Search Results (15)

In situ high-temperature Raman spectroscopy (up to 550 °C) and infrared spectroscopy (up to 700 °C) were employed to analyze hydrous Fe-rich ringwoodite (Fo76 composition containing 0.69 wt% H₂O). The results demonstrate that the hydrous Fe-rich ringwoodite sample undergoes irreversible structural transformation above 300 °C at ambient pressure, converting to an amorphous phase. This indicates a lower thermal stability threshold compared to Fe-bearing ringwoodite (Fo90) with equivalent water content. Notably, identical infrared spectral evolution patterns were observed during heating (25–500 °C) for the studied Fo76 sample and previously reported Fo82/Fo90 specimens, suggesting minimal influence of iron content variation on hydroxyl group behavior. The material derived from Fe-rich ringwoodite through structural transformation at ~350 °C retains the capacity to preserve water within a defined temperature window (400–550 °C). In situ high-pressure Raman spectroscopy experiments conducted up to 20 GPa detected no notable structural modifications, suggesting that hydrous Fe-rich ringwoodite, hydrous Fe-bearing ringwoodite, and hydrous Mg-endmember ringwoodite exhibit comparable structural stability within this pressure range. Full article

The Clapeyron slope is the slope of a phase boundary in P–T space and is essential for understanding mantle dynamics and evolution. The phase boundary is delineating instead of balancing a phase transition’s normal and reverse reactions. Many previous high pressure–temperature experiments determining the phase boundaries of major mantle minerals experienced severe problems due to instantaneous pressure increase by thermal pressure, pressure drop during heating, and sluggish transition kinetics. These complex pressure changes underestimate the transition pressure, while the sluggish kinetics require excess pressures to initiate or proceed with the transition, misinterpreting the phase stability and preventing tight bracketing of the phase boundary. Our recent study developed a novel approach to strictly determine phase stability based on the phase equilibrium definition. Here, we explain the details of this technique, using the post-spinel transition in Mg₂SiO₄ determined by our recent work as an example. An essential technique is to observe the change in X-ray diffraction intensity between ringwoodite and bridgmanite + periclase during the spontaneous pressure drop at a constant temperature and press load with the coexistence of both phases. This observation removes the complicated pressure change upon heating and kinetic problem, providing an accurate and precise phase boundary. Full article

As it descends into the Earth’s mantle, the olivine that constitutes the lithosphere of subducting slabs transforms to its high-pressure polymorphs, wadsleyite and ringwoodite, in the so-called transition zone. These transformations have important rheological consequences, since they may induce weakening, strain localization, and, in some cases, earthquakes. In this study, germanium olivine (Ge-olivine) was used as an analogue material to investigate the rheology of samples undergoing the olivine–ringwoodite transformation. Ge-olivine adopts a ringwoodite structure at pressures ~14 GPa lower than its silicate counterpart does, making the transformation accessible with a Griggs rig. Deformation experiments were carried out in a new-generation Griggs apparatus, where micro-seismicity was recorded in the form of acoustic emissions. A careful analysis of the obtained acoustic signal, combined with an extensive microstructure analysis of the recovered samples, provided major insights into the interplay between transformation and deformation mechanisms. The results show that significant reaction rates cause a weakening via the implementation of ductile shear zones that can be preceded by small brittle precursors. When kinetics are more sluggish, mechanical instabilities lead to transformational faulting, which stems from the unstable propagation of shear bands localizing both strain and transformation. The growth of these shear bands is self-sustained thanks to the negative volume change and the exothermic nature of the reaction, and leads to dynamic rupture, as attested by the acoustic emissions recorded. These micro-earthquakes share striking similarities with deep focus earthquakes, which may explain several seismological observations such as magnitude frequency relations and the occurrence of deep repeating earthquakes and foreshocks. Full article

