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At least 217 records · Page 12

Effects of composition and pressure on electronic states of iron in bridgmanite

Electronic states of iron in the lower mantle's dominant mineral, (Mg,Fe,Al)(Fe,Al,Si)O 3 bridgmanite, control physical properties of the mantle including density, elasticity, and electrical and thermal conductivity. However, the determination of electronic states of iron has been controversial, in part due to different interpretations of Mössbauer spectroscopy results used to identify spin state, valence state, and site occupancy of iron. We applied energy-domain Mössbauer spectroscopy to a set of four bridgmanite samples spanning a wide range of compositions: 10–50% Fe/total cations, 0–25% Al/total cations, 12–100% Fe 3+ /total Fe. Measurements performed in the diamond-anvil cell at pressures up to 76 GPa below and above the high to low spin transition in Fe 3+ provide a Mössbauer reference library for bridgmanite and demonstrate the effects of pressure and composition on electronic states of iron. Results indicate that although the spin transition in Fe 3+ in the bridgmanite B-site occurs as predicted, it does not strongly affect the observed quadrupole splitting of 1.4 mm/s, and only decreases center shift for this site to 0 mm/s at ~70 GPa. Thus center shift can easily distinguish Fe 3+ from Fe 2+ at high pressure, which exhibits two distinct Mössbauer sites with center shift ~1 mm/s and quadrupole splitting 2.4–3.1 and 3.9 mm/s at ~70 GPa. Correct quantification of Fe 3+ /total Fe in bridgmanite is required to constrain the effects of composition and redox states in experimental measurements of seismic properties of bridgmanite. Furthermore, in Fe-rich, mixed-valence bridgmanite at deep-mantle-relevant pressures, up to ~20% of the Fe may be a Fe 2.5+ charge transfer component, which should enhance electrical and thermal conductivity in Fe-rich heterogeneities at the base of Earth's mantle.

58 GEOSCIENCES↗

Atomic-scale mechanism of carbon nucleation from a deep crustal fluid by replica exchange reactive molecular dynamics simulation

Here we present a mechanistic model of carbon nucleation and growth from a fluid at elevated temperature (T) and pressure conditions, typical of those found in the shallow Earth’s lithosphere. Our model uses a replica exchange reactive molecular dynamics framework in which molecular configurations are swapped between adjacent T replica at regular intervals according to underlying statistical mechanics. This framework allows predicting complex molecular structures and thermodynamics while remaining computationally efficient. Here we simulate the reactivity of an unstable mixture of CO 2 and CH 4 at 1000 K and 1 GPa. We find that the path to thermodynamic equilibrium is initially entropy-driven, producing a diversity of short-lived species, including various alcohols with intermediate carbon oxidation states. Cyclic and polycyclic radicals that are sometimes resonance-stabilized form next and set the stage for carbon nucleation. The carbon exsolution process releases abundant water, is exothermic and starts with the nucleation of a large aggregate of hydrogenated graphene flakes from covalently bonded polycyclic units. The carbon backbone of this nucleus subsequently grows into a hydrogen-depleted fullerene-like structure, before evolving toward a partially bilayered graphene layer. Overall, our results show that the mechanism of graphitic C formation is certainly not bimolecular, and that it may involve a combination of key condensation and radical chain reactions. This will help understand the isotopic, and reactive characteristics of carbon-bearing fluids during their upward transit through the Earth’s mantle and crust. Moreover, the mechanistic insights outlined here present intriguing similarities with the process of soot and interstellar dust formation, which suggests that the widespread distribution of abiotic polyaromatic and graphitic material on Earth and beyond may reflect the prevalence of a fundamental chemical pathway.

58 GEOSCIENCES↗

Crustal influence in the generation of continental flood basalts

The suggestion that primordial undifferentiated material may exist in the earth's mantle has recently been revived on the strength of Nd isotope data for two types of young continental rocks - flood basalts and kimberlites. The limited published data show a clustering of Nd isotopic compositions close to those for meteorites with chondritic relative rare-earth (REE) abundance. In contrast, data are presented for samples from the Columbia flood basalt province of the northwestern United States which show large isotopic variability suggestive of mixing processes acting after the separation of the primary magmas from their mantle source.

Carlson, R. W.↗

Long-Period Tidal Variations of the Earth's Rotation Rate

Long-period tidal variations of the Earth's rotation rate are caused by the redistribution of mass associated with the respective elastic solid Earth tides, the ocean tide heights, and the anelasticity of the Earth's mantle, and by the relative angular momentum associated with the long-period ocean tide currents.

