Search for: All records

Abstract Fluids and melts in planetary interiors significantly influence geodynamic processes from volcanism to global‐scale differentiation. The roles of these geofluids depend on their viscosities (η). Constraining geofluidηat relevant pressures and temperatures relies on laboratory‐based measurements and is most widely done using Stokes' Law viscometry with falling spheres. Yet small sample chambers required by high‐pressure experiments introduce significant drag on the spheres. Several correction schemes are available for Stokes' Law but there is no consensus on the best scheme(s) for high‐pressure experiments. We completed high‐pressure experiments to test the effects of (a) the relative size of the sphere diameter to the chamber diameter and (b) the top and bottom of the chamber, that is, the ends, on the sphere velocities. We examined the influence of current correction schemes on the estimated viscosity using Monte Carlo simulations. We also compared previous viscometry work on various geofluids in different experimental setups/geometries. We find the common schemes for Stokes' Law produce statistically distinct values ofη. When inertia of the sphere is negligible, the most appropriate scheme may be the Faxén correction for the chamber walls. Correction for drag due to the chamber ends depends on the precision in the sinking distance and may be ineffective with decreasing sphere size. Combining the wall and end corrections may overcorrectη. We also suggest the uncertainty inηis best captured by the correction rather than propagated errors from experimental parameters. We develop an overlying view of Stokes' Law viscometry at high pressures. 

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 (ρ_hydrous < ρ_anhydrous) but increases the compressibility, that is, 1/K_hydrous>1/K_anhydrousorK_hydrous < K_anhydrous. We also find that the meltηdecreases with pressure and then increases with further compression. Water decreases the viscosity (η_hydrous < η_anhydrous) 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. 

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 Slab surface temperature is one of the key parameters that incur first-order changes in subduction dynamics. However, the current thermal models are based on empirical thermal parameters and do not accurately capture the complex pressure–temperature paths of the subducting slab, prompting significant uncertainties on slab temperature estimations. In this study, we investigate whether the dehydration-melting of glaucophane can be used to benchmark the temperature in the slab. We observe that dehydration and melting of glaucophane occur at relatively low temperatures compared to the principal hydrous phases in the slab and produce highly conductive Na-rich melt. The electrical properties of glaucophane and its dehydration products are notably different from the hydrous minerals and silicate melts. Hence, we conclude that the thermodynamic instability of glaucophane in the slab provides a unique petrological criterion for tracking temperature in the present-day subduction systems through magnetotelluric profiles. 

Abstract Evaluating carbon’s candidacy as a light element in the Earth’s core is critical to constrain the budget and planet-scale distribution of this life-essential element. Here we use first principles molecular dynamics simulations to estimate the density and compressional wave velocity of liquid iron-carbon alloys with ~4-9 wt.% carbon at 0-360 gigapascals and 4000-7000 kelvin. We find that for an iron-carbon binary system, ~1-4 wt.% carbon can explain seismological compressional wave velocities. However, this is incompatible with the ~5-7 wt.% carbon that we find is required to explain the core’s density deficit. When we consider a ternary system including iron, carbon and another light element combined with additional constraints from iron meteorites and the density discontinuity at the inner-core boundary, we find that a carbon content of the outer core of 0.3-2.0 wt.%, is able to satisfy both properties. This could make the outer core the largest reservoir of terrestrial carbon. 

Abstract The dehydration and decarbonation in the subducting slab are intricately related and the knowledge of the physical properties of the resulting C–H–O fluid is crucial to interpret the petrological, geochemical, and geophysical processes associated with subduction zones. In this study, we investigate the C–H–O fluid released during the progressive devolatilization of carbonate-bearing serpentine-polymorph chrysotile, with in situ electrical conductivity measurements at high pressures and temperatures. The C–H–O fluid produced by carbonated chrysotile exhibits high electrical conductivity compared to carbon-free aqueous fluids and can be an excellent indicator of the migration of carbon in subduction zones. The crystallization of diamond and graphite indicates that the oxidized C–H–O fluids are responsible for the recycling of carbon in the wedge mantle. The carbonate and chrysotile bearing assemblages stabilize dolomite during the devolatilization process. This unique dolomite forming mechanism in chrysotile in subduction slabs may facilitate the transport of carbon into the deep mantle. 

Abstract Amphiboles are hydrous minerals that are formed in the oceanic crust via hydrothermal alteration. The partial substitution of halogens for OH⁻makes amphibole one of the principal hosts of Cl and F in the subducting slab. In this study, we investigated the electrical conductivity of a suite of halogen bearing amphibole minerals at 1.5 GPa up to 1,400 K. The discontinuous electrical behavior indicates dehydration of amphibole at ∼915 K. This is followed by dehydration induced hydrous melting at temperatures above 1,070 K. We find that the released aqueous fluids have an electrical conductivity of ∼0.1 S/m. This high electrical conductivity is likely to explain anomalously high electrical conductivity observed in certain subduction zone settings. This high electrical conductivity of an order of magnitude greater than the electrical conductivity of pure aqueous fluids at similar conditions is likely due to the partitioning of the F and Cl into the aqueous fluids. We also noted that subsequent to the dehydration, secondary phases form due to the breakdown of the primary halogen bearing amphibole. Chemical analyses of these secondary phases indicate that they are repositories of F and Cl. Hence, we infer that upon dehydration of the primary halogen bearing amphibole, first the F and Cl are partitioned into the aqueous fluids and then the halogens are partitioned back to the secondary mineral phases. These secondary minerals are likely to transport the halogen to the deep Earth and may in part explain the halogen concentration observed in ocean island basalt. 

Abstract Liebermannite (KAlSi₃O₈) is a principal mineral phase expected to be thermodynamically stable in deeply subducted continental and oceanic crusts. The crystal structure of liebermannite exhibits tunnels that are formed between the assemblies of double chains of edge‐sharing (Si, Al) O₆octahedral units, which act as a repository for large incompatible alkali ions. In this study, we investigate the electrical conductivity of liebermannite at 12, 15, and 24 GPa and temperature of 1500 K to track subduction pathways of continental sediments into the Earth's lower mantle. Further, we looked at whether liebermannite could sequester incompatible H₂O at deep mantle conditions. We observe that the superionic conductivity of liebermannite due to the thermally activated hopping of K⁺ions results in high electrical conductivity of more than 1 S/m. Infrared spectral features of hydrous liebermannite indicate the presence of both molecular H₂O and hydroxyl (OH⁻) groups in its crystal structure. The observed high electrical conductivity in the mantle transition zone beneath Northeastern China and the lower mantle beneath the Philippine Sea can be attributed to the subduction pathways of continental sediments deep into the Earth's mantle. While major mineral phases in pyrolitic compositions are almost devoid of H₂O under lower mantle conditions, our study demonstrates that liebermannite could be an important host of H₂O in these conditions. We propose that the relatively high H₂O contents of ocean island basalts derived from deep mantle plumes are primarily related to deeply subducted continental sediments, in which liebermannite is the principal H₂O carrier. 

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. 

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.