The introduction of multigrain crystallography (MGC) applied in a laser-heated diamond anvil cell (LH-DAC) using synchrotron X-rays has provided a new path to investigate the microstructural evolution of materials at extreme conditions, allowing for simultaneous investigations of phase identification, strain state determination, and orientation relations across phase transitions in a single experiment. Here, we applied this method to a sample of San Carlos olivine beginning at ambient conditions and through the α-olivine → γ-ringwoodite phase transition. At ambient temperatures, by measuring the evolution of individual Bragg reflections, olivine shows profuse angular streaking consistent with the onset of yielding at a measured stress of ~1.5 GPa, considerably lower than previously reported, which may have implications for mantle evolution. Furthermore, γ-ringwoodite phase was found to nucleate as micron to sub-micron grains imbedded with small amounts of a secondary phase at 15 GPa and 1000 °C. Using MGC, we were able to extract and refine individual crystallites of the secondary unknown phase where it was found to have a structure consistent with the ε-phase previously described in chondritic meteorites. Full article

Synchrotron X-ray diffraction, as well as visual observations, in a diamond anvil cell (DAC) using soft metal gaskets or slightly reducing gas environment, have revealed that the olivine-ringwoodite transition in olivines of several compositions take place in two steps: step 1: displacive restacking of the oxygen layers, followed by step 2: diffusive reordering of the cations. The initiation of the phase transition was observed at temperatures as low as 200 °C below the reported temperature for the phase transition under hydrostatic conditions. These observations, especially residual disordered cations, have important implications for deep-focus earthquakes, the ability of ringwoodite to host surprising amounts of water, and possibly the observation of a blue olivine inclusion in a natural diamond from Brazil and in a pallasitic meteorite from Russia. Full article

Three batches of Mg₂SiO₄-ringwoodites (Mg-Rw) with different water contents (C_H2O = ~1019(238), 5500(229) and 16,307(1219) ppm) were synthesized by using conventional high-P experimental techniques. Thirteen thin sections with different thicknesses (~14–113 μm) were prepared from them and examined for water-related IR peaks using unpolarized infrared spectra at ambient P-T conditions, leading to the observation of 15 IR peaks at ~3682, 3407, 3348, 3278, 3100, 2849, 2660, 2556, 2448, 1352, 1347, 1307, 1282, 1194 and 1186 cm⁻¹. These IR peaks suggest multiple types of hydrogen defects in hydrous Mg-Rw. We have attributed the IR peaks at ~3680, 3650–3000 and 3000–2000 cm⁻¹, respectively, to the hydrogen defects [V_Si(OH)₄], [V_Mg(OH)₂Mg_SiSi_Mg] and [V_Mg(OH)₂]. Combining these IR features with the chemical characteristics of hydrous Rw, we have revealed that the hydrogen defects [V_Mg(OH)₂Mg_SiSi_Mg] are dominant in hydrous Rw at high P-T conditions, and the defects [V_Si(OH)₄] and [V_Mg(OH)₂] play negligible roles. Extensive IR measurements were performed on seven thin sections annealed for several times at T of 200–600 °C and quickly quenched to room T. They display many significant variations, including an absorption enhancement of the peak at ~3680 cm⁻¹, two new peaks occurring at ~3510 and 3461 cm⁻¹, remarkable intensifications of the peaks at ~3405 and 3345 cm⁻¹ and significant absorption reductions of the peaks at ~2500 cm⁻¹. These phenomena imply significant hydrogen migration among different crystallographic sites and rearrangement of the O-H dipoles in hydrous Mg-Rw at high T. From the IR spectra obtained for hydrous Rw both unannealed and annealed at high T, we further infer that substantial amounts of cation disorder should be present in hydrous Rw at the P-T conditions of the mantle transition zone, as required by the formation of the hydrogen defects [V_Mg(OH)₂Mg_SiSi_Mg]. The Mg-Si disorder may have very large effects on the physical and chemical properties of Rw, as exampled by its disproportional effects on the unit-cell volume and thermal expansivity. Full article

