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Toward the wider application of 29Si NMR spectroscopy to paramagnetic transition metal silicate minerals and glasses: Fe(II), Co(II), and Ni(II) silicates

  • Jonathan F. Stebbins EMAIL logo , Ryan J. McCarty and Aaron C. Palke
Published/Copyright: April 30, 2018
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American Mineralogist
From the journal American Mineralogist Volume 103 Issue 5

Abstract

In studies of the structures of silicate minerals and glasses, 29Si NMR spectroscopy has been applied almost exclusively to materials containing relatively low concentrations of ions with unpaired electrons spins, such as most transition metals and rare earths, because of sometimes severe broadening and shifting of resonances in such strongly paramagnetic systems. However, by adapting experimental methods to allow detection of very broad signals, and by examining a much expanded range of frequencies, we show here that accurate spectra can indeed be measured for a series of pure-phase transition metal silicates, including olivines (Fe2SiO4, Co2SiO4, Ni2SiO4), Co-akermanite (CoCa2Si2O7), and clinopyroxenes (CoCaSi2O6, NiCaSi2O6). For the latter two, we also present data for glasses of the same nominal compositions. For all of these phases, NMR peak broadening is large, in many cases to the point where magic angle spinning (MAS) does not enhance resolution; in all cases the observed paramagnetic shifts fall far outside the known range for diamagnetic silicates. There are clearly large effects of local structure on shift, suggesting great potential sensitivity to variations in chemical, electronic, and magnetic structure in both crystalline and amorphous phases. In particular, the spectra for the glasses are very different from those of crystals in both width and position. In most cases, measured spin-spin relaxation times are long enough to avoid major loss of signal during the NMR acquisition, but this may not always be the case in more magnetically dilute solid solutions, where small, broad paramagnetic resonances due to first cation neighbor interactions may in some systems be difficult to detect. To explore this issue, we present new data on a Ni-doped forsterite (Mg1.9Ni0.1SiO4) and on natural San Carlos olivine (Mg1.8Fe0.2SiO4), which improve upon the accuracy of our previous studies of these materials. It is clear that applications of NMR to paramagnetic silicates holds great promise not only for empirical studies of structure of a much wider range of compositions of minerals and glasses, but for future testing and application of advanced theoretical methods to more completely interpret such results.

Keywords: Nuclear magnetic resonance; contact shift; fayalite; olivine; clinopyroxene; akermanite; transition metal; glass

Acknowledgments

This research was supported by the National Science Foundation, EAR-1521055. We thank Dale Burns (Stanford University) for the electron microprobe analyses. The paper was improved by helpful comments from two anonymous reviewers.

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Received: 2017-11-8
Accepted: 2018-2-1
Published Online: 2018-4-30
Published in Print: 2018-5-25

© 2018 Walter de Gruyter GmbH, Berlin/Boston

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  32. New Mineral Names
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https://doi.org/10.2138/am-2018-6370
Keywords for this article
Nuclear magnetic resonance; contact shift; fayalite; olivine; clinopyroxene; akermanite; transition metal; glass

Articles in the same Issue

  1. Review
  2. Biosilica as a source for inspiration in biological materials science
  4. Ab initio study of water speciation in forsterite: Importance of the entropic effect
  6. Surface-modified phillipsite-rich tuff from the Campania region (southern Italy) as a promising drug carrier: An ibuprofen sodium salt trial
  8. Structure of low-order hemimorphite produced in a Zn-rich environment by cyanobacterium Leptolingbya frigida
  10. Formation of dolomite catalyzed by sulfate-driven anaerobic oxidation of methane: Mineralogical and geochemical evidence from the northern South China Sea
  12. Anisotropic growth of olivine during crystallization in basalts from Hawaii: Implications for olivine fabric development
  14. Melting experiments on Fe–Si–S alloys to core pressures: Silicon in the core?
  16. High-pressure phase behavior and equations of state of ThO2 polymorphs
  18. Mafic inputs into the rhyolitic magmatic system of the 2.08 Ma Huckleberry Ridge eruption, Yellowstone
  20. Toward the wider application of 29Si NMR spectroscopy to paramagnetic transition metal silicate minerals and glasses: Fe(II), Co(II), and Ni(II) silicates
  22. Equations of state and phase boundary for stishovite and CaCl2-type SiO2
  24. Insight on gem opal formation in volcanic ash deposits from a supereruption: A case study through oxygen and hydrogen isotopic composition of opals from Lake Tecopa, California, U.S.A
  26. Revisiting the crystal structure of dickite: X-ray diffraction, solid-state NMR, and DFT calculations study
  28. Temperature and pressure effects on the partitioning of V and Sc between clinopyroxene and silicate melt: Implications for mantle oxygen fugacity
  29. Letter
  30. Why natural monazite never becomes amorphous: Experimental evidence for alpha self-healing
  32. New Mineral Names
  33. Book Review
  34. Book Review: Glaciovolcanism on Earth and Mars: Products, Processes and Paleoenvironmental Significance
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