Ocean tides Earth Rotation↗

Forearc Carbon Sink Reduces Long-Term Volatile Recycling Into the Mantle

Carbon and other volatiles are transported from Earth’s surface into the mantle at subduction margins. The efficiency of this transfer has profound implications for the nature and scale of geochemical heterogeneities in Earth’s deep (mantle) and shallow (crustal) reservoirs, as well as Earth’s oxidation state. However, the proportion of volatiles released in the forearc and backarc are not well constrained compared to fluxes from the volcanic front. Here, we use helium and carbon isotope data from deeply sourced springs along two cross-arc transects to show that ~91% of carbon released from the slab/mantle beneath the Costa Rica forearc is sequestered within the crust by calcite deposition, and an additional ~3% is incorporated into biomass through microbial chemolithoautotrophy. We estimate that ~1.2 × 10(exp 8) to 1.3 × 10(exp 10) mol CO2/yr are released from the slab beneath the forearc, resulting in up to ~19% less carbon being transferred to Earth’s deep mantle than previously estimated.

Carbon cycle↗

First in-situ Nitrogen Isotope Measurements in Martian Meteorites

The origin and timing of the accretion of volatile elements on the terrestrial planets remains a subject of controversy. Nitrogen and hydrogen isotopes are powerful tools to constrain the source(s) of primordial volatiles accreted by planetary bodies because their isotope ratios (15N/14N; D/H) differ significantly between different solar system reservoirs (e.g., solar, chondritic, cometary). Hf-W data of martian samples indicate that Mars accreted very rapidly in the inner solar system and reached half ofits size in 1.8 Myr [1]. Therefore, martian samples are key to understand the distribution of volatile elements in the inner solar system during the early stages of planetary formation. Since no space missions have yet returned samples from Mars, martian meteorites (Shergottites, Nakhlites, Chassignites) are unique samples to constrain the source(s) of volatiles present in the martian mantle. The goal of this study was to target pristine phases(e.g., melt inclusions, mesostasis) for in-situ measurements of their nitrogen content and isotopic ratios to access the most primitive melt of the Chassignites and Nakhlites reservoirs. Five different Nakhlites (Nakhla, NWA 998, MIL 03346, Y 000593,NWA 6148) and Chassigny were analysed [2] using a recent high-resolution analytical technique that allows constraining the nitrogen composition of both carbon-bearing and carbon-free phases in natural and synthetic samples. Nitrogen was measured in the form of 14N16O- and 15N16O- with the CAMECA 1280-HR2 at the CRPG [3]. A significant amount of nitrogen was detected in melt inclusions in Chassigny and in the mesostasis of Nakhla, Y000593, MIL 03346, and NWA 6148. Nitrogen isotope signatures of Chassigny and Nakhlites exhibit a heavy isotope enrichment compared to Earth's mantle, and are consistent with a carbonaceous chondrite-like source [4]. This suggests that Earth and Mars accreted nitrogen from different chondritic sources. Overall, our in-situ technique is a unique and powerful tool to characterize the nitrogen abundance and isotopic composition of natural samples.

C Deligny↗

The source of the Earth's long wavelength geoid anomalies: Implications for mantle and core dynamics

The long wavelength components of the Earth's gravity field result mainly from density contrasts associated with convection in the mantle. Direct interpretation of the geoid for mantle convection is complicated by the fact that convective flow results in dynamically maintained deformation of the surface of the Earth, the core mantle boundary (CMB), and any interior chemical boundaries which might exist. These boundary deformations effect the geoid opposite in sign and are comparable in magnitude to those of the interior density contrasts driving the flow. The total difference of two relatively large quantities.

Hager, B. H.↗

Geochemical evidence for the formation of the Moon by impact induced fission of the proto-Earth

Geochemical evidence is discussed which advocates the theory that the Moon was formed by impact induced fission of the Earth. The Earth's mantle exhibits a number of geochemical peculiarities which make our planet a unique object in the solar system. Terrestrial basalts are compared with those from the Eucrite parent body and the Shergotty parent body. Also the Moon's composition is very close to the Earth's in all details except the lower FeO content which is explained. Evidence is discussed for the plausible physical process of formation of the Moon by impact induced fission. Also the theory that impact induced fission occurred at the moment at which accretion of the Earth was not totally complete is briefly discussed.