Trace elements play a significant role in interpretation of different processes in the deep Earth. However, the systematics of interphase rare-earth element (REE) partitioning under the conditions of the uppermost lower mantle are poorly understood. We performed high-pressure experiments to study the phase relations in key solid-phase reactions CaMgSi₂O₆ = CaSiO₃-perovskite + MgSiO₃-bridgmanite and (Mg,Fe)₂SiO₄-ringwoodite = (Mg,Fe)SiO₃-bridgmanite + (Mg,Fe)O with addition of 1 wt % of REE oxides. Atomistic modeling was used to obtain more accurate quantitative estimates of the interphase REE partitioning and displayed the ideal model for the high-pressure minerals. HREE (Er, Tm, Yb, and Lu) are mostly accumulated in bridgmanite, while LREE are predominantly redistributed into CaSiO₃. On the basis of the results of experiments and atomistic modeling, REE in bridgmanite are clearly divided into two groups (from La to Gd and from Gd to Lu). Interphase REE partition coefficients in solid-state reactions were calculated at 21.5 and 24 GPa for the first time. The new data are applicable for interpretation of the trace-element composition of the lower mantle inclusions in natural diamonds from kimberlite; the experimentally determined effect of pressure on the interphase (bridgmanite/CaSiO₃-perovskite) REE partition coefficients can be a potential qualitative geobarometer for mineral inclusions in super-deep diamonds. Full article

In this paper, we present the recent progress in the experimental studies of the electrical conductivity of dominant nominally anhydrous minerals in the upper mantle and mantle transition zone of Earth, namely, olivine, pyroxene, garnet, wadsleyite and ringwoodite. The main influence factors, such as temperature, pressure, water content, oxygen fugacity, and anisotropy are discussed in detail. The dominant conduction mechanisms of Fe-bearing silicate minerals involve the iron-related small polaron with a relatively large activation enthalpy and the hydrogen-related defect with lower activation enthalpy. Specifically, we mainly focus on the variation of oxygen fugacity on the electrical conductivity of anhydrous and hydrous mantle minerals, which exhibit clearly different charge transport processes. In representative temperature and pressure environments, the hydrogen of nominally anhydrous minerals can tremendously enhance the electrical conductivity of the upper mantle and transition zone, and the influence of trace structural water (or hydrogen) is substantial. In combination with the geophysical data of magnetotelluric surveys, the laboratory-based electrical conductivity measurements can provide significant constraints to the water distribution in Earth’s interior. Full article

To elucidate the water cycles in iron-rich Mars, we investigated the phase relation of a water-undersaturated (2 wt.%) analog of Martian mantle in simplified MgO-Al₂O₃-FeO-SiO₂-H₂O (MAFSH) system between 15 and 21 GPa at 900–1500 °C using a multi-anvil apparatus. Results showed that phase E coexisting with wadsleyite or ringwoodite was at least stable at 15–16.5 GPa and below 1050 °C. Phase D coexisted with ringwoodite at pressures higher than 16.5 GPa and temperatures below 1100 °C. The transition pressure of the loop at the wadsleyite-ringwoodite boundary shifted towards lower pressure in an iron-rich system compared with a hydrous pyrolite model of the Earth. Some evidence indicates that water once existed on the Martian surface on ancient Mars. The water present in the hydrous crust might have been brought into the deep interior by the convecting mantle. Therefore, water might have been transported to the deep Martian interior by hydrous minerals, such as phase E and phase D, in cold subduction plates. Moreover, it might have been stored in wadsleyite or ringwoodite after those hydrous materials decomposed when the plates equilibrated thermally with the surrounding Martian mantle. Full article

Knowledge of the thermal diffusivity D and thermal conductivity κ of olivine and its high-pressure polymorphs, wadsleyite and ringwoodite, is crucial to understand the heat transfer efficiency and thermal structure of Earth’s mantle. In the last few decades, great progress has been made in measurement techniques and experimental results seeking to determine the thermophysical properties of geomaterials. The aim of this paper is to provide a systematic overview of the current knowledge of the thermal transport properties of olivine and its high-pressure polymorphs, their dependence on factors, such as pressure, temperature, and composition, and physical models to describe their variations. Some related geoscience applications and perspectives for the future are also suggested. Full article

