Solubility of FeO in (Mg,Fe)SiO3 perovskite and the post-perovskite phase transition

Phase relations in Mg_0.5Fe_0.5SiO₃ and Mg_0.25Fe_0.75SiO₃ were investigated in a pressure range from 72 to 123 GPa on the basis of synchrotron X-ray diffraction measurements in situ at high-pressure and -temperature in a laser-heated diamond-anvil cell (LHDAC). Results demonstrate that Mg_0.5Fe_0.5SiO₃ perovskite is formed as a single phase at 85–108 GPa and 1800–2330 K, indicating a high solubility of FeO in (Mg,Fe)SiO₃ perovskite at high pressures. Post-perovskite appears coexisting with perovskite in Mg_0.5Fe_0.5SiO₃ above 106 GPa at 1410 K, the condition very close to the post-perovskite phase transition boundary in pure MgSiO₃. The coexistence of perovskite and post-perovskite was observed to 123 GPa. In addition, post-perovskite was formed coexisting with perovskite also in Mg_0.25Fe_0.75SiO₃ bulk composition at 106–123 GPa. In contrast to earlier experimental and theoretical studies, these results show that incorporation of FeO stabilizes perovskite at higher pressures. This could be due to a larger ionic radius of Fe²⁺ ion, which is incompatible with a small Mg²⁺ site in the post-perovskite phase.     

Net, actual, and potential sediment-water interface NH4 fluxes in the northern Gulf of Mexico (NGOMEX): Evidence for NH4 limitation of microbial dynamics

A new approach, combining ¹⁵NH₄⁺ isotope dilution and continuous-flow techniques, provided estimates of “actual” and “net” NH₄⁺ flux and sediment NH₄⁺ demand (SAD) at the sediment-water interface (SWI) of sites in the northern Gulf of Mexico (NGOMEX). The sites included a hypoxic site (C6), two sites with intermediate oxygen levels (B7 and F5), and a normoxic site (CT). Control cores without isotope addition and other cores from the same site treated with ¹⁵NH₄⁺ labeled overflowing water differentiated between net and actual regeneration flux and actual vs. potential uptake flux of NH₄⁺. Experiments were conducted in 2008 before (July) and after (September) two successive hurricanes (Gustav and Ike) and in January and August, 2009. Actual regeneration was significantly higher than net flux at most sites. Net flux did not differ significantly in most sites/dates, but the actual regeneration, and the actual and potential uptake, showed temporal and spatial variation; the flux at the hypoxic site was more active than non-hypoxic sites. SAD, the difference between potential and actual NH₄⁺ uptake flux, was higher at the hypoxic site than at non-hypoxic sites before and after the hurricanes in 2008 and during the hypoxia season in 2009. SAD related negatively to bottom water DO values. Conclusions: (1) net flux often underestimated actual regeneration, (2) hurricane activity decreased N dynamics, and (3) microbial N limitation status at the hypoxic site related to NH₄⁺ removal processes that were independent of oxygen (e.g., anaerobic heterotrophic uptake or anammox). These results indicate a rather consistent NH₄⁺ demand at the SWI during the hypoxic season and suggest that reduced nitrogen may limit microbial dynamics in the region.     

Garnet-ilmenite-perovskite transitions in the system Mg4Si4O12-Mg3Al2Si3O12 at high pressures and high temperatures: phase equilibria, calorimetry and implications for mantle structure