Waenke, H.↗

Polarity reversals and tilt of the Earth's magnetic dipole

There is evidence that the terrestrial magnetic field is connected with the Earth's mantle: (1) there are magnetic anomalies that do not take part in the westward drift of the main field, but are fixed with respect to the mantle; (2) the geomagnetic pole position flips in a particular way by preferred meridional paths during a reversal; and (3) magnetic polarity reversals are correlated with the activations of geological processes. These facts may be explained if we take into account that a significant horizontal temperature gradient can exist in the top levels of the liquid core because of the different thermoconductivity of the different areas of the core-mantle boundary. These temperature inhomogeneities can penetrate the core because fluxes along the core boundary (the thermal wind) can be strongly suppressed by a small redistribution of the chemical composition in the top of the core. The nonparallel gradients of the temperature, density, and composition on the top of the core create a curled electric field that produces a current and a magnetic field. This seed-field can be amplified by motions in the core. The resulting field does not forget the seed-field distribution and in this way the field on the Earth surface (that can be created only in regions with high conductivity, i.e. in the core) is connected with the core-mantle boundary. Contrary to the usual approach to the dynamo problem, we will take into account that the seed field of thermoelectric origin is acting not only at some initial moment of time but permanently.

Dolginov, A. Z.↗

What Should the FeO Content of a Terrestrial Planet Be?

Basalts from the Earth, the Moon, Mars, and Vesta are strongly depleted in elements that prefer to reside in the metallic state (siderophile elements). Therefore, it is believed that all these bodies have metallic cores. We do not yet have siderophile element analyses of venusian or mercurian basalts, but we assume that Venus, too, as a terrestrial planet, has a metallic core. For the Earth, Moon, Mercury, and Mars, the moments-of-inertia of these bodies are consistent with metallic cores of various sizes. Because Venus rotates so slowly, it may be difficult to determine the moment-of-inertia of Venus in order to confirm this assumption. However, despite many possible complexities, it seems likely that most of the major and minor terrestrial planets have experienced some sort of metal/silicate equilibration, and we will use this as a boundary condition. One immediate contrast between the Earth and Moon is the difference in FeO content between lunar and terrestrial basalts. Both bodies presumably formed near 1 AU and formed from the same feeding zone of planetesimals, judging by their oxygen isotopes [13]. If, for example, the Moon formed from the Earth by a giant impact, then this event must have occurred before high-pressure equilibria had the opportunity to deplete the Earth s mantle in FeO. Alternatively, the bulk silicate Moon may be dominated by material from the impactor. Regardless, it would be useful to know the pressures where FeO incorporation into a metallic core is not of interest. If the Giant Impact hypothesis is correct, this should set an upper limit for the size of the proto-Earth at the time of the impact.

Jones, John H.↗

Origin of the Moon: Constraints from volatile elements

Supporting arguments for the lunar fusion hypothesis include the low density of the Moon corresponding to the density of the Earth's mantle and the low volatile content of the lunar rocks vs. those of terrestrial origin. Vapor pressures of the alkali elements and their oxides increase in the following order: Na, K, Rb and Cs. The Moon should, therefore, be more depleted in Cs relative to Rb, Rb relative to K, and K relative to Na than the Earth if the fission model is correct. Analyses of lunar mare basalts and terrestrial mid-ocean ridge and other young basalts indicate that this behavior is not observed. It is possible that monovalent alkali elements might be lost from silicate materials in a different order than that inferred from elemental and oxide vapor pressures, as a result of differences in the way they are bound in silicate materials. To test this hypothesis a series of experiments was conducted to investigate alkali loss at high temperatures. Analyses indicate that the behavior of volatiles dissolved in a silicate melt is similar to that inferred from elemental and oxide vapor pressures. It is concluded that alkali element ratios in the Earth and Moon are not readily interpreted in terms of the fission hypothesis.

Kreutzberger, M. E.↗

Migration and accumulation of hydrous mantle incipient melt in the Earth's asthenosphere: Constraints from in-situ falling sphere viscometry measurements

The Earth's oceanic lithosphere-asthenosphere boundary (LAB) is marked by a notable decrease in seismic wave velocities and an increase in attenuation. This phenomenon is likely attributed to the accumulation of partial melt at the top of the asthenosphere. Nevertheless, the process involving the upward migration and aggregation of low-degree partial melts, highly likely to be mantle incipient melts in the asthenosphere, remains underexplored. Viscosity is a key factor controlling the flow of melts, thus in this study, we used In-situ X-ray falling sphere viscometry experiments to determine the viscosity of the mantle incipient melt containing 1.8–4.0 wt.% water at 1.5–6 GPa and 2100 K. We found that water and pressure can effectively decrease the viscosity of the mantle incipient melt. Therefore, the mantle incipient melts are highly mobile with a high segregation velocity in the deeper part of the asthenosphere. However, during ascent, their mobility diminishes due to an increase in viscosity and a decrease in water content. In conclusion, these mechanisms potentially contribute to the accumulation of partial melt at the top of the asthenosphere.