The metastable olivine (Ol) wedge hypothesis assumes that Ol may exist as a metastable phase at the P conditions of the mantle transition zone (MTZ) and even deeper regions due to inhibition of the phase transitions from Ol to wadsleyite and ringwoodite caused by low T in the cold subducting slabs. It is commonly invoked to account for the stagnation of the descending slabs, deep focus earthquakes and other geophysical observations. In the last few years, several new structures with the forsterite (Fo) composition, namely Fo-II, Fo-III and Fo-IV, were either experimentally observed or theoretically predicted at very low T conditions. They may have important impacts on the metastable Ol wedge hypothesis. By performing first-principles calculations, we have systematically examined their crystallographic characteristics, elastic properties and dynamic stabilities from 0 to 100 GPa, and identified the Fo-III phase as the most likely metastable phase to occur in the cold slabs subducted to the depths equivalent to the lower part of the MTZ (below the ~600 km depth) and even the lower mantle. As disclosed by our theoretical simulations, the Fo-III phase is a post-spinel phase (space group Cmc2₁), has all cations in sixfold coordination at P < ~60 GPa, and shows dynamic stability for the entire P range from 0 to 100 GPa. Further, our static enthalpy calculations have suggested that the Fo-III phase may directly form from the Fo material at ~22 GPa (0 K), and our high-T phase relation calculations have located the Fo/Fo-III phase boundary at ~23.75 GPa (room T) with an averaged Clapeyron slope of ~−1.1 MPa/K for the T interval from 300 to 1800 K. All these calculated phase transition pressures are likely overestimated by ~3 GPa because of the GGA method used in this study. The discrepancy between our predicted phase transition P and the experimental observation (~58 GPa at 300 K) can be explained by slow reaction rate and short experimental durations. Taking into account the P-T conditions in the cold downgoing slabs, we therefore propose that the Fo-III phase, rather than the Ol, highly possibly occurs as the metastable phase in the cold slabs subducted to the P conditions of the lower part of the MTZ (below the ~600 km depth) and even the lower mantle. In addition, our calculation has showed that the Fo-III phase has higher bulk seismic velocity, and thus may make important contributions to the high seismic speeds observed in the cold slabs stagnated near the upper mantle-lower mantle boundary. Future seismic studies may discriminate the effects of the Fo-III phase and the low T. Surprisingly, the Fo-III phase will speed up, rather than slow down, the subducting process of the cold slabs, if it metastably forms from the Ol. In general, the Fo-III phase has a higher density than the warm MTZ, but has a lower density than the lower mantle, as suggested by our calculations. Full article

A series of Si-bearing MgAl₂O₄-spinels were synthesized at 1500–1650 °C and 3–6 GPa. These spinels had SiO₂ contents of up to ~1.03 wt % and showed a substitution mechanism of Si⁴⁺ + Mg²⁺ = 2Al³⁺. Unpolarized Raman spectra were collected from polished single grains, and displayed a set of well-defined Raman peaks at ~610, 823, 856 and 968 cm⁻¹ that had not been observed before. Aided by the Raman features of natural Si-free MgAl₂O₄-spinel, synthetic Si-free MgAl₂O₄-spinel, natural low quartz, synthetic coesite, synthetic stishovite and synthetic forsterite, we infer that these Raman peaks should belong to the SiO₄ groups. The relations between the Raman intensities and SiO₂ contents of the Si-bearing MgAl₂O₄-spinels suggest that under some P-T conditions, some Si must adopt the M-site. Unlike the SiO₄ groups with very intense Raman signals, the SiO₆ groups are largely Raman-inactive. We further found that the Si cations primarily appear on the T-site at P-T conditions ≤~3–4 GPa and 1500 °C, but attain a random distribution between the T-site and M-site at P-T conditions ≥~5–6 GPa and 1630–1650 °C. This Si-disordering process observed for the Si-bearing MgAl₂O₄-spinels suggests that similar Si-disordering might happen to the (Mg,Fe)₂SiO₄-spinels (ringwoodite), the major phase in the lower part of the mantle transition zone of the Earth and the benchmark mineral for the very strong shock stage experienced by extraterrestrial materials. The likely consequences have been explored. Full article

