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Creators/Authors contains: "Mookherjee, Mainak"

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  1. The continental crust is rich in aluminosilicates and formed by the crystallization of arc magmas. However, the magma produced at sub-arc depths is often silica-poor. The chemical evolution of sub-arc magma from silica-poor to aluminosilicate-rich is perplexing. Magnetotelluric (MT) observations in subduction zones and complementary laboratory-based constraints of electrical conductivity (σ) are crucial to understanding this chemical evolution. The σ of a magma is sensitive to pressure (P), temperature (T), and chemistry (X). To date, laboratory-based measurements on the σ of silicate melts have helped to interpret MT observations at P ≤ 2 GPa. Yet, the melting in subduction zones could occur deeper, at P ≤ 6−7 GPa. The σ of melt at such pressures is poorly constrained. To address this, we performed experiments at P ≤ 6 GPa to examine the σ of basaltic to andesitic melts, which are common in subduction zones. We constrained the effects of silica, alumina, alkali, alkaline, and water (H2O) contents on the σ of melt. The activation volume of σ increases with silica contents. Hence, the σ of basaltic melt is overall greater than that of an andesitic counterpart. The σ of basaltic magma is also less sensitive to P than andesitic magma. Water lowers the activation energy and enhances σ for all melt compositions. Our results help constrain how the electrical properties of a magma change with an evolving composition in a subduction zone. 
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    Free, publicly-accessible full text available March 19, 2026
  2. Kaolinite is formed by weathering of continental crustal rocks and is also found in marine sediments in the tropical region. Kaolinite and other layered hydrous silicate minerals are likely to play a vital role in transporting water into the Earth’s interior via subducting slabs. Recent studies have experimentally documented the expansion of the interlayer region by intercalation of water molecules at high pressures i.e., pressure-induced hydration. This is counter-intuitive since the interlayer region in the layered silicates is quite compressible, so it is important to understand the underlying mechanism that causes intercalation and expansion of the interlayer region. To address this, we explore the high-pressure behavior of natural kaolinite from Keokuk, Iowa. This sample is free of anatase impurities and thus helps to examine both low-energy (0–1200 cm−1) and high-energy hydroxyl (3000–4000 cm−1) regions using Raman spectroscopy and synchrotron-based powder X-ray diffraction. Our results show that the pressure dependence of the hydroxyl modes exhibits discontinuities at ~3 GPa and ~ 6.5 GPa. This is related to the polytypic transformation of Kaolinite from K-1 to K-II and K-II to K-III phase. Several low-energy Raman modes’ pressure dependence also exhibits similar discontinuous behavior. The synchrotron-based powder X-ray diffraction results also indicate discontinuous behavior in the pressure dependence of the unit-cell volume and lattice parameters. The analysis of the bulk and the linear compressibility reveals that kaolinite is extremely anisotropic and is likely to aid its geophysical detectability in subduction zone settings. The K-I to K-II polytypic transition is marked by the snapping of hydrogen bonds, thus at conditions relevant to the Earth’s interior, water molecules intercalate in the interlayer region and stabilize the crystal structure and help form the super-hydrated kaolinite which can transport significantly more water into the Earth’s interior. 
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  3. 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. 
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  4. Abstract The viscosity of magma plays a crucial role in the dynamics of the Earth: from the crystallization of a magma ocean during its initial stages to modern-day volcanic processes. However, the pressure-dependence behavior of viscosity at high pressure remains controversial. In this study, we report the results of first-principles molecular dynamics simulations of basaltic melt to show that the melt viscosity increases upon compression along each isotherm for the entire lower mantle after showing minima at ~6 GPa. However, elevated temperatures of the magma ocean translate to a narrow range of viscosity, i.e., 0.01–0.03 Pa.s. This low viscosity implies that the crystallization of the magma ocean could be complete within a few million years. These results also suggest that the crystallization of the magma ocean is likely to be fractional, thus supporting the hypothesis that present-day mantle heterogeneities could have been generated during the early crystallization of the primitive mantle. 