58 GEOSCIENCES↗

Evidence for Dry Carbonatite Metasomatism in the Oceanic Lithosphere from Peridotite Xenoliths of Samoa and Lanzarote

Water in Earth’s mantle affects processes like magmatism and plate tectonics. Experiments show that CO2-rich fluids lower the water solubility in olivine, implying that CO2-rich melts/fluids may dehydrate the lithosphere during metasomatism. To test this hypothesis, we report water concentrations (by polarized FTIR) of olivines, orthopyroxenes (OPX) and clinopyroxenes (CPX) from Savai’i (Samoa) and Lanzarote (Canary Islands) peridotite xenoliths with evidence of carbonatite metasomatism. Savai’i peridotites are highly depleted harzburgites and dunites with spinel Cr# (Cr/(Cr+Al)) ranging from 0.4 to 0.76 (estimated degree of melting: 191.5%). Strong Light Rare Earth Element (LREE) enrichments with Ti and Zr depletions in OPX and CO2-rich fluid inclusions (via Raman spectroscopy) are consistent with carbonatite metasomatism. Olivine, OPX and reconstructed bulk rock water concentrations (0.67-3.8, 17-89 and 4-26 ppm H2O, respectively) are low and show no apparent relationship with extent of carbonatite metasomatism. Calculated water concentrations of melts in equilibrium with Savai’i OPX (OPX/melt partitioning of water 0.0063 to 0.011) are, on average (0.540.32 wt% H2O), lower than host Samoan lavas (0.63 to 1.5 wt% H2O), despite the LREE enrichments in OPX. Lanzarote peridotites are also highly depleted (degree of melting from spinel Cr#: 171.8%).Water concentrations are low in olivines (1.7-5.3 ppm H2O) and variable in pyroxenes (OPX: 42-103 ppm H2O; CPX: 105-301 ppm H2O), and show no apparent correlation with indicators of carbonatite metasomatism. Both Savai’i and Lanzarote peridotites show negative correlations between water and degree of melting (i.e. Mg/(Mg+Fe), Cr#), suggesting melt depletion rather than metasomatism may have influenced their water concentrations. Calculated water concentrations of melts in equilibrium with Lanzarote CPX (average 1.90.75 wt% H2O; CPX/melt partitioning of water 0.011 to 0.012) are similar to those for Western Canaries lavas (average 1.80.31 wt%; CPX/melt partitioning of water 0.016 to 0.021) inferred from their CPX phenocrysts. However, calculated Ce concentrations in such melts (352 to 378 ppm; CPX/melt partitioning of Ce 0.07) are an order of magnitude greater than the lavas, and similar to carbonatites. This leads to H2O/Ce to be an order of magnitude lower in the inferred melts (26 to 57) than estimates for Western Canary lavas (280150). These low H2O/Ce ratios may suggest H2O loss from CPX during ascent, but the lack of strong water diffusion gradients in Lanzarote minerals does not support this. Instead we hypothesize that carbonatite metasomatism resulted in greater enrichment of Ce over H2O. Assuming carbonatite magmas are water rich, this implies a lower partitioning of water between minerals and melts during metasomatism, as suggested by experiments. Our data suggests carbonatite metasomatism does not result in significant re-hydration of the lithosphere, in contrast to silicate metasomatism as previously observed in Hawaiian peridotites.

Ashley, Aaron↗

On the penetration of the 660 km phase change by mantle downflows

We present a simple analytic model of the interaction of cold convective downwelling currents with an endothermic phase change. The model describes the ponding and lateral spreading of downflows along the phase transition interface. A simple comparison of the vertical forces on the ponding material provides a necessary condition for a downflow to penetrate the phase boundary. This condition is fundamentally dependent on the geometry of the downflow. For planar downwellings, the model predicts a minimum ponding time before the structure can penetrate the phase boundary. For columnar (axisymmetric) downflows, there is no minimum time of spreading required before penetration can proceed. The model thus provides an explanation for the observation that in numerical models of three-dimensional convection with an endothermic phase change, cylindrical downflows penetrate the phase interface while planar ones do not. Since descending slabs in the Earth's mantle display a wide spectrum of geometries between planar and cylindrical (given various trench curvatures, as well as intersections of two or more subduction zones), this phenomenon may explain, in part, why some slabs appear to extend into the lower mantle while others are deflected at the 660 km discontinuity.

