Cation distribution in Mg-Zn olivine solid solution: A 29Si MAS NMR and first-principles calculation study

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Abstract

In order to clarify cation distributions in the M1 and M2 sites of (Mg,Zn)2SiO4 olivine solid solution, 29Si MAS NMR spectroscopic measurement and first-principles NMR parameter calculation were conducted. The 29Si MAS NMR spectra of (Mg0.95Zn0.05)2SiO4 and (Mg0.90Zn0.10)2SiO4 olivine samples reveled three new peaks at relative chemical shift differences of 0.2, 1.1 and 2.3 ppm from the main peak of forsterite (-61.8 ppm). These shifts can be attributed to changes in the second-nearest-neighbors of Si due to substitution of Mg by Zn. Based on first-principles calculations, these peaks can be assigned to the following three groups of local Si environments in the order of increasing shift from the main peak of forsterite: i) Si tetrahedra with one corner-shared Zn in M1 or M2 octahedron, ii) Si tetrahedra with one edge-shared Zn in M2 octahedron, and iii) Si tetrahedra with one edge-shared Zn in M1 octahedron. Since the last two peaks are well separated from the others, the relative abundances of Zn in the M1 and M2 sites can be quantified using these peaks. Preference of Zn for M1 site over M2 site was inferred from the observed peak intensities. The present study demonstrated the usefulness of 29Si MAS NMR spectroscopy for quantitatively studying cation distributions in solid solutions.

Original languageEnglish
Pages (from-to)292-296
Number of pages5
JournalJournal of Mineralogical and Petrological Sciences
Volume111
Issue number4
DOIs
Publication statusPublished - 2016

Fingerprint

MAS
solid solution
olivine
nuclear magnetic resonance
solid solutions
cation
cations
forsterite
tetrahedrons
relative abundance
substitution
spectroscopy
shift
distribution
calculation
chemical equilibrium
substitutes

Keywords

  • (Mg,Zn)SiO
  • Cation distribution
  • First-principles calculation
  • NMR
  • Olivine

ASJC Scopus subject areas

  • Geophysics
  • Geology

Cite this

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title = "Cation distribution in Mg-Zn olivine solid solution: A 29Si MAS NMR and first-principles calculation study",
abstract = "In order to clarify cation distributions in the M1 and M2 sites of (Mg,Zn)2SiO4 olivine solid solution, 29Si MAS NMR spectroscopic measurement and first-principles NMR parameter calculation were conducted. The 29Si MAS NMR spectra of (Mg0.95Zn0.05)2SiO4 and (Mg0.90Zn0.10)2SiO4 olivine samples reveled three new peaks at relative chemical shift differences of 0.2, 1.1 and 2.3 ppm from the main peak of forsterite (-61.8 ppm). These shifts can be attributed to changes in the second-nearest-neighbors of Si due to substitution of Mg by Zn. Based on first-principles calculations, these peaks can be assigned to the following three groups of local Si environments in the order of increasing shift from the main peak of forsterite: i) Si tetrahedra with one corner-shared Zn in M1 or M2 octahedron, ii) Si tetrahedra with one edge-shared Zn in M2 octahedron, and iii) Si tetrahedra with one edge-shared Zn in M1 octahedron. Since the last two peaks are well separated from the others, the relative abundances of Zn in the M1 and M2 sites can be quantified using these peaks. Preference of Zn for M1 site over M2 site was inferred from the observed peak intensities. The present study demonstrated the usefulness of 29Si MAS NMR spectroscopy for quantitatively studying cation distributions in solid solutions.",
keywords = "(Mg,Zn)SiO, Cation distribution, First-principles calculation, NMR, Olivine",
author = "Masami Kanzaki and Xianyu Xue",
year = "2016",
doi = "10.2465/jmps.151104a",
language = "English",
volume = "111",
pages = "292--296",
journal = "Journal of Mineralogical and Petrological Sciences",
issn = "1345-6296",
publisher = "Tohoku University",
number = "4",

}

TY - JOUR

T1 - Cation distribution in Mg-Zn olivine solid solution

T2 - A 29Si MAS NMR and first-principles calculation study

AU - Kanzaki, Masami

AU - Xue, Xianyu

PY - 2016

Y1 - 2016

N2 - In order to clarify cation distributions in the M1 and M2 sites of (Mg,Zn)2SiO4 olivine solid solution, 29Si MAS NMR spectroscopic measurement and first-principles NMR parameter calculation were conducted. The 29Si MAS NMR spectra of (Mg0.95Zn0.05)2SiO4 and (Mg0.90Zn0.10)2SiO4 olivine samples reveled three new peaks at relative chemical shift differences of 0.2, 1.1 and 2.3 ppm from the main peak of forsterite (-61.8 ppm). These shifts can be attributed to changes in the second-nearest-neighbors of Si due to substitution of Mg by Zn. Based on first-principles calculations, these peaks can be assigned to the following three groups of local Si environments in the order of increasing shift from the main peak of forsterite: i) Si tetrahedra with one corner-shared Zn in M1 or M2 octahedron, ii) Si tetrahedra with one edge-shared Zn in M2 octahedron, and iii) Si tetrahedra with one edge-shared Zn in M1 octahedron. Since the last two peaks are well separated from the others, the relative abundances of Zn in the M1 and M2 sites can be quantified using these peaks. Preference of Zn for M1 site over M2 site was inferred from the observed peak intensities. The present study demonstrated the usefulness of 29Si MAS NMR spectroscopy for quantitatively studying cation distributions in solid solutions.

AB - In order to clarify cation distributions in the M1 and M2 sites of (Mg,Zn)2SiO4 olivine solid solution, 29Si MAS NMR spectroscopic measurement and first-principles NMR parameter calculation were conducted. The 29Si MAS NMR spectra of (Mg0.95Zn0.05)2SiO4 and (Mg0.90Zn0.10)2SiO4 olivine samples reveled three new peaks at relative chemical shift differences of 0.2, 1.1 and 2.3 ppm from the main peak of forsterite (-61.8 ppm). These shifts can be attributed to changes in the second-nearest-neighbors of Si due to substitution of Mg by Zn. Based on first-principles calculations, these peaks can be assigned to the following three groups of local Si environments in the order of increasing shift from the main peak of forsterite: i) Si tetrahedra with one corner-shared Zn in M1 or M2 octahedron, ii) Si tetrahedra with one edge-shared Zn in M2 octahedron, and iii) Si tetrahedra with one edge-shared Zn in M1 octahedron. Since the last two peaks are well separated from the others, the relative abundances of Zn in the M1 and M2 sites can be quantified using these peaks. Preference of Zn for M1 site over M2 site was inferred from the observed peak intensities. The present study demonstrated the usefulness of 29Si MAS NMR spectroscopy for quantitatively studying cation distributions in solid solutions.

KW - (Mg,Zn)SiO

KW - Cation distribution

KW - First-principles calculation

KW - NMR

KW - Olivine

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SP - 292

EP - 296

JO - Journal of Mineralogical and Petrological Sciences

JF - Journal of Mineralogical and Petrological Sciences

SN - 1345-6296

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