Melting and thermal expansion in the Fe–FeO system at high pressure

Melting in the Fe–FeO system was investigated at pressures up to 93 GPa using synchrotron X-ray diffraction (XRD) and a laser heated diamond anvil cell (DAC). The criteria for melting were the disappearance of reflections associated with one of the end-member phases upon raising the temperature above the eutectic and the reappearance of those reflections on dropping the temperature below the eutectic. The Fe–FeO system is a simple eutectic at 50 GPa and remains eutectic to at least 93 GPa. The eutectic temperature was bound at several pressure points between 19 and 93 GPa, and in some cases the liquidus temperature was also determined. The eutectic temperature rises rapidly with pressure closely following the melting curve of pure Fe. A detailed phase diagram at 50 GPa is presented; the eutectic temperature is 2500 ± 150 K and the eutectic composition is bound between 7.6 ± 1.0 and 9.5 ± 1.0 wt.% O. The coefficient of thermal expansion of FeO is a strong function of volume and decreases with pressure according to a simple power law.     

Sound velocity measurement in liquid water up to 25 GPa and 900 K: Implications for densities of water at lower mantle conditions

We extended the pressure range of sound velocity measurements for liquid water to 25 GPa and 900 K along the melting curve using a laser heated diamond anvil cell with a combined system of Brillouin scattering and synchrotron X-ray diffraction. Experimental pressure and temperature were obtained by solving simultaneous equations: the melting curve of ice and the equation of state for gold. The sound velocities obtained in liquid water at high pressures and melting temperatures were converted to density using Murnaghan's equation of state by fitting a parameter of the pressure derivative of bulk modulus at 1 GPa. The results are in good agreement with the values predicted by a previously reported equation of state for water based on sound velocity measurements. The equation of state for water obtained in this study could be applicable to water released by dehydration reactions of dense hydrous magnesium silicate phases in cold subducting slabs at lower mantle conditions, although the validity of Murnaghan's equation of state for water should be evaluated in a wider pressure and temperature ranges. The present velocity data provides the basis for future improvement of the accurate thermodynamic model for water at high pressures.     

Determination of post-perovskite phase transition boundary up to 4400 K and implications for thermal structure in D″ layer

We have determined the post-perovskite phase transition boundary in MgSiO₃ in a wide temperature range from 1640 to 4380 K at 119–171 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). The results show a considerably high positive Clapeyron slope of + 13.3 ± 1.0 MPa/K and a transition temperature of about 3520 ± 70 K at the core–mantle boundary (CMB) pressure. The thermal structure in D″ layer can be tightly constrained from precisely determined post-perovskite phase transition boundary and the depths of paired seismic discontinuities. These suggest that temperature at the CMB may be around 3700 K, somewhat lower than previously thought. A minimum bound on the global heat flow from the core is estimated to be 6.6 ± 0.5 TW.     

Effect of hydrogen on the melting temperature of FeS at high pressure: Implications for the core of Ganymede

We have carried out in situ X-ray diffraction experiments on the FeS–H system up to 16.5 GPa and 1723 K using a Kawai-type multianvil high-pressure apparatus employing synchrotron X-ray radiation. Hydrogen was supplied to FeS from the thermal decomposition of LiAlH₄, and FeSH_x was formed at high pressures and temperatures. The melting temperature and phase relationships of FeSH_x were determined based on in situ powder X-ray diffraction data. The melting temperature of FeSH_x was reduced by 150–250 K comparing with that of pure FeS. The hydrogen concentration in FeSH_x was determined to be x = 0.2–0.4 just before melting occurred between 3.0 and 16.5 GPa. It is considered that sulfur is the major light element in the core of Ganymede, one of the Galilean satellites of Jupiter. Although the interior of Ganymede is differentiated today, the silicate rock and the iron alloy mixed with H₂O, and the iron alloy could react with H₂O (as ice or water) or the hydrous silicate before the differentiation occurred in an early period, resulting in a formation of iron hydride. Therefore, Ganymede's core may be composed of an Fe–S–H system. According to our results, hydrogen dissolved in Ganymede's core lowers the melting temperature of the core composition, and so today, the core could have solid FeSH_x inner core and liquid FeH_x–FeSH_x outer core and the present core temperature is considered to be relatively low.     