Phase relations in the system Mg₄Si₄O₁₂-Mg₃Al₂Si₃O₁₂ were examined at pressures of 19-27 GPa and relatively low temperatures of 800-1000 °C using a multianvil apparatus to clarify phase transitions of pyroxene-garnet assemblages in the mantle. Both of glass and crystalline starting materials were used for the experiments. At 1000 °C, garnet solid solution (s.s.) transforms to aluminous ilmenite s.s. at 20-26 GPa which is stable in the whole compositional range in the system. In Mg₄Si₄O₁₂-rich composition, ilmenite s.s. transforms to a single-phase aluminous perovskite s.s., while Mg₃Al₂Si₃O₁₂-rich ilmenite s.s. dissociates into perovskite s.s. and corundum s.s. These newly determined phase relations at 1000 °C supersede preliminary phase relations determined at about 900 °C in the previous study. The phase relations at 1000 °C are quite different from those reported previously at 1600 °C where garnet s.s. transforms directly to perovskite s.s. and ilmenite is stable only very close to Mg₄Si₄O₁₂. The stability field of Mg₃Al₂Si₃O₁₂ ilmenite was determined at 800-1000 °C and 25-27 GPa by reversed phase boundaries. In ilmenite s.s., the a-axis slightly increases but the c-axis and molar volume decrease substantially with increasing Al₂O₃ content. Enthalpies of ilmenite s.s. were measured by differential drop-solution calorimetry method using a high-temperature calorimeter. The excess enthalpy of mixing of ilmenite s.s. was almost zero within the errors. The measured enthalpies of garnet-ilmenite and ilmenite-perovskite transitions at 298 K were 105.2±10.4 and 168.6±8.2 kJ/mol, respectively, for Mg₄Si₄O₁₂, and 150.2±15.9 and 98.7±27.3 kJ/mol, respectively, for Mg₃Al₂Si₃O₁₂. Thermodynamic calculations using these data give rise to phase relations in the system Mg₄Si₄O₁₂-Mg₃Al₂Si₃O₁₂ at 1000 and 1600 °C that are generally consistent with those determined experimentally, and confirm that the single-phase field of ilmenite expands from Mg₄Si₄O₁₂ to Mg₃Al₂Si₃O₁₂ with decreasing temperature. The earlier mentioned phase relations in the simplified system as well as those in the Mg₂SiO₄-Fe₂SiO₄ system are applied to estimate mineral proportions in pyrolite as a function of depth along two different geotherms: one is a horizontally-averaged temperature distribution in a normal mantle, and the other being 600 °C lower than the former as a possible representative geotherm in subducting slabs. Based on the previously described estimated mineral proportions versus depth along the two geotherms, density and compressional and shear wave velocities are calculated as functions of depth, using available mineral physics data. Along a normal mantle geotherm, jumps of density and velocities at about 660 km corresponding to the post-spinel transition are followed by steep gradients due to the garnet-perovskite transition between 660 and 710 km. In contrast, along a low-temperature geotherm, the first steep gradients of density and velocities are due to the garnet-ilmenite transition between 610 and 690 km. This is followed by abrupt jumps at about 690 km for the post-spinel transition, and steep gradients between 700 and 740 km that correspond to the ilmenite-perovskite transition. In the latter profile along the low-temperature geotherm, density and velocity increases for garnet-ilmenite and ilmenite-perovskite transitions are similar in magnitude to those for the post-spinel transition. The likely presence of ilmenite in cooler regions of subducting slabs is suggested by the fact that the calculated velocity profiles along the low-temperature geotherm are compatible with recent seismic observations indicating three discontinuities or steep velocity gradients at around 600-750 km depth in the regions of subducting slabs.     

A comparative overview of weathering intensity and HCO3 flux in the world's major rivers with emphasis on the Changjiang,Huanghe, Zhujiang (Pearl) and Mississippi Rivers

In this paper, general relationships of riverine bicarbonate concentrations and fluxes as a function of drainage basin mineral content and runoff are examined using a database of the 25 largest rivers in the world. Specific HCO₃⁻ flux normalized to unit basin area, which peaks in the mid latitudes, was found to be strongly correlated with the carbonate mineral content of river basins, while river HCO₃⁻ concentration was related to the balance of precipitation and evaporation. Within this global context, the weathering patterns of CO₂ in a few large rivers (Changjiang, Huanghe, Pearl, and Mississippi rivers) were examined in further detail. The Zhujiang (Pearl River), especially its largest branch (Xijiang), was characterized by the highest specific weathering rate among all the world's large rivers due to an exceptionally high carbonate mineral content (over 80%) in its drainage basin and its warm and wet environment. It has a moderate level of HCO₃⁻ concentration, however, due to dilution by relatively high precipitation in the watershed. In stark contrast, the Huanghe (Yellow River) has one of the lowest specific weathering rates because of low carbonate mineral content and a dry climate. However, it has a high HCO₃⁻ concentration due largely to the concentrating effects of high evaporative water loss, as a result of arid weather and the agricultural use of water through irrigation systems, as well as carbonate-containing surficial deposits (i.e., loess). The strong correlation between specific HCO₃⁻ fluxes and discharge in all four rivers with different discharge seasonality suggests that higher precipitation in drainage basins promotes higher weathering rates.