Anton Shatskiy

Solidus of alkaline carbonatite in the deep mantle

Minor amounts of alkalies (Na and K) can reduce drastically the solidus temperatures of carbonated silicate mantle, by as much as 400–500 °C. Low-degree melting of carbonated peridotite and eclogite at pressures of 3–10 GPa produces Na- and K-bearing carbonatite melt. Mass-balance calculations of samples obtained below apparent solidi show clear deficits of alkalies, suggesting the presence of minor alkali-rich liquid or solid carbonate phases. Here we determine the true solidi in Na- and K-bearing carbonate systems and report the stability of alkaline carbonate phases. Melting of subducting alkaline carbonates would likely occur at transition zone depths to produce mobile carbonatite melt diapirs that migrate upward, modifying and oxidizing the upper mantle and initiating volcanism at the surface.

The system K2CO3-MgCO3 at 6 GPa and 900–1450 °C

Abstract Phase relations in the K2CO3-MgCO3 system have been studied in high-pressure high-temperature (HPHT) multi-anvil experiments using graphite capsules at 6.0 ± 0.5 GPa pressures and 900-1450 °C temperatures. Subsolidus assemblies comprise the fields K2CO3+K2Mg(CO3)2 and K2Mg(CO3)2+MgCO3 with the transition boundary near 50 mol% MgCO3 in the system. The K2CO3-K2Mg(CO3)2 eutectic is established at 1200 °C and 25 mol% MgCO3. Melting of K2CO3 occurs between 1400 and 1450 °C. We propose that K2Mg(CO3)2 disappears between 1200 and 1300 °C via congruent melting. Magnesite is observed as a subliquidus phase to temperatures in excess of 1300 °C. At 6 GPa, melting of the K2Mg(CO3)2+MgCO3 assemblage can be initiated either by heating to 1300 °C under “dry” conditions or by adding a certain amount of water at 900-1000 °C. Thus, the K2Mg(CO3)2 could control the solidus temperature of the carbonated mantle under “dry” conditions and cause formation of the K- and Mg-rich carbonatite melts similar to those found as microinclusions in “fibrous” diamonds. The K2Mg(CO3)2 compound was studied using in situ X‑ray coupled with a DIA-type multi-anvil apparatus. At 6.5 GPa and 1000 °C, the structure of K2Mg(CO3)2 was found to be orthorhombic with lattice parameters a = 8.8898(7), b = 7.8673(7), and c = 5.0528(5), V = 353.39(4). No structure change was observed during pressure decrease down to 1 GPa. However, recovered K2Mg(CO3)2 exhibited a trigonal R3̅m structure previously established at ambient conditions.

Dense hydrous magnesium silicates, phase D, and superhydrous B: New structural constraints from one- and two-dimensional 29Si and 1H NMR

Abstract To gain new structural insights into phase D and superhydrous B, two phases of potential mantle water reservoir, we have applied a range of one- (1D) and two-dimensional (2D) 1H and 29Si NMR techniques, as well as Raman spectroscopy, to samples synthesized at 24 GPa and 900~1100 °C. These data have revealed that phase D is characterized by disordered and varying local structures around both Si and H. The 29Si NMR spectra of phase D contain a nearly symmetric, broad peak near -177.7 ppm, attributable to octahedral Si with local structural disorder. The high-resolution 1H CRAMPS spectra of phase D contain a main broad peak near 12.6 ppm with shoulders near 10 and 7 ppm, suggesting a distribution of hydrogen bonding distances. For superhydrous B, our comprehensive 2D 1H and 29Si NMR results have clearly revealed that it contains dissimilar hydrogen (H1-H2) pairs and one tetrahedral Si site, consistent with space group Pnn2.