Spin state of ferric iron in MgSiO3 perovskite and its effect on elastic properties

Recent studies have indicated that a significant amount of iron in MgSiO₃ perovskite (Pv) is Fe³⁺ (Fe³⁺/ΣFe = 10–60%) due to crystal chemistry effects at high pressure (P) and that Fe³⁺ is more likely than Fe²⁺ to undergo a high-spin (HS) to low-spin (LS) transition in Pv in the mantle. We have measured synchrotron Mössbauer spectroscopy (SMS), X-ray emission spectroscopy (XES), and X-ray diffraction (XRD) of Pv with all iron in Fe³⁺ in the laser-heated diamond-anvil cell to over 100 GPa. Fe³⁺ increases the anisotropy of the Pv unit cell, whereas Fe²⁺ decreases it. In Pv synthesized above 50 GPa, Fe³⁺ enters into both the dodecahedral (A) and octahedral (B) sites approximately equally, suggesting charge coupled substitution. Combining SMS and XES, we found that the LS population in the B site gradually increases with pressure up to 50–60 GPa where all Fe³⁺ in the B site becomes LS, while Fe³⁺ in the A site remains HS to at least 136 GPa. Fe³⁺ makes Pv more compressible than Mg-endmember below 50 GPa because of the gradual spin transition in the B site together with lattice compression. The completion of the spin transition at 50–60 GPa increases bulk modulus with no associated change in density. This elasticity change can be a useful seismic probe for investigating compositional heterogeneities associated with Fe³⁺.     

Aluminum incorporation in α-PbO2 type TiO2 at pressures up to 20 GPa

Aluminum incorporation into the high pressure polymorph of TiO₂ with the structure of α-PbO₂ has been studied from 10 to 20 GPa and 1300 °C by XRD, high-resolution ²⁷Al MAS-NMR and TEM. Al-doped α-PbO₂ type TiO₂ can be recovered at atmospheric pressure. Al₂O₃ solubility in α-PbO₂ type TiO₂ increases with increasing the synthesis pressure. The α-PbO₂ type TiO₂ polymorph is able to incorporate up to 35 wt.% Al₂O₃ at 13.6 GPa and 1300 °C, being the substitution of Ti⁴⁺ by Al³⁺ on normal octahedral sites the mechanism of solubility. The transition to the higher pressure TiO₂ polymorph with the ZrO₂ baddeleyite structure, Akaogiite, has not been observed in the quenched samples at room pressure. The microstructure of the recovered sample synthesized at 16 GPa and 1300 °C points to the existence of a non-quenchable aluminum titanium oxide phase at these conditions.     

High-pressure phase relations in the system CaAl4Si2O11–NaAl3Si3O11 with implication for Na-rich CAS phase in shocked Martian meteorites

High-pressure phase relations in the system NaAl₃Si₃O₁₁–CaAl₄Si₂O₁₁ were examined at 13–23 GPa and 1600–1900 °C, using a multianvil apparatus. A Ca-aluminosilicate with CaAl₄Si₂O₁₁ composition, designated CAS phase, is stable above about 13 GPa at 1600 °C. In the system NaAl₃Si₃O₁₁–CaAl₄Si₂O₁₁, the CAS phase dissolving NaAl₃Si₃O₁₁ component coexists with jadeite, corundum and stishovite below 22 GPa, above which the CAS phase coexists with Na-rich calcium ferrite, corundum and stishovite. At 1600 °C, the solubility of NaAl₃Si₃O₁₁ component in the CAS solid solution increases with increasing pressure up to about 50 mol% at about 22 GPa, above which the solubility decreases with pressure. The maximum solubility of NaAl₃Si₃O₁₁ component in the CAS phase increases with temperature up to around 70 mol% at 1900 °C at 22 GPa. The dissociation of NaAlSi₂O₆ jadeite to NaAlSiO₄ calcium ferrite plus stishovite occurs at about 22 GPa. Lattice parameters of the CAS phase with the hexagonal Ba-ferrite structure change with increase of the NaAl₃Si₃O₁₁ component: a-axis decreases and c-axis slightly increases, resulting in decrease of molar volume. Enthalpies of the CAS solid solutions were measured by high-temperature drop-solution calorimetry techniques. The results show that enthalpy of hypothetical NaAl₃Si₃O₁₁ CAS phase is much higher than the mixture of NaAlSi₂O₆ jadeite, corundum and stishovite and is close to that of the mixture of NaAlSiO₄ calcium ferrite, corundum and stishovite. When we adopt the Na:Ca ratio of 75:25 of the natural Na-rich CAS phase in a shocked Martian meteorite, Zagami, the phase relations determined above suggest that the natural CAS phase crystallized from melt at pressure around 22 GPa and temperature close to or higher than 2000–2200 °C. The inferred P, T conditions are consistent with those estimated using other high-pressure minerals in the shocked meteorite.     

