environment and Mn oxidation state, the 23Na NMR spectra of metastable buserite and two birnessite samples, NaBi-H-I and NaBi-II, were analyzed to determine the nature of the bound interlayer sodium ions in these materials. The small 23Na chemical shift of buserite shows that its interlayer sodium is fully hydrated. X-ray diffraction indicates that NaBi-H-I is a disordered birnessite while NaBi-II is highly crystalline. High-field (14.1 T) fast MAS NMR spectra of NaBi-H-I and NaBi-II supports these observations, resolving multiple sodium environments for NaBi-H-I and only two sodium environments for NaBi-II. The observed hyperfine shifts were less than expected for sodium environments with manganate layers composed of 2/3 Mn4+ and 1/3 Mn3+ ions, and the 23Na line shapes indicated that the Na+ ions are in distorted environments. Both these factors suggest that the sodium ions are offset in the interlayers toward a single oxide layer and located near Mn3+-rich environments within the layer.

Keywords: Manganese oxides; birnessite; NMR; paramagnetic
Received: 2011-7-1
Accepted: 2012-1-16
Published Online: 2015-4-2
Published in Print: 2012-5-1

© 2015 by Walter de Gruyter Berlin/Boston

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https://doi.org/10.2138/am.2012.3933
Keywords for this article
Manganese oxides; birnessite; NMR; paramagnetic

Articles in the same Issue

  1. Dana medal lecture: Tilts and tetrahedra: The origin of the anisotropy of feldspars
  2. Amorphous Materials: Determination of water content in silicate glasses using Raman spectrometry: Implications for the study of explosive volcanism
  3. Density functional calculations of the enthalpies of formation of rare-earth orthophosphates
  4. U-Pb ID-TIMS dating applied to U-rich inclusions in garnet
  5. Wassonite: A new titanium monosulfide mineral in the Yamato 691 enstatite chondrite
  6. Determination of Mn valence states in mixed-valent manganates by XANES spectroscopy
  7. The morphology of the reaction front of the dissolutionprecipitation reaction rutile + wollastonite = titanite in time series experiments at 600 °C/400 MPa
  8. Precipitation of rutile and ilmenite needles in garnet: Implications for extreme metamorphic conditions in the Acadian Orogen, U.S.A.
  9. The genesis of mantle-derived sapphirine
  10. Experimental investigation of smectite interaction with metal iron at 80 °C: Structural characterization of newly formed Fe-rich phyllosilicates
  11. High-pressure study of a natural cancrinite
  12. Investigation of cation ordering in triclinic sodium birnessite via 23Na MAS NMR spectroscopy
  13. The dual behavior of the β-As4S4 altered by light
  14. Pressure-induced changes in local electronic structures of SiO2 and MgSiO3 polymorphs: Insights from ab initio calculations of O K-edge energy-loss near-edge structure spectroscopy
  15. Structural stability, cation ordering, and local relaxation along the AlNbO4-Al0.5Cr0.5NbO4 join
  16. Europium oxidation state and local structure in silicate glasses
  17. Kinetics of partial dehydroxylation in dioctahedral 2:1 layer clay minerals
  18. Determination of Fe3+/Fe using the electron microprobe: A calibration for amphiboles
  19. Characterization of smectite to NH4-illite conversion series in the fossil hydrothermal system of Harghita Bãi, East Carpathians, Romania
  20. Allanite-(Nd), CaNdAl2Fe2+(SiO4)(Si2O7)O(OH), a new mineral from Åskagen, Sweden
  21. Tsilaisite, NaMn3Al6(Si6O18)(BO3)3(OH)3OH, a new mineral species of the tourmaline supergroup from Grotta d’Oggi, San Pietro in Campo, island of Elba, Italy
  22. Letter. A nanoscopic approach to the kinetics of anhydrite (100) surface growth in the range of temperatures between 60 and 120 °C
  23. Letter. High-pressure phase transitions in Ca-Mn carbonates (Ca,Mn)CO3 studied by Raman spectroscopy
  24. Letter. Actinides in Geology, Energy, and the Environment: Thermally induced transformation of vorlanite to “protovorlanite”: Restoration of cation ordering in self-irradiated CaUO4
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