Melting and subsolidus phase relations in the system Na2CO3-MgCO3±H2O at 6 GPa and the stability of Na2Mg(CO3)2 in the upper mantle

Abstract Phase relations in the Na2CO3-MgCO3 system have been studied in high-pressure high-temperature (HPHT) multi-anvil experiments using graphite capsules at 6.0 ± 0.5 GPa pressures and 900-1400 °C temperatures. Sub-solidus assemblages are represented by Na2CO3+Na2Mg(CO3)2 and Na2Mg(CO3)2+MgCO3, with the transition boundary near 50 mol% MgCO3 in the system. The Na2CO3-Na2Mg(CO3)2 eutectic is established at 1200 °C and 29 mol% MgCO3. Melting of Na2CO3 occurs between 1350 and 1400 °C. We propose that Na2Mg(CO3)2 disappears between 1200 and 1250 °C via congruent melting. Magnesite remains as a liquidus phase above 1300 °C. Measurable amounts of Mg in Na2CO3 suggest an existence of MgCO3 solid-solutions in Na2CO3 at given experimental conditions. The maximum MgCO3solubility in Na-carbonate of about 9 mol% was established at 1100 and 1200 °C. The Na2CO3 and Na2Mg(CO3)2 compounds have been studied using in situ X‑ray coupled with a DIA-type multi-anvil apparatus. The studies showed that eitelite is a stable polymorph of Na2Mg(CO3)2 at least up to 6.6 GPa and 1000 °C. In contrast, natrite, γ-Na2CO3, is not stable at high pressure and is replaced by β-Na2CO3. The latter was found to be stable at pressures up to 11.7 GPa at 27 °C and up to 15.2 GPa at 1200 °C and temperatures at least up to 800 °C at 2.5 GPa and up to 1000 °C at 6.4 GPa. The X‑ray and Raman study of recovered samples showed that, under ambient conditions, β-Na2CO3 transforms back to γ-Na2CO3. Eitelite [Na2Mg(CO3)2] would be an important mineral controlling insipient melting in subducting slab and upwelling mantle. At 6 GPa, melting of the Na2Mg(CO3)2+MgCO3 assemblage can be initiated, either by heating to 1300 °C under “dry” conditions or at 900-1100 °C under hydrous conditions. Thus, the Na2Mg(CO3)2 could control the solidus temperature of the carbonated mantle under “dry” conditions and cause formation of the Na- and Mg-rich carbonatite melts similar to those found as inclusions in olivines from kimberlites and the deepest known mantle rock samples-sheared peridotite xenoliths (190-230 km depth).

Pressure-volume-temperature equation of state of tungsten carbide to 32 GPa and 1673 K

We have obtained pressure-volume-temperature (P-V-T) equation of state for hexagonal tungsten carbide (α-WC) up to 32 GPa and 1673 K using synchrotron x-ray diffraction in a multianvil apparatus at the SPring-8 facility. MgO and Au were used as pressure calibrants. A least-squares fit of the P-V-T-data to a high-temperature Birch–Murnaghan equation of state yielded V0=20.750±0.002 A3, KT=384±4 GPa, K′=4.65±0.32, temperature derivative of the bulk modulus (∂KT/∂T)P=−0.014±0.002 GPa/K, and thermal expansion α=a0+a1T with a0=0.96(±0.05)×10−5 K−1 and a1=0.48(±0.05)×10−8 K−2. The data showed an anisotropic nature of compressibility, with the a-axis (KTa=341±6 GPa) more compressible than the c-the axis (KTc=506±12 GPa) as well as an anisotropic temperature dependence of KT. The estimated thermal Gruneisen parameters are 1.44–1.64 and the Debye temperature is calculated to be 1220 K, which is different from previous estimates.

