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Abstract The 3.65 Å phase [MgSi(OH)6] is a hydrous phase that is predicted to be stable in a simplified MgO-SiO2-H2O (MSH) ternary system at pressures exceeding 9 GPa. Along cold subduction zones, it is likely to transport water, bound in its crystalline lattice, into the Earth’s interior. The 3.65 Å phase consists of Mg and Si octahedral sites attached to the hydroxyl group that forms a hydrogen bond and is predicted to undergo pressure-induced symmetrization of the hydrogen bond. Therefore, in this study, we investigate the high-pressure behavior of the 3.65 Å phase using Raman spectroscopy. We have conducted five distinct compressions up to ~60 GPa using two different pressure-transmitting media—alcohol mixture and neon. At ambient conditions, we identified vibrational modes using complementary first-principles simulations based on density functional perturbation theory. Upon compression, we note that the first derivative of the vibrational modes in the lattice region stiffens, i.e., b1lattice > 0. In contrast, the hydroxyl region softens, i.e., b1OH > 0. This is indicative of the strengthening of hydrogen bonding upon compression. We noticed a significant broadening of vibrational modes related to hydroxyl groups that are indicative of proton disorder. However, within the maximum pressures explored in this study, we did not find evidence for pressure-induced symmetrization of the hydrogen bonds. We used the pressure derivative of the vibrational modes to determine the ratio of the bulk moduli and their pressure derivative. We note that the smaller bulk moduli of hydrous phases compared to the major mantle phases are compensated by significantly larger pressure derivatives of the bulk moduli for the hydrous phases. This leads to a significant reduction in the elasticity contrast between hydrous and major mantle phases. Consequently, the detection of the degree of mantle hydration is likely to be challenging at greater depths. 

Abstract Inclusions of relic high-pressure melts provide crucial information on the fate of crustal rocks in the deep roots of orogens during collision and crustal thickening, including at extreme temperature conditions exceeding 1000 °C. However, discoveries of high-pressure melt inclusions are still a relative rarity among case studies of inclusions in metamorphic minerals. Here we present the results of experimental and microchemical investigations of nanogranitoids in garnets from the felsic granulites of the Central Maine Terrane (Connecticut, U.S.A.). Their successful experimental re-homogenization at ~2 GPa confirms that they originally were trapped portions of deep melts and makes them the first direct evidence of high pressure during peak metamorphism and melting for these felsic granulites. The trapped melt has a hydrous, granitic, and peraluminous character typical of crustal melts from metapelites. This melt is higher in mafic components (FeO and MgO) than most of the nanogranitoids investigated previously, likely the result of the extreme melting temperatures—well above 1000 °C. This is the first natural evidence of the positive correlation between temperature and mafic character of the melt; a trend previously supported only by experimental evidence. Moreover, it poses a severe caveat against the common assumption that partial melts from metasediments at depth are always leucogranitic in composition. NanoSIMS measurement on re-homogenized inclusions show significant amounts of CO2, Cl, and F. Halogen abundance in the melt is considered to be a proxy for the presence of brines (strongly saline fluids) at depth. Brines are known to shift the melting temperatures of the system toward higher values and may have been responsible for delaying melt production via biotite dehydration melting until these rocks reached extreme temperatures of more than 1000 °C, rather than 800–850 °C as commonly observed for these reactions. 

Phase egg, [AlSiO3(OH)], is an aluminosilicate hydrous mineral that is thermodynamically stable in lithological compositions represented by Al2O3-SiO2-H2O (ASH) ternary, i.e., a simplified ternary for the mineralogy of subducted sediments and continental crustal rocks. High-pressure and high-temperature experiments on lithological compositions resembling hydrated sedimentary layers in subducting slabs show that phase egg is stable up to pressures of 20–30 GPa, which translates to the transition zone to lower mantle depths. Thus, phase egg is a potential candidate for transporting water into the Earth’s mantle transition zone. In this study, we use first-principles simulations based on density functional theory to explore the pressure dependence of crystal structure and how it influences energetics and elasticity. Our results indicate that phase egg exhibits anomalous behavior of the pressure dependence of the elasticity at mantle transition zone depths (~15 GPa). Such anomalous behavior in the elasticity is related to changes in the hydrogen bonding O-H···O configurations, which we delineate as a transition from a low-pressure to a high-pressure structure of phase egg. Full elastic constant tensors indicate that phase egg is very anisotropic resulting in a maximum anisotropy of compressional wave velocity, AvP ≈ 30% and of shear wave velocity, AvS ≈ 17% at zero pressures. Our results also indicate that the phase egg has one of the fastest bulk sound velocities (vP and vS) compared to other hydrous aluminous phases in the ASH ternary, which include topaz-OH, phase Pi, and d-AlOOH. However, the bulk sound velocity of phase egg is slower than that of stishovite. At depths corresponding to the base of mantle transition zone, phase egg decomposes to a mixture of d-AlOOH and stishovite. The changes in compressional DvP and shear DvS velocity associated with the decomposition is ~0.42% and –1.23%, respectively. Although phase egg may be limited to subducted sediments, it could hold several weight percentages of water along a normal mantle geotherm.