Equilibrium interface segregation in the diopside-forsterite system II: Applications of interface enrichment to mantle geochemistry

Segregation of incompatible elements at grain interfaces may have considerable influence on the physical and chemical properties of mantle rocks. Using a recently developed predictive model to estimate the interface enrichment of elements based on their mineral/melt partitioning (Hiraga and Kohlstedt, companion paper), we consider interface enrichment for a simplified model peridotite consisting of olivine, orthopyroxene, and clinopyroxene. Our calculated results reveal the following: (1) Significant amounts of heavy alkali elements and rare gases likely reside at grain-grain interfaces, whereas interface concentrations of less incompatible are less pronounced. (2) The contribution of the chemical components stored at interfaces to whole-rock chemistry strongly depends on mineral mode and, most importantly, on grain size. (3) Grain size reduction resulting from dynamic recrystallization can increase the total storage of highly incompatible elements on grain interfaces and thereby will diminish their concentration in mineral grains. (4) Analysis of Cs concentrations in mantle clinopyroxenes potentially provides estimates of the grain size of mantle rocks. (5) Transport through peridotite will be dominated by diffusion along interfaces rather than through grain interiors for elements less compatible than Lu.     

The use of sintered diamond anvils in the MA8 type high-pressure apparatus

A new multi-anvil type high-presure apparatus has been developed using sintered diamond anvils to generate pressures over 30 GPa and temperatures up to about 2000°C. A maximum sample volume of about 1 mm³ is available in this system. The pressure was confirmed by dissociation of forsterite into Mg-perovskite and periclase. The basic techniques and problems in utilizing sintered diamond in the MA8 type high-pressure apparatus are discussed with an emphasis on the future prospect of incorporating simultancous X-ray diffraction observation.     

Synthesis of highly dense and fine-grained aggregates of mantle composites by vacuum sintering of nano-sized mineral powders

Synthesized mineral powders with particle size of <100 nm are vacuum sintered to obtain highly dense and fine-grained polycrystalline mantle composites: single phase aggregates of forsterite (iron-free), olivine (iron containing), enstatite and diopside; two-phase composites of forsterite + spinel and forsterite + periclase; and, three-phase composites of forsterite + enstatite + diopside. Nano-sized powders of colloidal SiO₂ and highly dispersed Mg(OH)₂ with particle size of ≤50 nm are used as chemical sources for MgO and SiO₂, which are common components for all of the aggregates. These powders are mixed with powders of CaCO₃, MgAl₂O_4, and Fe(CO₂CH₃)₂ to introduce mineral phases of diopside, spinel, and olivine to the aggregates, respectively. To synthesize highly dense composites through pressureless sintering, we find that calcined powders should be composed of particles that have: (1) fully or partially reacted to the desired minerals, (2) a size of <100 nm and (3) less propensity to coalesce. Such calcined powders are cold isostatically pressed and then vacuum sintered. The temperature and duration of the sintering process are tuned to achieve a balance between high density and fine grain size. Highly dense (i.e., porosity ≤1 vol%) polycrystalline mantle mineral composites with grain size of 0.3–1.1 μm are successfully synthesized with this method.     

Effect of hydrostatic pressure on the lattice parameters of Fe2SiO4 olivine up to 70 kbar

The pressure dependence of the three lattice parameters and unit cell volume of fayalite (Fe₂SiO₄ olivine) was determined by X-ray diffraction under hydrostatic pressures up to 70 kbar. In order to eliminate stress inhomogeneity within a composite material consisting of a specimen mixed with an internal-pressure standard, a liquid (1 : 1 mixture of ethanol and methanol) was used as a pressure-transmitting medium. The isothermal bulk modulus calculated on the basis of the second-order Birch-Murnaghan equation of state gives the values K₀ = 1.19 ± 0.10 Mbar and K₀′ = 7 ± 4, and if we assume K₀′ = 5: K₀ = 1.24 ± 0.02 Mbar. Three axes of fayalite were found to be compressible in the following order, b >c >a. Comparisons with the results obtained under non-hydrostatic compression are made.     

Elasticity of CaIrO<Subscript>3</Subscript> with perovskite and post-perovskite structure

Compression behaviors of CaIrO₃ with perovskite (Pv) and post-perovskite (pPv) structures have been investigated up to 31.0(1.0) and 35.3(1) GPa at room temperature, respectively, in a diamond-anvil cell with hydrostatic pressure media. CaIrO₃ Pv and pPv phases were compressed with the axial compressibility of β _a > β _c > β _b and β _b > β _a > β _c, respectively and no phase transition was observed in both phases up to the highest pressure in the present study. The order of axial compressibility for pPv phase is consistent with the crystallographic consideration for layer structured materials and previous experimental results. On the other hand, Pv phase shows anomalous compression behavior in b axis, which exhibit constant or slightly expanded above 13 GPa, although the applied pressure remained hydrostatic. Volume difference between Pv and pPv phases was gradually decreased with increasing pressure and this is consistent with the results of theoretical study based on the ab initio calculation. Present results, combined with theoretical study, suggest that these complicate compression behaviors in CaIrO₃ under high pressure might be caused by the partially filled electron of Ir⁴⁺. Special attention must be paid in case of using CaIrO₃ as analog materials to MgSiO₃, although CaIrO₃ exhibits interesting physical properties under high pressure.     

High-pressure phase behavior of MnTiO<Subscript>3</Subscript>: decomposition of perovskite into MnO and MnTi<Subscript>2</Subscript>O<Subscript>5</Subscript>

The phase relations and compression behavior of MnTiO₃ perovskite were examined using a laser-heated diamond-anvil cell, X-ray diffraction, and analytical transmission electron microscopy. The results show that MnTiO₃ perovskite becomes unstable and decomposes into MnO and orthorhombic MnTi₂O₅ phases at above 38 GPa and high temperature. This is the first example of ABO₃ perovskite decomposing into AO + AB₂O₅ phases at high pressure. The compression behavior of volume, axes, and the tilting angle of TiO₆ octahedron of MnTiO₃ perovskite are consistent with those of other A²⁺B⁴⁺O₃ perovskites, although no such decomposition was observed in other perovskites. FeTiO₃ is also known to decompose into two phases, instead of transforming into the CaIrO₃-type post-perovskite phase and we argue that one of the reasons for the peculiar behavior of titanate is the weak covalency of the Ti–O chemical bonds.     

Synthesis of kosmochlor and phase equilibria in the join CaMgSi2O6-NaCrSi2O6

Kosmochlor (NaCrSi₂O₆) was synthesized by the flux method from melts along the join Na₂O·2 SiO₂-Na₂O·Cr₂O₃·4 SiO₂ at 1000° C in air, and isolated by dissolving the glassy matrix with hydrofluoric and perchloric acids. The join CaMgSi₂O₆-NaCrSi₂O₆ was studied at 1 atmosphere in air by the quenching technique at temperatures between 900° and 1450° C, using mixtures of kosmochlor and diopside crystals or diopside glass as starting materials. The phases are diopside solid solution, kosmochlor, spinel (Mg-chromite), eskolaite (Cr₂O₃) and glass. The maximum solubility of kosmochlor in diopside is 24 wt percent at 1140° C, while diopside is not soluble at all in kosmochlor, resulting in the existence of a wide range of immiscibility. Petrologic significance of the results is discussed.