The Effect of Fe-Al Substitution on the Crystal Structure of MgSiO3 Bridgmanite

The crystal chemistry of ten well-characterized bridgmanite single-crystals with Fe and Al contents ranging from 0 to 0.40 atoms per two-cation formula units were investigated by single-crystal X-ray diffraction. Structural refinements indicate that Fe3+ and Al mainly occupy the Mg and Si sites, respectively, when present in similar proportions. Molar volumes of bridgmanite endmember components were refined using data from this and previous studies and found to decrease in the order Fe3+Fe3+O3 > MgFe3+O2.5 > Fe3+AlO3 > MgAlO2.5 > AlAlO3 > Fe2+SiO3 > MgSiO3. Fe3+AlO3 charge-coupled substitution leads to an anisotropic increase of B-O bond distances, resulting in more distorted octahedral B sites and in a more significant increase of the c-axis with respect to the a- and b-axes. Valence bond calculations indicate that the A site is more compressible than the B site for all bridgmanite samples studied, implying that octahedral tilting and distortion will dominate the bridgmanite compression mechanism. Guided by these crystal chemical observations, bulk moduli of bridgmanite endmember components were estimated using results of previous studies. The volume changes of equilibria controlling the speciation of bridgmanite components were then calculated at conditions relevant to the top of Earth's lower mantle. The proportion of oxygen vacancy components is predicted to decrease with pressure. While the stability of the bridgmanite Fe3+AlO3 component will drive charge disproportionation to produce iron metal at the top of the lower mantle, this appears to be much less favorable by 50 GPa. An increase in the proportion of the Fe3+Fe3+O3 bridgmanite component, however, may favor the formation of iron metal at higher pressures

Estimating the viscosity of volcanic melts from the vibrational properties of their parental glasses

Abstract The numerical modelling of magma transport and volcanic eruptions requires accurate knowledge of the viscosity of magmatic liquids as a function of temperature and melt composition. However, there is growing evidence that volcanic melts can be prone to nanoscale modification and crystallization before and during viscosity measurements. This challenges the possibility of being able to quantify the crystal-free melt phase contribution to the measured viscosity. In an effort to establish an alternative route to derive the viscosity of volcanic melts based on the vibrational properties of their parental glasses, we have subjected volcanologically relevant anhydrous glasses to Brillouin and Raman spectroscopic analyses at ambient conditions. Here, we find that the ratio between bulk and shear moduli and the boson peak position embed the melt fragility. We show that these quantities allow an accurate estimation of volcanic melts at eruptive conditions, without the need for viscosity measurements. An extensive review of the literature data confirms that our result also holds for hydrous systems; this study thus provides fertile ground on which to develop new studies of the nanoscale dynamics of natural melts and its impact on the style of volcanic eruptions

Oxygen Vacancy Ordering in Aluminous Bridgmanite in the Earth's Lower Mantle

Oxygen vacancies (OVs), that charge-balance the replacement of octahedrally coordinated Si4+ by Al3+ in the mineral bridgmanite, will influence transport properties in the lower mantle but little is known about their stability and local structure. Using 27Al nuclear magnetic resonance (NMR) spectroscopy we have characterized OVs within six aluminous bridgmanite samples. In the resulting NMR spectra sixfold, fivefold, and fourfold coordinated Al species are resolved, in addition to near eightfold coordinated Al substituting for Mg. Fivefold coordinated Al is formed by single OV sites but fourfold coordination must result from short range ordering of OVs, producing OV clusters that may form through migration into twin domain walls. Characterizing the occurrence of such OV structures is an important prerequisite for understanding how transport properties change with depth and composition in the lower mantle

Static disorder in a perovskite mixed-valence metal–organic framework

ariable-temperature and variable-pressure single-crystal diffraction studies are carried out on a mixed-valence perovskite dimethylammonium (DMA) iron formate compound, with the formula [(DMA3)(H2O)][FeII3FeIII(HCOO)12], in order to investigate potential electric ordering of the DMA cation from its fourfold type of dynamic disorder at ambient conditions. Mössbauer spectroscopy is additionally carried out at ambient conditions to confirm the presence and ratio of Fe2+ and Fe3+ cations. Below 200 K, a dynamic to static disorder of the DMA cation is observed, while the crystal symmetry and iron formate framework structure remain the same. Upon application of pressure, however, a phase transition occurs that lowers the symmetry above 3.3 GPa. This work highlights the further chemical modifications that are possible within the dimethylammonium metal formates family, i.e. doping upon the A-site with neutral molecules, leading to additional opportunities to tune their physical properties

Sound velocities and single-crystal elasticity of hydrous Fo90 olivine to 12 GPa

Nominally anhydrous minerals (NAMs) may contain significant amounts of water and constitute an important reservoir for mantle hydrogen. The colloquial term ‘water’ in NAMs is related to the presence of hydroxyl-bearing (OH-) point defects in their crystal structure, where hydrogen is bonded to lattice oxygen and is charge-balanced by cation vacancies. This hydrous component may therefore have substantial effects on the thermoelastic parameters of NAMs, comparable to other major crystal-chemical substitutions (e.g., Fe, Al). Assessment of water concentrations in natural minerals from mantle xenoliths indicates that olivine commonly stores ~0 – 200 ppm of water. However, the lack of samples originating from depths exceeding ~250 km coupled with the rapid diffusion of hydrogen in olivine at magmatic temperatures makes the determination of the olivine water content in the upper mantle challenging. On the other hand, numerous experimental data show that, at pressures and temperatures corresponding to deep upper mantle conditions, the water storage capacity of olivine increases to 0.2 – 0.5 wt.%. Therefore, determining the elastic properties of olivine samples with more realistic water contents for deep upper mantle conditions may help in interpreting both seismic velocity anomalies in potentially hydrous regions of Earth's mantle as well as the observed seismic velocity and density contrasts across the 410-km discontinuity. Here, we report simultaneous single-crystal X-ray diffraction and Brillouin scattering experiments at room temperature up to 11.96(2) GPa on hydrous (0.20(3) wt.% H2O) Fo90 olivine to assess its full elastic tensor, and complement these results with a careful re-analysis of all the available single-crystal elasticity data from the literature for anhydrous Fo90 olivine. While the bulk (K) and shear (G) moduli of hydrous Fo90 olivine are virtually identical to those of the corresponding anhydrous phase, their pressure derivatives K´ and G´ are slightly larger, although consistent within mutual uncertainties. We then defined linear relations between the water concentration in Fo90 olivine, the elastic moduli and their pressure derivatives, which were then used to compute the sound velocities of Fo90 olivine with higher degrees of hydration. Even for water concentrations as high as 0.5 wt.%, the sound wave velocities of hydrous and anhydrous olivines were found to be identical within uncertainties at pressures corresponding to the base of the upper mantle. Contrary to previous claims, our data suggest that water in olivine is not seismically detectable, at least for contents consistent with deep upper mantle conditions. In addition to that, our data reveal that the hydration of olivine is unlikely to be a key factor in reconciling seismic velocity and density contrasts across the 410-km discontinuity with a pyrolitic mantle