The mantle transition zone represents an important layer in the interior of the Earth that is characterized by phase transformations of olivine polymorphs. Constraining the rheology difference between wadsleyite and ringwoodite is important in determining the viscosity contrast at a depth of 520 km. In this study, we perform a post-mortem by transmission electron microscopy of a wadsleyite + ringwoodite aggregate, deformed at high-pressure and high-temperature, in a deformation-DIA apparatus. From orientation maps acquired by scanning precession electron diffraction, we calculate local misorientations and misorientation-gradients, which are used as a proxy of plastic strain. We show that at 17.3 GPa, 1700 K, the plastic responses of wadsleyite and ringwoodite are comparable, although recovery by subgrain boundary migration is more easily activated in wadsleyite. Full article

Shock metamorphism of minerals in meteorites could help to understand the shock history of its parent body and also provide a window into the interior of the Earth. Although shock features in olivine have been well known within and adjacent to shock melt veins and shock melt pockets in meteorites, there are processes that are not yet completely understood. Ringwoodite is formed by crystallization from olivine melts or solid-state phase transformation of olivine. Typically, olivine clasts with a ringwoodite rim around an olivine core have been documented from only a handful of meteorites. Here we report results from GRV053684, a highly shocked L6 chondrite that was collected by Chinese Antarctic Research Expedition in 2006 to Antarctica. The investigations of the shock pressure history and the transformation mechanism of olivine to ringwoodite use optical microscope, electron probe microanalyzer (backscattered electron images, major element quantitative analyses, and quantitative wavelength-dispersive spectrometry elemental X-ray maps), and Raman spectrograph. Ringwoodite in the shock melt vein generally displays as Fe-rich (Fa_37-43) polycrystalline rims around Fe-poor (Fa_11-20) olivine core and as small individual clasts embedded in shock melt vein matrix. The difference in FeO between ringwoodite rim and olivine core implies that Fe was preferentially partitioned to ringwoodite. The occurrence of maskelynite (An₁₇) indicates a shock pressure ~30 GPa. The FeO and MgO diffusion indicates the transformation process of olivine to ringwoodite is a diffusion-controlled incoherent nucleation and growth. The spatial association between ringwoodite and the shock melt vein matrix suggests that high temperature plays a key role in prompting phase transformation. Full article

Ab initio thermodynamic properties, equation of state and phase stability of periclase (MgO, B1-type structure) have been investigated in a broad P–T range (0–160 GPa; 0–3000 K) in order to set a model reference system for phase equilibria simulations under deep Earth conditions. Phonon dispersion calculations performed on large supercells using the finite displacement method and in the framework of quasi-harmonic approximation highlight the performance of the Becke three-parameter Lee-Yang-Parr (B3LYP) hybrid density functional in predicting accurate thermodynamic functions (heat capacity, entropy, thermal expansivity, isothermal bulk modulus) and phase reaction boundaries at high pressure and temperature. A first principles Mie–Grüneisen equation of state based on lattice vibrations directly provides a physically-consistent description of thermal pressure and P–V–T relations without any need to rely on empirical parameters or other phenomenological formalisms that could give spurious anomalies or uncontrolled extrapolations at HP–HT. The post-spinel phase transformation, Mg₂SiO₄ (ringwoodite) = MgO (periclase) + MgSiO₃ (bridgmanite), is taken as a computational example to illustrate how first principles theory combined with the use of hybrid functionals is able to provide sound results on the Clapeyron slope, density change and P–T location of equilibrium mineral reactions relevant to mantle dynamics. Full article