Partitioning of U and Th during garnet pyroxenite partial melting: Constraints on the source of alkaline ocean island basalts

Uranium series disequilibria in ocean island basalts (OIB) provide evidence for the presence of garnet in their source region. It has been suggested that enriched OIB signatures derive from mantle lithologies other than peridotite, such as eclogite or pyroxenite, and, in particular, that silica-poor garnet pyroxenite is the source lithology for alkali basalts. To test the ability of such a source to produce the U–Th disequilibria observed in alkali OIB, we determined experimentally clinopyroxene-melt and garnet-melt partition coefficients for a suite of trace elements, including U and Th, at 2.5 GPa and 1420–1450 °C. The starting composition for the experiments was a 21% partial melt of a silica-poor garnet pyroxenite. Experimentally determined clinopyroxene-melt partition coefficients range from 0.0083 ± 0.0006 to 0.020 ± 0.002 for Th and from 0.0094 ± 0.0006 to 0.024 ±0.002 for U, and garnet-melt partition coefficients are 0.0032 ± 0.0004 for Th and 0.013 ± 0.002 for U. Comparison of our experimental results with partition coefficients from previous experimental studies shows that the relative compatibilities of U and Th in both garnet and clinopyroxene are different for different mineral compositions, leading to varying degrees of U/Th fractionation with changing lithology. For a given melting rate and extent of partial melting, mafic lithologies tend to produce larger ²³⁰Th excesses than peridotite. However, this effect is minimized by the greater overall extents of melting experienced by eclogites and pyroxenites relative to peridotite. Results from chromatographic, batch, and fractional melting calculations with binary mixing between partial melts of pyroxenite and peridotite, carried out using our new partitioning data for the pyroxenite component and taking into account variable productivities and different solidus depths for the two lithologies, suggest that OIB are not the product of progressive melting of a source containing a fixed quantity of garnet pyroxenite. Melting a peridotite with enriched signatures, and mixing those melts with melts of a depleted, “normal” peridotite, is an alternative explanation for the trends seen in Hawaiian, Azores and Samoan lavas.     

Forsterite to wadsleyite phase transformation under shear stress and consequences for the Earth's mantle transition zone

