Startseite Constraints on aluminum and scandium substitution mechanisms in forsterite, periclase, and larnite: High-resolution NMR
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Constraints on aluminum and scandium substitution mechanisms in forsterite, periclase, and larnite: High-resolution NMR

  • Ryan J. McCarty EMAIL logo und Jonathan F. Stebbins
Veröffentlicht/Copyright: 1. Juni 2017
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American Mineralogist
Aus der Zeitschrift American Mineralogist Band 102 Heft 6

Abstract

The incorporation of incompatible Al in forsterite is particularly interesting due to its relevance in Al olivine-spinel geobarometry techniques as well as the proposed influence of Al on upper mantle diffusion and water storage capacity.However, determining the site preference and substitution mechanisms of aluminum in forsterite presents considerable challenge, because the incompatibility of Al in the olivine structure results in correspondingly low Al concentrations. In this work we use solid state nuclear magnetic resonance (NMR) to directly observe Al coordination in synthetic samples from which we can constrain site preferences. We investigate Al in MgO and clinoenstatite to confirm that the forsterite spectra do not contain contributions from these impurity phases. To better interpret our results we used the independent component analysis (ICA) algorithm, SIMPLISMA, which accurately deconvoluted complex NMR line shapes, separating spectral components from known impurities and enabling the identification of unknown spectral components that in some cases we can assign to substituting Al. We additionally investigate Al in larnite, which has a tetrahedral environment similar to that of forsterite and that presents an another ICA test case, and investigate Sc in forsterite and periclase to add context to our Al observations. Our 27Al and 45Sc MAS NMR spectra place new constraints on the site preferences of Al in synthetic forsterite, clinoenstatite, periclase, and larnite as well as Sc in forsterite and periclase.

In forsterite, we identified Al in the tetrahedral site and at least three distinct octahedral environments. The overall ratio of contents of AlO4 to AlO6 is about 1:3; the excess of the latter suggesting that at least two substitution mechanisms are necessary for Al3+ incorporation. In some cases the estimated species abundance for observed features are as low as 70 μg/g Al3+, but were readily detected by NMR. Also in forsterite, we identified Sc in a single MgO6 environment. In larnite (also known as belite or C2S in cement chemist notation), a single, ordered tetrahedral Al species is detected. In enstatite samples, primarily composed of clinoenstatite, 27Al NMR spectra look very similar to previous observations of orthoenstatite, likely indicating a similar coupled AlO6 and AlO4 substitution. In periclase, Al is observed in an undistorted MgO6 site with cubic or nearly cubic point symmetry, in addition to a lower symmetry, sixfold-coordinated site. This work provides new insight into incompatible element substitutions mechanism in minerals, in forsterite's case indicating complex behavior involving multiple species despite compositional simplicity.

Keywords: Forstente; periclase; enstatite; larnite; belite; independent component analysis; nuclear magnetic resonance; trace elements; SIMPLISMA

Acknowledgments

This research was supported by NSF grants EAR-1521055 and EAR-1019596 awarded to J.F.S. We thank Bob Jones (Stanford) for assistance with EPMA analyses, Lars Hansen (Oxford) for useful discussions, Namjun Kim for his thoughtful response to NMR spectroscopy questions, and Harris Mason (Lawrence Livermore National Laboratory) for introducing us to component analysis methods. We also thank two anonymous reviewers for thoughtful responses and constructive comments.

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Received: 2016-10-5
Accepted: 2017-1-20
Published Online: 2017-6-1
Published in Print: 2017-6-27

© 2017 by Walter de Gruyter Berlin/Boston

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https://doi.org/10.2138/am-2017-5976
Schlagwörter für diesen Artikel
Forstente; periclase; enstatite; larnite; belite; independent component analysis; nuclear magnetic resonance; trace elements; SIMPLISMA

Artikel in diesem Heft

  1. Actinides in geology, energy, and the environment
  2. Thermodynamic investigation of uranyl vanadate minerals: Implications for structural stability
  3. Actinides in geology, energy, and the environment
  4. Uranium-bearing opals: Products of U-mobilization, diffusion, and transformation processes
  5. Special Collection: Olivine
  6. Quantifying and correcting the effects of anisotropy in XANES measurements of chromium valence in olivine: Implications for a new olivine oxybarometer
  7. Special collection: Dynamics of magmatic processes
  8. High-resolution geochemistry of volcanic ash highlights complex magma dynamics during the Eyjafjallajökull 2010 eruption
  9. Special collection: Water in nominally hydrous and anhydrous minerals
  10. Evidence for post-depositional diffusional loss of hydrogen in quartz phenocryst fragments within ignimbrites
  11. Special collection: Martian rocks and minerals: Perspectives from rovers, orbiters, and meteorites
  12. Visible to near-infrared MSL/Mastcam multispectral imaging: Initial results from select high-interest science targets within Gale Crater, Mars
  14. Multi-stage formation of REE minerals in the Palabora Carbonatite Complex, South Africa
  16. Spin orientation in solid solution hematite-ilmenite
  18. Constraints on aluminum and scandium substitution mechanisms in forsterite, periclase, and larnite: High-resolution NMR
  20. Shock-induced P-T conditions and formation mechanism of akimotoite-pyroxene glass assemblages in the Grove Mountains (GRV) 052082 (L6) meteorite
  22. The spin state of Fe3+ in lower mantle bridgmanite
  24. Reaction pathways and textural aspects of the replacement of anhydrite by calcite at 25 °C
  26. Majorite-olivine–high-Ca pyroxene assemblage in the shock-melt veins of Pervomaisky L6 chondrite
  28. Cu and Fe diffusion in rhyolitic melts during chalcocite “dissolution”: Implications for porphyry ore deposits and tektites
  30. Field-based accounting of CO2 sequestration in ultramafic mine wastes using portable X-ray diffraction
  32. NanoSIMS study of seismically deformed zircon: Evidence of Y, Yb, Ce, and P redistribution and resetting of radiogenic Pb
  34. Study on structure variations of incommensurately modulated labradorite feldspars with different cooling histories
  36. Carbocernaite from Bear Lodge, Wyoming: Crystal chemistry, paragenesis, and rare-earth fractionation on a microscale
  38. Magma mush chemistry at subduction zones, revealed by new melt major element inversion from calcic amphiboles
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