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  5. Abstract A plausible origin of the seismically observed mid-lithospheric discontinuity (MLD) in the subcontinental lithosphere is mantle metasomatism. The metasomatized mantle is likely to stabilize hydrous phases such as amphiboles. The existing electrical conductivity data on amphiboles vary significantly. The electrical conductivity of hornblendite is much higher than that of tremolite. Thus, if hornblendite truly represents the amphibole varieties in MLD regions, then it is likely that amphibole will cause high electrical conductivity anomalies at MLD depths. However, this is inconsistent with the magnetotelluric observations across MLD depths. Hence, to better understand this discrepancy in electrical conductivity data of amphiboles and to evaluate whether MLD could be caused by metasomatism, we determined the electrical conductivity of a natural metasomatized rock sample. The metasomatized rock sample consists of ~87% diopside pyroxene, ~9% sodium-bearing tremolite amphibole, and ~3% albite feldspar. We collected the electrical conductivity data at ~3.0 GPa, i.e., the depth relevant to MLD. We also spanned a temperature range between 400 to 1000 K. We found that the electrical conductivity of this metasomatized rock sample increases with temperature. The temperature dependence of the electrical conductivity exhibits two distinct regimes. At low temperatures <700 K, the electrical conductivity is dominated by the conduction in the solid state. At temperatures >775 K, the conductivity increases, and it is likely to be dominated by the conduction of aqueous fluids due to partial dehydration. The main distinction between the current study and the prior studies on the electrical conductivity of amphiboles or amphibole-bearing rocks is the sodium (Na) content in amphiboles of the assemblage. Moreover, it is likely that the higher Na content in amphiboles leads to higher electrical conductivity. Pargasite and edenite amphiboles are the most common amphibole varieties in the metasomatized mantle, and our study on Na-bearing tremolite is the closest analog of these amphiboles. Comparison of the electrical conductivity results with the magnetotelluric observations constrains the amphibole abundance at MLD depths to <1.5%. Such a low-modal proportion of amphiboles could only reduce the seismic shear wave velocity by 0.4–0.5%, which is significantly lower than the observed velocity reduction of 2–6%. Thus, it might be challenging to explain both seismic and magnetotelluric observations at MLD simultaneously. 
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  6. Abstract The continental crust is produced by the solidification of aluminosilicate‐rich magmas which are sourced from deep below the surface. Migration of the magma depends on the density (ρ) contrast to source rocks and the melt viscosity (η). At the surface, these silica‐rich melts are typically sluggish due to highη > 1,000 Pa s. Yet at their source regions, the melt properties are complexly influenced by pressure (P), temperature (T), and water contents (). In this study, we examined the combinedP‐T‐ effects on the behavior of melts with an albite stoichiometry (NaAlSi3O8). We usedfirst‐principlesmolecular dynamics simulations to examine anhydrous (0 wt % H2O) and hydrous (5 wt % H2O) melts. To constrain thePandTeffects, we exploredP ≤ 25 GPa across several isotherms between 2500 and 4000 K. The melts show anomalousP‐ρrelationships at lowP ∼ 0 GPa and highT ≥ 2500 K, consistent with vaporization. At lithospheric conditions, meltρincreases with compression and is well described by a finite‐strain formalism. Water lowers the melt density (ρhydrous < ρanhydrous) but increases the compressibility, that is, 1/Khydrous>1/KanhydrousorKhydrous < Kanhydrous. We also find that the meltηdecreases with pressure and then increases with further compression. Water decreases the viscosity (ηhydrous < ηanhydrous) by depolymerizing the melt structure. The ionic self‐diffusivities are increased by the presence of water. The decreasedρandηby H2O increase the mobility of magma at crustal conditions, which could explain the rapid eruption and migration timescales for rhyolitic magmas as observed in the Chaitén volcano in Chile. 
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