We have studied the phase transformation of forsterite to wadsleyite under shear stress at the Earth's transition zone pressure and temperature conditions. Two-step experiments were performed using a multi-anvil press. First, we hot pressed iron-free forsterite at 6 or 11 GPa and 1100 °C. Then we deformed a slab of this starting material using a direct simple shear assembly at 16 GPa and 1400 °C for 1, 15, 35, 40, or 60 min. Both the starting material and the deformed samples were characterized using optical and scanning electron microscopy including measurements of crystal preferred orientations (CPO) by electron back scattered diffraction (EBSD), transmission electron microscopy (TEM), and Fourier transform infrared spectroscopy (FTIR). The phase transformation occurs very rapidly, in less than 1 min, and metastable forsterite relics are not observed after deformation. The grain size of wadsleyite is slightly smaller than the forsterite starting material. The water contents obtained from FTIR analyses in forsterite and wadsleyite are 65–124 wt ppm H₂O and 114–736 wt ppm H₂O, respectively, which are well below water solubility at similar conditions in the presence of free water. Wadsleyite aggregates display weak CPO patterns with [1 0 0] axes concentrated at low angle to the shear direction, [0 1 0] axes perpendicular to the shear plane and nearly random [0 0 1] axes. Only a few dislocations were observed in wadsleyite with TEM. This observation is consistent with the assumption that most dislocations formed during the initial high-stress stages of these stress-relaxation experiments, were consumed in the phase transformation, probably enhancing the transformation rate. CPO patterns vary as a function of the water content: with increasing water content the density of [1 0 0] axes parallel to the shear direction decreases, and the density of [0 0 1] axes increases. Viscoplastic self-consistent modeling of CPO evolution using previously reported glide systems for wadsleyite, i.e., [1 0 0]{0 k l} and 1/2 〈1 1 1〉{1 0 1}, cannot reproduce the measured CPO, unless the [0 0 1](0 1 0) system, for which dislocations have not been observed by TEM, is also activated. In addition, wadsleyite grain growth suggests the participation of diffusion-assisted processes in deformation. Calculated anisotropies for P and S-waves using measured CPO are always below 1%. This very low anisotropy is due to both the low finite strain achieved in the experiments, which leads to weak wadsleyite CPO, and to the diluting effect of added majorite. The present experiments emphasize the importance of stress, grain size evolution and water content in the forsterite to wadsleyite phase transformation and subsequent deformation in the transition zone.     

Low-temperature magnetic properties of rhodochrosite (MnCO3)

We have measured magnetic hysteresis loops, zero-field-cooled (ZFC) and field-cooled (FC) remanence, and low-field AC susceptibility as a function of temperature between 2 and 40 K for a single crystal several mm in size and for two powders of manganese carbonate (mineral rhodochrosite, MnCO₃), one ground from a natural precipitate (grainsize ∼100 μm) and another synthesized in the laboratory (grainsize ∼10 μm). For the single crystal, measurements carried out both in the basal (easy magnetization) plane and along the trigonal (hard magnetization) axis yielded, expectedly, grossly different magnetic properties. In the basal plane, hysteresis appears to be mostly controlled by domain wall movement at the two lowest temperatures studied, 5 and 15 K, as indicated by a fairly broad switching field distribution. At 25 K and above, however, magnetization reversal occurs at a single, well defined magnetic field, which we interpret as a characteristic field of the in-plane magnetic anisotropy. Hysteresis in the basal plane is observed up to 36 K which is above the nominal Néel temperature of rhodochrosite (34.3 K). In addition, a sharp coercivity peak occurs at 34.5 K. Rather unexpectedly, hysteresis is also observed for the magnetic field applied along the trigonal axis. It is very small at 5 K but develops gradually with increasing temperature, coercivity reaching maximum of 100 mT at 28 K and remanence peaking at slightly higher temperature (30–31 K). Hysteresis along the trigonal axis is observed up to 37 K. Hysteresis temperature dependence conforms with the AC susceptibility versus temperature curve which shows a maximum at 36.5 K. ZFC/FC remanence curves also closely match the temperature dependence of remanence extracted from hysteresis loops. We suggest that this behavior could be due to the presence of a minor, about 1 at.% amount of Fe²⁺ substituting for Mn in the crystalline lattice of rhodochrosite. Hysteresis measurements on powders have revealed a significant enhance in coercivity, up to 50 mT for the 100-μm powder and up to 150 mT for the 10-μm one. FC/ZFC ratio amounts to about 2 for the natural powder, while for the synthetic one, which is essentially pure material, it barely exceeds unity. FC/ZFC ratio can thus be viewed as a sensitive indicator of iron incorporation into rhodochrosite.     

Tectono-metamorphic evolution of the Briançonnais zone (Modane-Aussois and Southern Vanoise units,Lyon Turin transect,Western Alps)

