- OH point defects (1) (remove)
- Water solubility in diopside (2008)
- (1) Water solubility in pure diopside was measured. Water-saturated diopside crystals were synthesized using piston-cylinder and multi-anvil presses at 20-30 and 100 kbar and 800-1100oC from an oxide and hydroxide starting mixture containing 10 % excess silica. The water concentration in diopside was determined from polarized infrared measurements on doubly polished single crystals. Water contents were calculated by integrating the absorption bands and using published extinction coefficients for water in diopside. All measured infrared spectra of pure diopside fall into two groups. The differences in the spectra point towards substitution mechanisms involving different vacancies, which in turn could be the result of different oxide activities in the starting material. Therefore, a separate series of experiments was carried out with starting materials with an excess or deficiency of MgO or SiO2. These experiments yielded diopside with different absorption spectra. Starting materials with low silica activity yielded Type I bands, which are therefore likely to be related to Si vacancies. Type II bands form at high silica activity and may therefore be related to Mg or Ca vacancies. Water solubility in pure diopside varies from 121 up to 568 ppm H2O. Water solubility at 30 kbar increases from 700 to 1000oC and drops again above 1000oC. At 900oC, water solubility increases to a maximum at 25 kbar and then decreases rapidly to higher pressures. Due to the low solubility of aluminum in clinopyroxene at high pressure, the data on pure diopside are probably a good guide for the water solubility in clinopyroxenes under the conditions of the deeper upper mantle. Since water solubility in diopside under those conditions is order of magnitude below the water solubility in olivine, clinopyroxene is not expected to be a major storage site for water in the deeper upper mantle, even if its modal abundance is significant. (2) Water-saturated Al-containing diopside was synthesized in an end-loaded piston-cylinder apparatus at 1.5-2.5 GPa and 900-1100oC. The compositions of the starting materials for Al-bearing diopside are along the join diopside (CaMgSi2O6) – Ca-Tschermak’s component (CaAl2SiO6) with different ratios of these two end members. The water solubility strongly increases with the presence of Al up to 2500 ppm H2O. The water solubility in aluminous diopside increasing with decreasing temperature. Estimated partition coefficients of water between clinopyroxene and orthopyroxene are close to unity, with Dcpx/opx possibly increasing with temperature. Together with previously published data on water in orthopyroxene, the results of this study clearly show that in the uppermost mantle, most of the water is dissolved in the pyroxenes. The relative importance of clinopyroxene and orthopyroxene is primarily a function of their modal abundance. This observation is consistent with the model of Mierdel et al (2007), which suggests that the Earth’s asthenosphere is due to a minimum in water solubility in nominally anhydrous minerals. (3) In order to determine the effect of water on the equation of state of diopsides, high-pressure single crystal X-ray diffraction experiments with a diamond anvil cell were performed. The compressibility of diopside decreases with increasing water and Al content in the structure. The bulk modulus Ko and its first pressure derivative K’ for the four diopside crystals are 106(1) GPa and 6.1(5) for pure anhydrous diopside (0 ppm H2O); 107(1) GPa and 6.5(4) for pure diopside with 63 ppm of H2O; 108(1) GPa and 6.3(4) for pure diopside with 600 ppm H2O; and 113(1) GPa and 5.7(5) for Al-bearing hydrous (containing 0.374 Al a.p.f.u.) diopside with 2510 ppm H2O. The results on compressibility of diopside contrast with previous work, which showed that compressibility of most other main mantle phases increases with water content. In addition, from the refinement of the crystal structures of both hydrous and dry diopside and comparison with the structure of Ca-Tschermak’s pyroxene it was possible to see the influence of protonation of oxygen atoms. Because of the contrasting effect of water on the equation of state of olivine and of pyroxenes in the upper mantle, detecting water from observations of seismic velocities alone is probably nearly impossible.