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

A rare massive yellowish-green serpentinized dunite, covering a minimum area up to ~50 m², has been found in Ji’an County, Jilin Province, Northeast China. It contains primary olivine and secondary serpentine (antigorite) and brucite. Other primary minerals like orthopyroxene, clinopyroxene, and aluminum-rich phase (such as garnet, spinel, and plagioclase), frequently appearing in ultramafic rocks, have not been identified. The olivine is essentially pure forsterite, with an Mg# (100 × Mg/(Mg + Fe)) of ~99.6–99.7. Due to these distinct features, we especially name the protolith of this dunite as jianite (集安岩). The forsterite grains range up to ~2 mm, show clear equilibrium textures such as nearly straight grain boundaries and ~120° dihedral angles at their triple junctions, and display no intragranular or intergranular composition variations. They are extensively ruptured and hydrated (i.e., serpentinized), with the fractures (and the grain boundaries as well) filled by fine-grained antigorite (ideally Mg₆(Si₄O₁₀)(OH)₈) and brucite (ideally Mg(OH)₂). These secondary phases are also extremely poor in Fe, indicating a good chemical equilibrium with the forsterite. The serpentinization reaction may have proceeded as forsterite + fluid = antigorite + brucite at temperatures of ~425(25) °C and at relatively low but undetermined pressures. The fluid was likely a B-rich, but Si-poor dilute aqueous fluid, as implied by the trace element characteristics and water-related infrared features of the forsterites in equilibrium. The petrogenesis of the jianite is presently unclear. Full article

Serpentinization produces molecular hydrogen (H₂) that is capable of supporting communities of microorganisms in hydrothermal fields, which suggests that serpentinization may be closely related to the origin of life at the early history of the Earth and possibly other planets. In this study, serpentinization experiments were performed at 300 °C and 3.0 kbar with natural olivine and peridotite as starting reactants to quantify the influence of acidic and alkaline solutions on the processes of serpentinization. The results reveal that acidic and alkaline solutions greatly influence molecular hydrogen (H₂) generation and the rates of serpentinization. Acidic (pH = 2.50) and alkaline solutions (pH = 13.5) increased H₂ production and the rates of peridotite serpentinization. Highly acidic solutions (2 M HCl), however, decreased the production of H₂ after peridotite serpentinization by around two orders of magnitude. The decrease in H₂ production was associated with a sharp decline in the rates of reaction; e.g., when peridotite was reacted with neutral solutions (0.5 M NaCl), 88% of reaction progress was achieved after an experimental duration of 27 days, and the reaction extent decreased by ~50% for experiments with highly acidic solutions (2 M HCl) over the same period. In contrast, for experiments with solely olivine, highly acidic solutions (2 M HCl) promoted the rates of olivine serpentinization and H₂ production. The contrasting effect of highly acidic solutions (2 M HCl) on the processes of olivine and peridotite serpentinization may reflect the influence of pyroxene minerals, which could release SiO₂ during peridotite serpentinization and, consequently, hydrogen generation and reaction rates may decrease. The experimental results of this study suggest that H₂ production and the rates of serpentinization can be greatly influenced by acidic and alkaline solutions and co-existing minerals (e.g., pyroxene). Full article

Eastern Australia contains a widespread suite of primitive (MgO ≥ 7.5 wt.%) intraplate basaltic provinces, including those sited along the longest continental hotspot track on Earth (≈2000 km), the Cosgrove track. The Buckland volcanic province is the most southerly basaltic province on the Cosgrove track before a >1600 km stretch that contains only sparse leucitite volcanism. Buckland is also situated just northeast of the edge of thick cratonic lithosphere where it transitions to a thinner continental lithosphere (<110 km) to the east, which may influence the production of plume-derived melts. Here, analysis of minor and trace elements in olivines in alkali basalts and basanites from the Buckland Province are combined with whole-rock compositions to elucidate the mantle source assemblages, and to calibrate minor and trace element indicators in olivine for application to source mineralogy. Olivine xenocrysts show element concentration ranges typical for peridotites; Mn and Al concentrations indicate that the ambient mantle is spinel, rather than garnet, peridotite. High modal pyroxene content is indicated by high Ni, Zn/Fe, and Fe/Mn in olivines, while high Ti/Sc is consistent with amphibole in the source. Residual phlogopite in the source of the basanites is indicated by low K/Nb in whole rocks, while apatite contains high P₂O₅ and low Rb/Sr (≥0.015) and Sr/La (≥13). The basanite source assemblage probably contains apatite, phlogopite, olivine, clinopyroxene and orthopyroxene, whereas the alkali basalt source assemblage is probably amphibole, olivine, orthopyroxene and clinopyroxene ± phlogopite ± apatite. Both source assemblages correspond broadly to olivine websterite, with the basanite source lying deeper than that for alkali basalt, explaining the occurrence of phlogopite in the source. This mineralogy, along with whole-rock Ti/Eu, Zr/Hf and P₂O₅/TiO₂ values approaching those of natural carbonatites, provide evidence showing that the Buckland source consists of a peridotite that has interacted with a carbonate-rich melt whose origin may be in the deep lithosphere or asthenosphere beneath the craton. Similar enrichment processes are probably common throughout eastern Australia, controlling trace element characteristics in basaltic provinces. The topography of the underside of the lithosphere may play a significant role in determining mantle source assemblages by diverting and concentrating melt flow, and thus influence the location of basaltic provinces. Full article

