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We report the synthesis, at 7 GPa and 923 K, and the thermoelastic characterization, up to 16 GPa and 850 K, of a single crystal of Mg-sursassite, Mg5Al5Si6O21(OH)7. In situ high-pressure and high-temperature single-crystal diffraction allowed the study of structural variation at non-ambient conditions and the determination of bulk elastic properties. The refined parameters of a second-order Birch-Murnaghan equation of state (BM-II EoS) are V0= 446.02(1) Å3and KT0= 135.6(7) GPa. The thermal expansion coefficients of a Berman-type EoS are α0= 3.14 (5) × 10−5K−1, α1= 2.50(16) × 10−8K−2, and V0= 445.94(3). For comparison, the P-VEoS is determined for a natural sursassite sample, ideally Mn4Al6Si6O22(OH)6. The refined parameters of BM-II EoS [V0= 470.2(3) Å3, KT0= 128(4) GPa] indicate that composition has a minimal effect on elastic properties. The similarity of density and bulk properties of Mg-sursassite if compared to olivine and other anhydrous mantle minerals suggests that this phase could be overseen by geophysical methods.

The crystal structure of a new high-pressure hydrous phase, Si-rich Mg-sursassite, of ideal composition Mg4Al5Si7O23(OH)5, that was produced by sub-solidus reaction at 24 GPa and 1400 °C in an experiment using a model sedimentary bulk composition, has been determined by single-crystal X‑ray diffraction. The phase was found to be topologically identical to Mg-sursassite, Mg5Al5Si6O21(OH)7, and has space group P21/mand lattice parameters a= 8.4222(7), b= 5.5812(3), c= 9.4055(9) Å, β = 106.793(8)°, V= 423.26(6) Å3, and Z= 1. The empirical formula determined by electron microprobe analysis of the same crystal as was used in the X‑ray experiment is [Mg3.93(3)Fe0.03(1)]S3.96[Al4.98(3)Cr0.04(1)]S5.02Si7.02(4)O23(OH)5, with hydroxyl content implied by the crystal-structure analysis. The most significant aspect of the structure of Si-rich Mg-sursassite is the presence of octahedrally coordinated Si. Its structural formula is M1,VIIMg2M2VIMg22+M3,VI(Al0.5Si0.5)2M4,VIAl2M5,VIAl2T1,IVSi2T2,IVSi2T3,IVSi2O23(OH)5.$^{M1,\text{VII}}M{{g}_{2}}{{\,}^{{{M}_{2}}\text{VI}}}\text{Mg}{{_{2}^{2+}}^{\,M3\text{,VI}}}{{\left( \text{A}{{\text{l}}_{\text{0}\text{.5}}}\text{S}{{\text{i}}_{\text{0}\text{.5}}} \right)}_{2}}{{\,}^{M4\text{,VI}}}\text{A}{{\text{l}}_{2}}{{\,}^{{{M}_{5}}\text{,VI}}}\text{A}{{\text{l}}_{2}}^{T1\text{,IV}}\text{S}{{\text{i}}_{\text{2}}}{{\,}^{T2\text{,IV}}}\text{S}{{\text{i}}_{2}}{{\,}^{T3\text{,IV}}}\text{S}{{\text{i}}_{2}}\,\,{{\text{O}}_{\text{23}}}{{\left( \text{OH} \right)}_{\text{5}}}.$Si-rich Mg-sursassite joins the group of hydrous ultrahigh-pressure phases with octahedrally coordinated Si that have been discovered by experiment, and that may play a significant role in the distribution and hosting of water in the deep mantle at subduction zones. The reactions defining the stability of Si-rich Mg-sursassite are unknown, but are likely to be fundamentally diferent from those of Mg-sursassite, and involve other ultrahigh-pressure dense structures such as phase D, rather than phase A.

Abstract:  Calorimetric and P–V–T data for the high-pressure phase Mg5Al5Si6O21(OH)7 (Mg-sursassite) have been obtained. The enthalpy of drop solution of three different samples was measured by high-temperature oxide melt calorimetry in two laboratories (UC Davis, California, and Ruhr University Bochum, Germany) using lead borate (2PbO·B2O3) at T=700 ∘C as solvent. The resulting values were used to calculate the enthalpy of formation from different thermodynamic datasets; they range from −221.1 to −259.4 kJ mol−1 (formation from the oxides) respectively −13892.2 to −13927.9 kJ mol−1 (formation from the elements). The heat capacity of Mg5Al5Si6O21(OH)7 has been measured from T=50 ∘C to T=500 ∘C by differential scanning calorimetry in step-scanning mode. A Berman and Brown (1985)-type four-term equation represents the heat capacity over the entire temperature range to within the experimental uncertainty: C P (Mg-sursassite) =(1571.104 −10560.89×T −0.5−26217890.0 ×T −2+1798861000.0×T −3) J K−1 mol−1 (T in K). The P V T behaviour of Mg-sursassite has been determined under high pressures and high temperatures up to 8 GPa and 800 ∘C using a MAX 80 cubic anvil high-pressure apparatus. The samples were mixed with Vaseline to ensure hydrostatic pressure-transmitting conditions, NaCl served as an internal standard for pressure calibration. By fitting a Birch-Murnaghan EOS to the data, the bulk modulus was determined as 116.0±1.3 GPa, (K ′=4), V T,0 =446.49 3 exp[∫(0.33±0.05) × 10−4 + (0.65±0.85)×10−8 T dT], (K T/T) P  = −0.011± 0.004 GPa K−1. The thermodynamic data obtained for Mg-sursassite are consistent with phase equilibrium data reported recently (Fockenberg 1998); the best agreement was obtained with Δf H 0298 (Mg-sursassite) = −13901.33 kJ mol−1, and S 0298 (Mg-sursassite) = 614.61 J K−1 mol−1.