Growth of large (1 mm) MgSiO3 perovskite single crystals: A thermal gradient method at ultrahigh pressure

Abstract Large single crystals of MgSiO3 perovskite were successfully synthesized by a thermal gradient method at 24 GPa and 1500 °C. This was achieved by an improvement of high-pressure synthesis technique that allowed us to grow single crystals under such ultrahigh-pressure conditions in relatively large volumes (e.g., 10 mm3). Since crystal growth is hindered by neighboring crystals, the nucleation density was suppressed by reducing the thermal gradient to 20 °C/mm, permitting an increase in free space for large crystal growth. KHCO3-Mg(OH)2 solvent can be used to grow perovskite crystals. However, the carbonate solvent produces melt inclusions. Silicate sources with MgSiO3 composition produce stishovite inclusions, which in turn cause splitting of perovskite crystals. The formation of these inclusions is avoided by using H2O as a solvent and 85MgSiO3-15Mg2SiO4 as a silicate source. The H2O also allows homogeneous crystal growth, probably because of its low viscosity and high silicate solubility. High-quality single crystals larger than 1 mm were successfully synthesized through these technical developments.

Thermal equation of state and thermodynamic properties of molybdenum at high pressures

A comprehensive P-V-T dataset for bcc-Mo was obtained at pressures up to 31 GPa and temperatures from 300 to 1673 K using MgO and Au pressure calibrants. The thermodynamic analysis of these data was performed using high-temperature Birch-Murnaghan (HTBM) equations of state (EOS), Mie-Gruneisen-Debye (MGD) relation combined with the room-temperature Vinet EOS, and newly proposed Kunc-Einstein (KE) approach. The analysis of room-temperature compression data with the Vinet EOS yields V0 = 31.14 ± 0.02 A3, KT = 260 ± 1 GPa, and KT′ = 4.21 ± 0.05. The derived thermoelastic parameters for the HTBM include (∂KT/∂T)P = −0.019 ± 0.001 GPa/K and thermal expansion α = a0 + a1T with a0 = 1.55 ( ± 0.05) × 10−5 K−1 and a1 = 0.68 ( ± 0.07) × 10−8 K−2. Fitting to the MGD relation yields γ0 = 2.03 ± 0.02 and q = 0.24 ± 0.02 with the Debye temperature (θ0) fixed at 455-470 K. Two models are proposed for the KE EOS. The model 1 (Mo-1) is the best fit to our P-V-T data, whereas the second model (Mo-2) is derived by including the shock compression and other experimental measurements. Nevertheless, both models provide similar thermoelastic parameters. Parameters used on Mo-1 include two Einstein temperatures ΘE10 = 366 K and ΘE20 = 208 K; Gruneisen parameter at ambient condition γ0 = 1.64 and infinite compression γ∞ = 0.358 with β  = 0.323; and additional fitting parameters m = 0.195, e0 = 0.9 × 10−6 K−1, and g = 5.6. Fixed parameters include k = 2 in Kunc EOS, mE1 = mE2 = 1.5 in expression for Einstein temperature, and a0 = 0 (an intrinsic anharmonicity parameter). These parameters are the best representation of the experimental data for Mo and can be used for variety of thermodynamic calculations for Mo and Mo-containing systems including phase diagrams, chemical reactions, and electronic structure.A comprehensive P-V-T dataset for bcc-Mo was obtained at pressures up to 31 GPa and temperatures from 300 to 1673 K using MgO and Au pressure calibrants. The thermodynamic analysis of these data was performed using high-temperature Birch-Murnaghan (HTBM) equations of state (EOS), Mie-Gruneisen-Debye (MGD) relation combined with the room-temperature Vinet EOS, and newly proposed Kunc-Einstein (KE) approach. The analysis of room-temperature compression data with the Vinet EOS yields V0 = 31.14 ± 0.02 A3, KT = 260 ± 1 GPa, and KT′ = 4.21 ± 0.05. The derived thermoelastic parameters for the HTBM include (∂KT/∂T)P = −0.019 ± 0.001 GPa/K and thermal expansion α = a0 + a1T with a0 = 1.55 ( ± 0.05) × 10−5 K−1 and a1 = 0.68 ( ± 0.07) × 10−8 K−2. Fitting to the MGD relation yields γ0 = 2.03 ± 0.02 and q = 0.24 ± 0.02 with the Debye temperature (θ0) fixed at 455-470 K. Two models are proposed for the KE EOS. The model 1 (Mo-1) is the best fit to our P-V-T data, whereas the second model (Mo-2) is derived by including...