In the central Western Alps, a combined structural, petrological and ⁴⁰Ar–³⁹Ar geochronological study of the Modane-Aussois and Southern Vanoise units yields important constraints on the timing of deformation and exhumation of the Briançonnais zone. These data help to decipher the respective roles of oceanic subduction, continental subduction and collision in the burial and exhumation of the main units through time. In the Modane-Aussois unit top to the NW thrusting (D1) was followed by top to the east shearing (D2) interpreted by some as normal faulting and by others as backthrusting. Pseudosection calculations imply that D1 deformation occurred at 1.0 ± 0.1 GPa and 350 ± 30 °C. Analysis of chlorite–phengite pairs yield P–T estimates between 0.15 and 0.65 GPa and between 220 and 350 °C for the D2 event. Phengites along the D1 schistosity (sample M80) yields an ⁴⁰Ar–³⁹Ar age of 37.12 ± 0.39 Ma, while D2 phengites yield ages of 35.42 ± 0.38 (sample M173) and 31.60 ± 0.33 Ma (sample M196). It was not possible to test whether these ages are altered by excess argon or not. Our interpretation is that the D1/D2 transition occurred at ∼37 Ma at the beginning of decompression, and that D2 lasted until at least ∼32 Ma. Pseudosection calculation suggests that the Southern Vanoise unit was buried at 1.6 ± 0.2 GPa and 500–540 °C. D1 deformation occurred during exhumation until 0.7–10.5 GPa and 370 ± 30 °C. Published ages suggest that D1 deformation possibly started at ∼50 Ma and lasted until ∼37 Ma. D2 deformations started at P–T conditions close to that recorded in Modane-Aussois unit and lasted until 0.2 ± 0.1 GPa and 280 ± 30 °C at ∼28 Ma. The gap of 0.6 ± 0.3 GPa and 150 ± 130 °C between peak metamorphic conditions in the two units was concealed by thrusting of the South Vanoise unit on top of the Modane-Aussois unit during D1 Deformation. Top to the east deformation (D2) affects both units and is interpreted as backthrusting.Based on these data, we propose a geodynamic reconstruction where the oceanic subduction of the Piedmont unit until ∼50 Ma, is followed by its exhumation at the time of continental subduction of the continental Southern Vanoise unit until ∼45 Ma. The Southern Vanoise is in turn underthrusted by the Modane-Aussois unit until ∼37 Ma (D1). Between 37 and 31 Ma the Modane-Aussois and Southern Vanoise units exhume together during backthrusting to the east (D2). This corresponds to the collision stage and to the activation of the Penninic Thrust. In the ∼50 Ma to ∼31 Ma time period the main thrusts propagated westward as the tectonic context switched from oceanic to continental subduction and finally to collision. During each stage, external units are buried while internal ones are exhumed.     

Distribution of dissolved labile and particulate iron and copper in Terra Nova Bay polynya (Ross Sea,Antarctica) surface waters in relation to nutrients and phytoplankton growth

The distribution of the dissolved labile and of the particulate Fe and Cu together with dissolved oxygen, nutrients, chlorophyll a and total particulate matter was investigated in the surface waters of Terra Nova Bay polynya in mid-January 2003. The measurements were conducted within the framework of the Italian Climatic Long-term Interactions of the Mass balance in Antarctica (CLIMA) Project activities. The labile dissolved fraction was operationally defined by employing the chelating resin Chelex-100, which retains free and loosely bound trace metal species. The dissolved labile Fe ranges from below the detection limit (0.15 nM) to 3.71 nM, while the dissolved labile Cu from below the detection limit (0.10 nM) to 0.90 nM. The lowest concentrations for both metals were observed at 20 m depth (the shallowest depth for which metals were measured). The concentration of the particulate Fe was about 5 times higher than the dissolved Fe concentration, ranging from 0.56 to 24.83 nM with an average of 6.45 nM. The concentration of the particulate Cu ranged from 0.01 to 0.71 nM with an average of 0.17 nM. The values are in agreement with the previous data collected in the same area. We evaluated the role of the Fe and Cu as biolimiting metals. The N:dissolved labile Fe ratios (18,900–130,666) would or would not allow a complete nitrate removal, on the basis of the N:Fe requirement ratios that we calculated considering the N:P and the C:P ratios estimated for diatoms. This finding partially agrees with the Si:N ratio that we found (2.29). Moreover we considered a possible influence of the dissolved labile Cu on the Fe uptake process.     