Hydrogen substitution has significant effect on the physical properties of olivine, the most abundant mineral in the upper mantle. We collected high-temperature polarized Fourier Transform infrared (FTIR) spectra on hydrous forsterite (Mg-pure olivine) crystals, which were synthesized at 12 GPa, 1473–1673 K. The modes at 3612, 3578, 3566, 3551 cm⁻¹ show comparable negative temperature dependence, and the magnitude of (∂v_i/∂T)_P decreases dramatically with frequency increasing. Whereas, the peak at 3477 cm⁻¹, which is attributed to protonation along the O1...O2 edge on the Si tetrahedron, has a positive temperature dependence. The absorbance intensities of all these OH bands remained almost the same when quenched to room temperature. On the other hand, we also evaluate the hydration effect on the thermodynamic properties (heat capacities). For the anhydrous forsterite sample, the intrinsic anharmonicity could significantly increase the heat capacity by 5~6% when extrapolated to 2000 K. Hydration further increase such difference to ~9%, in both the cases of M-substitution or Si-substitution. Hence, hydration in olivine has significant impact on the anharmonic contribution to the thermodynamic properties, as well as Equations of State and equilibrium isotope fractionation β-factor at high-P,T conditions in the deep mantle. 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

The electrical conductivity of dry sintered olivine aggregates with various contents of magnetite (0, 3, 5, 7, 10, 20, and 100 vol. %) was measured at temperatures of 873–1273 K and a pressure of 2.0 GPa within a frequency range of 0.1–10⁶ Hz. The changes of the electrical conductivity of the samples with temperature followed an Arrhenius relation. The electrical conductivity of the sintered olivine aggregates increased as the magnetite-bearing content increased, and the activation enthalpy decreased, accordingly. When the content of interconnected magnetite was higher than the percolation threshold (~5 vol. %), the electrical conductivity of the samples was markedly enhanced. As the pressure increased from 1.0 to 3.0 GPa, the electrical conductivity of the magnetite-free olivine aggregates decreased, whereas the electrical conductivity of the 5 vol. % magnetite-bearing sample increased. Furthermore, the activation energy and activation volume of the 5 vol. % magnetite-bearing sintered olivine aggregates at atmospheric pressure were calculated to be 0.16 ± 0.04 eV and −1.50 ± 0.04 cm³/mole respectively. Due to the high value of percolation threshold (~5 vol. %) in the magnetite impurity sample, our present results suggest that regional high conductivity anomalies in the deep Earth’s interior cannot be explained by the presence of the interconnected magnetite-bearing olivine aggregates. Full article

Plastic deformation of peridotites in the mantle involves large strains. Orthorhombic olivine does not have enough slip systems to satisfy the von Mises criterion, leading to strong hardening when polycrystals are deformed at rather low temperatures (i.e., below 1200 °C). In this study, we focused on the recovery mechanisms involving grain boundaries and recrystallization. We investigated forsterite samples deformed at large strains at 1100 °C. The deformed microstructures were characterized by transmission electron microscopy using orientation mapping techniques (ACOM-TEM). With this technique, we increased the spatial resolution of characterization compared to standard electron backscatter diffraction (EBSD) maps to further decipher the microstructures at nanoscale. After a plastic strain of 25%, we found pervasive evidence for serrated grain and subgrain boundaries. We interpreted these microstructural features as evidence of occurrences of grain boundary migration mechanisms. Evaluating the driving forces for grain/subgrain boundary motion, we found that the surface tension driving forces were often greater than the strain energy driving force. At larger strains (40%), we found pervasive evidence for discontinuous dynamic recrystallization (dDRX), with nucleation of new grains at grain boundaries. The observations reveal that subgrain migration and grain boundary bulging contribute to the nucleation of new grains. These mechanisms are probably critical to allow peridotitic rocks to achieve large strains under a steady-state regime in the lithospheric 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