High-temperature single-crystal neutron diffraction study of natural chondrodite

The H-atom environment in a Tilly Foster chondrodite was analyzed using single-crystal neutron-diffraction data collected at 500, 700 and 900 K and previously published low temperature data collected at 10, 100 and 300 K on the same crystal (Mg_4.64Fe_0.28Mn_0.014Ti_0.023(Si_1.01O₄)₂F_1.16(OH)_0.84; Friedrich et al. in Am Mineral 86:981–989, 2001). The full mean square displacement matrix Σ of the O–H pair was determined from the temperature dependence of the anisotropic displacement parameters, enabling a proper correction of the O–H bond for thermal vibration without assumptions about the correlation of O and H movements. The results show that the perpendicular O–H motions in chondrodite are intermediate between the riding and the independent motion models. The corrected O–H bond lengths do not change with temperature whereas the corrected H···F distances show an increase of ~0.02 Å with temperature, as do the Mg–O distances. This result shows that spectroscopic observations on the strength of the covalent O–H bond cannot be interpreted unambiguously in terms of a corresponding behaviour of the associated H···O/F hydrogen bond.     

Single-crystal elastic properties of chondrodite: implications for water in the upper mantle

Chondrodite, a member of the humite group of minerals, forms by hydration of olivine and is stable over a range of temperatures and pressures that includes a portion of the uppermost mantle. We have measured the single crystal elastic properties of a natural chondrodite specimen at ambient conditions using Brillouin spectroscopy. The isotropic aggregate bulk (K) and shear (μ) moduli calculated from the single-crystal elastic moduli, C_ij, are: K_S=118.4(16) GPa and μ=75.6(7) GPa. A comparison of the structures and elasticity of olivine and chondrodite indicate that the replacement of O with (OH,F) in M²⁺O₆ octahedra has a small effect on the elasticity of humite-group minerals. The slightly diminished elastic moduli of humite-group minerals (as compared to olivine) are likely caused by a smaller ratio of strong structural elements (SiO₄ tetrahedra) to weaker octahedra, and perhaps a more flexible geometry of edge-sharing MO₄(O,OH,F)₂ octahedra. In contrast to the humite-olivine group minerals, the incorporation of water into garnets and spineloids leads to a more substantial decrease in the elastic properties of these minerals. This contrasting behavior is due to formation of O₄H₄ tetrahedra and vacant hydroxyl-bearing octahedra in the garnets and spineloids, respectively. Therefore, the mechanism of incorporation of H/OH into mineral phases, not only degree of hydration, should be taken into account when estimating the effect of water on the elastic properties of minerals. The bulk elastic wave velocities of chondrodite and olivine are very similar. If humite-like incorporation of OH is predominant in the upper mantle, then the reaction of OH with olivine will have a minor or possibly no detectable effect on seismic velocities. Thus, it may be difficult to distinguish chondrodite-bearing rocks from “anhydrous” mantle on the basis of seismically determined velocities for the Earth. Received: 25 February 1998 / Revised, accepted: 18 August 1998     

High-pressure Raman spectroscopic study of chondrodite

Variation of Raman spectra of both natural (F-bearing) and synthetic (F-free) chondrodite samples were studied up to 400 kbar at room temperature. Ambient Raman frequencies for the synthetic sample are in general lower than those for the natural one. This is correlated with a slight expansion of the volume of the synthetic sample due to substitution of OH for F. The frequencies of all Raman bands for both samples increase monotonically with increasing pressure. The positive pressure dependences in the O−H stretch frequencies for both F-free and F-bearing samples are contrary to those for other dense hydrous magnesium silicates. A mechanism involving both the hydrogen-hydrogen repulsion and hydrogen bondings is proposed to explain the abnormal behavior. The effects of substitution of F for OH on both the ambient and high-pressure Raman spectra of chondrodite are also discussed. Received: 19 February 1998 / Revised accepted: 26 June 1998