Seasonal and diurnal variation of electron and iron concentrations at the meteor heights above Arecibo

We report observations of seasonal and local time variation of the averaged electron and iron concentrations, as well as simultaneous measurements of the two species, above the Arecibo Observatory (18.35°N, 66.75°N), Puerto Rico. The average Fe profile between 21:00 and 24:00 LT has a single peak at about 85 km with the exception of the summer when an additional peak exists at about 95 km. The higher Fe peak in the summer is correlated with higher electron concentrations in this season. The three nights of simultaneous measurements of electron and iron concentrations show that narrow layers of Fe and electrons are well correlated. Comparison of the climatological and simultaneous Fe and electron data suggests that recombination of Fe⁺ plays an important role in determining the Fe profile in the upper part of the Fe layer. Above 93 km, the Fe concentration appears to increase after sunset if the electron concentration exceeds about 4000 electrons cm⁻³. The average rate of Fe production is about 0.1 atom cm⁻³ s⁻¹ for all seasons at 100 km in the early evening hours. A chemical model reveals that the concentration of Fe⁺ must be 50–80% of the total ionization over Arecibo for typical equinox conditions to explain the observed rate of Fe production. These high relative Fe⁺ concentrations are consistent with in situ observations that Fe⁺ is usually the dominant ion in sporadic E layers in the nighttime lower E region. This suggests that the source of Fe⁺ is provided by sporadic E layers descending over Arecibo after sunset. The Fe density between 80 and 85 km decreases during the night, for all seasons. This is attributed to the formation of stable molecular Fe species, such as FeOH, due to the increase in O₃ and decrease in atomic O and H during the night at these altitudes.     

Anisotropic thermal properties of talc under high temperature and pressure

The anisotropic thermal conductivity and diffusivity of talc were simultaneously measured up to 5.3 GPa and 900 K using the pulse transient method. Although significant anisotropy was observed in the thermal conductivity of talc, the average thermal conductivity is comparable to that of olivine and roughly three times greater than that of antigorite. From the ratio of the thermal conductivity to the thermal diffusivity, the heat capacity of talc was evaluated. The pressure derivative of heat capacity was found to be positive, which is related to the anomaly of thermal expansivity of talc above 50 °C at atmospheric pressure.     

Electrical conductivities of pyrolitic mantle and MORB materials up to the lowermost mantle conditions

The electrical conductivities of natural pyrolitic mantle and MORB materials were measured at high pressure and temperature covering the entire lower mantle conditions up to 133 GPa and 2650 K. In contrast to the previous laboratory-based models, our data demonstrate that the conductivity of pyrolite does not increase monotonically but varies dramatically with depth in the lower mantle; it drops due to high-spin to low-spin transition of iron in both perovskite and ferropericlase in the mid-lower mantle and increases sharply across the perovskite to post-perovskite phase transition at the D″ layer. We also found that the MORB exhibits much higher conductivity than pyrolite. The depth–conductivity profile measured for pyrolite does not match the geomagnetic field data below about 1500-km depth, possibly suggesting the existence of large quantities of subducted MORB crust in the deep lower mantle. The observations of geomagnetic jerks suggest that the electrical conductivity may be laterally heterogeneous in the lowermost mantle with high anomaly underneath Africa and the Pacific, the same regions as large low shear-wave velocity provinces. Such conductivity and shear-wave speed anomalies are also possibly caused by the deep subduction and accumulation of dense MORB crust above the core–mantle boundary.     

Temperature dependence of the elastic moduli of ringwoodite

The elastic moduli of polycrystalline ringwoodite, (Mg_0.91Fe_0.09)₂SiO₄, were measured up to 470 K by means of the resonant sphere technique. The adiabatic bulk (K_S) and shear (μ) moduli were found to be 185.1(2) and 118.22(6) GPa at room temperature, and the average slopes of dK_S/dT and dμ/dT in the temperature range of the study were determined to be −0.0193(9) and −0.0148(3) GPa/K, respectively. Using these results, we estimate seismic wave velocity jumps for a pure olivine mantle model at 520 km depth. We find that the jump for the S-wave velocity is about 1.5 times larger than that for the P-wave velocity at this depth. This suggests that velocity jumps at the 520 km discontinuity are easier to detect using S-waves than P-waves.     

