Thermodynamic properties of Mg_2SiO_4 liquid at ultra-high pressures from shock measurements to 200 GPa on forsterite and wadsleyite

Polycrystalline samples of Mg_2SiO_4 forsterite and wadsleyite were synthesized and then dynamically loaded to pressures of 39–200 GPa. Differences in initial density and internal energy between these two phases lead to distinct Hugoniots, each characterized by multiple phase regimes. Transformation to the high-pressure phase assemblage MgO + MgSiO_3 perovksite is complete by 100 GPa for forsterite starting material but incomplete for wadsleyite. The datum for wadsleyite shocked to 136 GPa, however, is consistent with the assemblage MgO + MgSiO_3 post-perovksite. Marked increases in density along the Hugoniots of both phases between ∼130 and 150 GPa are inconsistent with any known solid-solid phase transformation in the Mg_2SiO_4 system but can be explained by melting. Density increases upon melting are consistent with a similar density increase observed in the MgSiO_3 system. This implies that melts with compositions over the entire Mg/Si range likely for the mantle would be negatively or neutrally buoyant at conditions close to the core-mantle boundary, supporting the partial melt hypothesis to explain the occurrence of ultra-low velocity zones at the base of the mantle. From the energetic difference between the high-pressure segments of the two Hugoniots, we estimate a Grüneisen parameter (γ) of 2.6 ± 0.35 for Mg_2SiO_4-liquid between 150 and 200 GPa. Comparison to low-pressure data and fitting of the absolute pressures along the melt Hugoniots both require that γ for the melt increases with increasing density. Similar behavior was recently predicted in MgSiO_3 liquid via molecular dynamics simulations. This result changes estimates of the temperature profile, and hence the dynamics, of a deep terrestrial magma ocean

Simultaneous aluminum, silicon, and sodium coordination changes in 6 GPa sodium aluminosilicate glasses

We present the first direct observation of high-coordinated Si and Al occurring together in a series of high-pressure sodium aluminosilicate glasses, quenched from melts at 6 GPa. Using ^(29)Si MAS NMR, we observe that a small amount of Al does not have a significant effect on the amount of ^VSi or ^(VI)Si generated, but that larger Al concentrations lead to a gradual decrease in both these species. ^(27)Al MAS NMR spectra show that samples with small amounts of Al have extremely high mean Al coordination values of up to 5.49, but that larger Al concentrations cause a gradual decrease in both ^VAl and ^(VI)Al. Although mean Al and Si coordination numbers both decrease with increasing Al contents, the weighted combined (Al+Si) coordination number increases. Silicon and Al resonances shift in frequency with increasing pressure or changing Al concentration, indicating additional structural changes, including compression of network bond angles. Increases in the ^(23)Na isotropic chemical shifts indicate decreases in the mean Na-O bond lengths with increasing pressure, which are more dramatic at higher Al contents. Recovered glass densities are about 10 to 15% greater than those of similar ambient pressure samples. However, the density increases due to the combined coordination changes of Al and Si are estimated to total only about 1 to 2%, and are roughly constant with composition despite the large effects of Al content on the individual coordinations of the two cations. Thus, effects of other structural changes must be significant to the overall densification. Apparent equilibrium constants for reactions involving the generation of high-coordinated species show systematic behavior, which suggests an internal consistency to the observed Si and Al coordination number shifts

Direct shock wave loading of Stishovite to 235 GPa: Implications for perovskite stability relative to an oxide assemblage at lower mantle conditions

Pure stishovite and coesite samples with zero porosity and dimensions appropriate for planar shock wave experiments have been synthesized with multi-anvil high-pressure techniques. The equation of state of stishovite is obtained by direct shock wave loading up to 235 GPa: K_(0T) = 306 ± 5 GPa and K'_(0T) = 5.0 ± 0.2 where K_(0T) and K'_(0T) are ambient bulk modulus and its pressure derivative, respectively. The Hugoniots (shock equations of state) for stishovite, coesite and quartz achieve widely differing internal energy states at equal volume and therefore allow us to determine the Gruneisen parameter of stishovite. On the basis of the resulting P-V-T equation of state for stishovite and previous studies on other phases on the MgO-SiO_2 binary, the breakdown reaction of MgSiO_3-perovskite to MgO and SiO_2 was calculated. Our calculations show that perovskite is thermodynamically stable relative to the stishovite and periclase assemblage at lower mantle conditions. We obtain similar results for a range of models, despite the appreciable differences among these experiment-based thermodynamic parameters