Stishovite single-crystal growth and application to silicon self-diffusion measurements

Abstract Large single crystals of stishovite were successfully synthesized at 11 GPa from a silica solution in water. The potential of both slow cooling and thermal gradient methods were examined. The thermal gradient method provided crystals of 0.8 × 0.8 × 1.3 mm in size grown at 1350 °C and a thermal gradient of 50 °C/mm using stishovite as a silica source. The use of quartz as a source resulted in the appearance of numerous stishovite crystals in the solution interior resulting in diminished space for the growth of large crystals. This can be explained by a significant difference in the solubility of metastable quartz and stishovite in water, estimated to be 85.3 and 5.6 wt% SiO2 at 1000 °C and 11 GPa, respectively. Crystals up to 0.8 × 1.3 × 1.5 mm were grown by the slow cooling method in the system SiO2 + 14.7 wt% H2O as temperature was decreased from 1600 to 1000 °C with a cooling rate of 2 °C/min. The size of single crystals obtained was large enough to carry out silicon self-diffusion experiments, which were performed at a pressure of 14 GPa and temperatures from 1400 to 1800 °C. The lattice diffusion coefficients along the [110] and [001] directions can be expressed as D[110] (m2/s) = 4.10 × 10-12 exp [-322 (kJ/mol)/RT] and D[001] (m2/s) = 5.62 × 10-12 exp [-334 (kJ/mol)/RT], respectively, where R is the gas constant and T is the absolute temperature.

Crystal chemistry of sodium in the Earth’s interior: The structure of Na2MgSi5O12 synthesized at 17.5 GPa and 1700 °C

Abstract The crystal structure and chemical composition of a crystal of Na2MgSi5O12 garnet synthesized in the model system Mg3Al2Si3O12-Na2MgSi5O12 at 17.5 GPa and 1700 °C have been investigated. Quantitative analysis leads to the following formula: Na1.98Mg1.00Si5.01O12. Na2MgSi5O12 garnet was found to be tetragonal, space group I41/acd, with lattice parameters a = 11.3966(6), c = 11.3369(5) Å, V = 1472.5(1) Å3. The structure was refined to R = 5.13% using 771 independent reflections. Sodium and Mg are disordered at the X sites (with a mean bond distance of 2.308 Å for both the sites), whereas Si is ordered at both the Y (mean: 1.793 Å) and Z sites (means: 1.630 and 1.624 Å). Na-bearing majoritic garnet may be an important potential sodium concentrator in the lower parts of the upper mantle and transition zone. The successful synthesis of the Na2MgSi5O12 end-member and its structural characterization is of key importance because the study of its thermodynamic constants combined with the data of computer modeling provides new constraints on thermobarometry of majorite garnet assemblages

Boron-doped diamond heater and its application to large-volume, high-pressure, and high-temperature experiments

A temperature of 3500 degrees C was generated using a diamond resistance heater in a large-volume Kawai-type high-pressure apparatus. Re and LaCrO(3) have conventionally been used for heaters in high-pressure studies but they cannot generate temperatures higher than 2900 degrees C and make in situ x-ray observations difficult due to their high x-ray absorption. Using a boron-doped diamond heater overcomes these problems and achieves stable temperature generation for pressure over 10 GPa. The heater starting material is a cold-compressed mixture of graphite with boron used to avoid the manufacturing difficulties due to the extreme hardness of diamond. The diamond heater was synthesized in situ from the boron-graphite mixture at temperature of 1600+/-100 degrees C and pressure of 20 GPa. By using the proposed technique, we have employed the diamond heater for high-temperature generation in a large-volume high-pressure apparatus. Achievement of temperatures above 3000 degrees C allows us to measure the melting points of the important constituents in earths mantle (MgSiO(3), SiO(2), and Al(2)O(3)) and core (Fe and Ni) at extremely high pressures.