Compressibility of brownmillerite (Ca2Fe2O5): effect of vacancies on the elastic properties of perovskites

The evolution with pressure of the unit-cell parameters brownmillerite (Ca₂Fe₂O₅), a stoichiometric defect perovskite structure, has been determined to a maximum pressure of 9.46 GPa, by single-crystal X-ray diffraction measurements at room temperature. Brownmillerite does not exhibit any phase transitions in this pressure range. A fit of a third-order Birch–Murnaghan equation-of-state to the P–V data yields values of K_T0=127.0(5) GPa and K₀′=5.99(13). Analysis of the unit-cell parameter data shows that the structure compresses anisotropically. Compressional moduli for the axes are K_a0=141(1) GPa, K_b0=118(3) GPa and K_c0=122.2(2) GPa, with K_a0′=8.9(3), K_b0′=6.2(6) and K_c0′=4. The stiffest direction (i.e. along a) coincides with the direction of the FeO₄ tetrahedral chains. Comparison of these data with the elasticity systematics of Ca-perovskites shows that the presence of oxygen vacancies in the brownmillerite structure softens the structure by ∼25% and that the ordering of vacancies in the perovskite structure increases the anisotropy of compression.     

Co-sequestration of SO2 with supercritical CO2 in carbonates: An experimental study of capillary trapping,relative permeability,and capillary pressure

In this study we performed three categories of steady- and unsteady-state core-flooding experiments to investigate capillary trapping, relative permeability, and capillary pressure, in a scCO₂ + SO₂/brine/limestone system at elevated temperature and pressure conditions, i.e., 60 °C and 19.16 MPa. We used a Madison limestone core sample acquired from the Rock Springs Uplift in southwest Wyoming. We carried out two sets of steady-state drainage-imbibition relative permeability experiments with different initial brine saturations to study hysteresis. We found that the final scCO₂ + SO₂ drainage relative permeability was very low, i.e., 0.04. We also observed a rapid reduction in the scCO₂-rich phase imbibition relative permeability curve, which resulted in a high residual trapping. The results showed that between 62.8% and more than 76% of the initial scCO₂ + SO₂ at the end of drainage was trapped by capillary trapping mechanism (trapping efficiency). We found that at higher initial brine saturations, the trapping efficiency was higher. The maximum initial and residual scCO₂-rich phase saturations at the end of primary drainage and imbibition were 0.525 and 0.329, respectively. Each drainage-imbibition cycle was followed by a dissolution process to re-establish S_w = 1. The dissolution brine relative permeabilities for both cycles were also obtained. We characterized the scCO₂ + SO₂/brine capillary pressure hysteresis behavior through unsteady-state primary drainage, imbibition, and secondary drainage experiments. We observed negative imbibition capillary pressure curve indicative of possible wettability alteration throughout the experiments due to contact with scCO₂ + SO₂/brine fluid system. The trapping results were compared to those reported in literature for other carbonate core samples. We noticed slightly more residual trapping in our sample, which might be attributed to heterogeneity, different viscosity ratio, and pore-space topologies. The impact of dynamic effects, i.e., high brine flow rate imbibition tests, on trapping of the scCO₂-rich phase was also explored. We performed two imbibition experiments with relatively high brine flow rates. The residual scCO₂ saturation dropped to 0.291 and 0.262 at the end of the first and second imbibition tests, i.e., 11.5% and 20.4%, respectively, compared to 0.329 under capillary-dominated regime.     

Elastic anisotropy of ferromagnesian post-perovskite in Earth's D” layer

We report experimental observation of a sizable elastic anisotropy in a polycrystalline sample of ferromagnesian silicate in post-perovskite (ppv) structure. Using a novel composite X-ray transparent gasket to contain and synthesize ppv in a panoramic diamond-anvil cell along with oblique X-ray diffraction geometry, we observed the anisotropic lattice strain and {1 0 0} or {1 1 0} slip-plane texture in the sample at 140 GPa. We deduced the elasticity tensor (c_ij), orientation-dependent compressional wave velocities, polarization-dependent shear-wave velocities, and the velocity anisotropy of the silicate ppv. Our results are consistent with calculations and indicate that with sufficient preferred orientation, the elastic anisotropy of this phase can produce large shear-wave splitting.