The MgSiO_3 system at high pressure: Thermodynamic properties of perovskite, postperovskite, and melt from global inversion of shock and static compression data

We present new equation-of-state (EoS) data acquired by shock loading to pressures up to 245 GPa on both low-density samples (MgSiO_3 glass) and high-density, polycrystalline aggregates (MgSiO_3 perovskite + majorite). The latter samples were synthesized using a large-volume press. Modeling indicates that these materials transform to perovskite, postperovskite, and/or melt with increasing pressure on their Hugoniots. We fit our results together with existing P-V-T data from dynamic and static compression experiments to constrain the thermal EoS for the three phases, all of which are of fundamental importance to the dynamics of the lower mantle. The EoS for perovskite and postperovskite are well described with third-order Birch-Murnaghan isentropes, offset with a Mie-Grüneisen-Debye formulation for thermal pressure. The addition of shock data helps to distinguish among discrepant static studies of perovskite, and for postperovskite, constrain a value of K' significantly larger than 4. For the melt, we define for the first time a single EoS that fits experimental data from ambient pressure to 230 GPa; the best fit requires a fourth-order isentrope. We also provide a new EoS for Mg_2SiO_4 liquid, calculated in a similar manner. The Grüneisen parameters of the solid phases decrease with pressure, whereas those of the melts increase, consistent with previous shock wave experiments as well as molecular dynamics simulations. We discuss implications of our modeling for thermal expansion in the lower mantle, stabilization of ultra-low-velocity zones associated with melting at the core-mantle boundary, and crystallization of a terrestrial magma ocean

Advances in Shock Compression of Mantle Materials and Implications

Hugoniots of lower mantle mineral compositions are sensitive to the conditions where they cross phase boundaries including both polymorphic phase transitions and partial to complete melting. For SiO_2, the Hugoniot of fused silica passes from stishovite to partial melt (73 GPa, 4600 K) whereas the Hugoniot of crystal quartz passes from CaCi_2 structure to partial melt (116 GPa, 4900 K). For Mg_2SiO_4, the forsterite Hugoniot passes from the periclase +MgSiO_3 (perovskite) assemblage to melt before 152 GPa and 4300 K, whereas the wadsleyite Hugoniot transforms first to periclase +MgSiO_3 (post-perovskite) and then melts at 151 GPa and 4160 K. Shock states achieved from crystal enstatite are molten above 160 GPa. High-pressure Grüneisen parameters for molten states of MgSiO_3 and Mg_2SiO_4 increase markedly with compression, going from 0.5 to 1.6 over the 0 to 135 GPa range. This gives rise to a very large (>2000 K) isentropic rise in temperature with depth in thermal models of a primordial deep magma ocean within the Earth. These magma ocean isentropes lead to models that have crystallization initiating at mid-lower mantle depths. Such models are consistent with the suggestion that the present ultra-low velocity zones, at the base of the lowermost mantle, represent a dynamically stable, partially molten remnant of the primordial magma ocean. The new shock melting data for silicates support a model of the primordial magma ocean that is concordant with the Berkeley-Caltech iron core model [1] for the temperature at the center of the Earth

Configurational entropy of basaltic melts in Earth’s mantle

Although geophysical observations of mantle regions that suggest the presence of partial melt have often been interpreted in light of the properties of basaltic liquids erupted at the surface, the seismic and rheological consequences of partial melting in the upper mantle depend instead on the properties of interstitial basaltic melt at elevated pressure. In particular, basaltic melts and glasses display anomalous mechanical softening upon compression up to several GPa, suggesting that the relevant properties of melt are strongly pressure-dependent. A full understanding of such a softening requires study, under compression, of the atomic structure of primitive small-degree basaltic melts at their formation depth, which has proven to be difficult. Here we report multiNMR spectra for a simplified basaltic glass quenched at pressures up to 5 GPa (corresponding to depths down to ∼150 km). These data allow quantification of short-range structural parameters such as the populations of coordination numbers of Al and Si cations and the cation pairs bonded to oxygen atoms. In the model basaltic glass, the fraction of ^([5,6])Al is ∼40% at 5 GPa and decreases to ∼3% at 1 atm. The estimated fraction of nonbridging oxygens at 5 GPa is ∼84% of that at ambient pressure. Together with data on variable glass compositions at 1 atm, these results allow us to quantify how such structural changes increase the configurational entropy of melts with increasing density. We explore how configurational entropy can be used to explain the anomalous mechanical softening of basaltic melts and glasses