Bercovici, David↗

Measurement and Interpretation of Crustal Deformation Rates Associated with Postglacial Rebound

This project involves obtaining GPS measurements in Scandinavia, and using the measurements to estimate the viscosity profile of the Earth's mantle and to correct tide-gauge measurements for the rebound effect. Below, we report on several aspects of this project. The DSGS was occupied in August 1993. This campaign also inaugurated SWEPOS, the Swedish permanent GPS network. Initial results are presented in Johansson et al., a copy of which is contained in Appendix A. An important technical advance we intend for this project is to use the full three dimensional site velocity information for inferring geophysical parameters. To this end, we have investigated using VLBI determined baseline length rates in North America to constraining proposed combinations of ice history and earth rheology, and presented this work in Mitrovica et al., a copy of which is contained in Appendix B.

Davis, James L.↗

Influence of heating mode on three-dimensional mantle convection

Numerical models of three-dimensional thermal convection in highly viscous spherical shells with different combinations of internal and basal heating consistently have upwelling concentrations in the form of cylindrical plumes and downwelling in planar sheets. As the proportion of internal heating increases, the number of upwelling plumes increases, and downwelling sheets become more vigorous and time-dependent. With any amount of basal heating, the entire convective pattern, during its evolution, is anchored to the upwelling plumes. As the proportion of internal heating increases, the heat flow carried by the upwelling plumes remains a large fraction of the basal heat flow. Downwelling sheets carry only a minor fraction (approximately 30 percent) of the basal heat flow (even when the shell is entirely heated from below), but they advect almost all of the internally generated heat. The relatively large number of plumes in the earth's mantle (inferred from hotspots), the possibility that downwelling slabs are vigorous enough to penetrate the lower mantle, and the small fraction of terrestrial surface heat flow carried by plumes all suggest that the mantle is predominantly heated from within.

Bercovici, D.↗

Deformation of Polycrystalline MgO Up to 8.3 GPa and 1270 K: Microstructures, Dominant Slip-Systems, and Transition to Grain Boundary Sliding

Ferropericlase is the second most abundant mineral in the Earth’s lower mantle and its mechanical properties have a strong influence on the rheology of this region. Here, we deform polycrystalline MgO, the magnesium end-member of ferropericlase, at conditions ranging from 1.6 to 8.3 GPa and 875–1,270 K. We analyse the flow laws and microstructures of the recovered samples using electron microscopy and compare our observations with predictions from the literature. We identify a first mechanism for samples deformed at 1,270 K, attributed to a regime controlled by grain boundary sliding accommodated by diffusion, and characterized by a small grain size, an absence of texture, and no intracrystalline deformation. At 1,070 K and below, the deformation regime is controlled by dislocations. The samples show a more homogeneous grain size distribution, significant texture, and intracrystalline strains. In this regime, deformation is controlled by the ⟨110⟩{110} slip system and a combined ⟨110⟩{110} and ⟨110⟩{100} slip, depending on pressure and temperature. Based on these results, we propose an updated deformation map for polycrystalline MgO at mantle conditions. The implications for ferropericlase and seismic observations in the Earth’s lower mantle are discussed.

Ledoux, Estelle Elisa↗

Electron Density Changes across the Pressure-Induced Iron Spin Transition

High-pressure single-crystal x-ray diffraction is used to experimentally map the electron-density distribution changes in (Fe,Mg)O as ferrous iron undergoes a pressure-induced transition from high- to low-spin states. As the bulk density and elasticity of magnesiowustite—one of the dominant mineral phases of Earth’s mantle—are affected by this electronic transition, our results have applications to geophysics as well as to validating first-principles calculations. Furthermore, the observed changes in diffraction intensities indicate a spin-transition-induced change in orbital occupancies of the Fe ion in general accord with crystal-field theory, illustrating the use of electron density measurements for characterizing high-pressure d-block chemistry and motivating further studies characterizing chemical bonding under pressure.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