Shock Synthesis of Decagonal Quasicrystals

Abstract The Khatyrka meteorite contains both icosahedral and decagonal quasicrystals. In our previous studies, icosahedral quasicrystals have been synthesized and recovered from shock experiments at the interface between CuAl5 and stainless steel 304 alloys. In this study, we report a new shock recovery experiment aimed at synthesizing decagonal quasicrystals similar to decagonite, natural Al71Ni24Fe5. Aluminum 2024 and permalloy 80 alloys were stacked together and shocked in a stainless steel 304 recovery chamber. Abundant decagonal quasicrystals of average composition Al73Ni19Fe4Cu2Mg0.6Mo0.4Mn0.3 with traces of Si and Cr were found along the recovered interface between the Al and permalloy. The experiment also synthesized AlNiFe alloy with the B2 (CsCl-type) structure and the metastable Al9Ni2 phase. We present chemical (scanning electron microscopy and electron microprobe) and structural (electron backscatter diffraction and transmission electron microscopy) characterization of the recovered phases and discuss the implications of this shock synthesis for the stability of quasicrystals during high-pressure shocks and for the interpretation of the phase assemblage found in Khatyrka

Configurational entropy of basaltic melts in Earth’s mantle

Although geophysical observations of mantle regions that suggest the presence of partial melt have often been interpreted in light of the properties of basaltic liquids erupted at the surface, the seismic and rheological consequences of partial melting in the upper mantle depend instead on the properties of interstitial basaltic melt at elevated pressure. In particular, basaltic melts and glasses display anomalous mechanical softening upon compression up to several GPa, suggesting that the relevant properties of melt are strongly pressure-dependent. A full understanding of such a softening requires study, under compression, of the atomic structure of primitive small-degree basaltic melts at their formation depth, which has proven to be difficult. Here we report multiNMR spectra for a simplified basaltic glass quenched at pressures up to 5 GPa (corresponding to depths down to ∼150 km). These data allow quantification of short-range structural parameters such as the populations of coordination numbers of Al and Si cations and the cation pairs bonded to oxygen atoms. In the model basaltic glass, the fraction of ^([5,6])Al is ∼40% at 5 GPa and decreases to ∼3% at 1 atm. The estimated fraction of nonbridging oxygens at 5 GPa is ∼84% of that at ambient pressure. Together with data on variable glass compositions at 1 atm, these results allow us to quantify how such structural changes increase the configurational entropy of melts with increasing density. We explore how configurational entropy can be used to explain the anomalous mechanical softening of basaltic melts and glasses

Shock Experiments on Basalt - Ferric Sulfate Mixes at 21 GPa & 49 GPa and their Relevance to Martian Meteorite Impact Glasses

Large abundance of Martian atmospheric gases and neutron-induced isotopic excesses as well as Rb-Sr isotopic variations determined in some impact glasses in basaltic shergottites (e.g., Shergotty #DBS, Zagami #H1 and EET79001 #27, #8 and #104) provide definitive evidence for the occurrence of a Martian regolith component in their constituent mineral assemblages. Some of these glass-es, known as gas-rich impact-melts (GRIM), contain numerous micron-sized iron sulfide blebs along with minor amounts of iron sulfate particulates. As these GRIM glasses contain a Martian regolith component and as iron sulfates (but not sulfides) are found to occur abundantly on the Mars surface, we suggested that the sulfide blebs in GRIMs were likely generated by shock-reduction of the parental iron sulfate bearing regolith material that had been incorporated into the cavities/crevices of basaltic host rock prior to the impact event on Mars. To test whether the sulfates could be reduced to sulfides by impact shock, we carried out laboratory shock experiments on a basalt plus ferric sulfate mixture at 49 GPa at the Caltech Shock Wave Laboratory and at 21 GPa at Johnson Space Center (JSC) Experimental Impact Laboratory. The experimental details and the preliminary results for the Caltech 49 GPa experiment were presented at LPSC last year. Here, we report the results for the 21 GPa experiment at JSC and compare these results to obtain further insight into the mechanism of the bleb formation in the GRIM glasses