Lower Mantle Minerals Research Articles

Thermal conductivity of ferropericlase in the Earth's lower mantle

(Mg, Fe)O ferropericlase (Fp) is one of the important minerals comprising Earth's lower mantle, and its thermal conductivity could be strongly influenced by the iron content and its spin state. We examined the lattice thermal conductivity of (Mg, Fe)O Fp containing 19 mol% iron up to 111 GPa and 300 K by means of the pulsed light heating thermoreflectance technique in a diamond anvil cell. We confirmed a strong reduction in the lattice thermal conductivity of Fp due to iron substitution as reported in previous studies. Our results also show that iron spin crossover in Fp reduces its lattice thermal conductivity as well as its radiative conduction. We also measured the electrical conductivity of an identical Fp sample up to 140 GPa and 2730 K, and found that Fp remained an insulator throughout the experimental conditions, indicating the electronic thermal conduction in Fp is negligible. Because of the effects of strong iron impurity scattering and spin crossover, the total thermal conductivity of Fp at the core–mantle boundary conditions is much smaller than that of bridgmanite (Bdg). Our findings indicate that Bdg (and post-perovskite) is the best heat conductor in the Earth's lower mantle, and distribution of iron and its valence state among the lower mantle minerals are key factors to control the lower mantle thermal conductivity.

Two-phase deformation of lower mantle mineral analogs

The lower mantle is estimated to be composed of mostly bridgmanite and a smaller percentage of ferropericlase, yet very little information exists for two-phase deformation of these minerals. To better understand the rheology and active deformation mechanisms of these lower mantle minerals, especially dislocation slip and the development of crystallographic preferred orientation (CPO), we deformed mineral analogs neighborite (NaMgF3, iso-structural with bridgmanite) and halite (NaCl, iso-structural with ferropericlase) together in the deformation-DIA at the Advanced Photon Source up to 51% axial shortening. Development of CPO was recorded in situ with X-ray diffraction, and information on microstructural evolution was collected using X-ray microtomography. Results show that when present in as little as 15% volume, the weak phase (NaCl) controls the deformation. Compared to single phase NaMgF3 samples, samples with just 15% volume NaCl show a reduction of CPO in NaMgF3 and weakening of the aggregate. Microtomography shows both NaMgF3 and NaCl form highly interconnected networks of grains. Polycrystal plasticity simulations were carried out to gain insight into slip activity, CPO evolution, and strain and stress partitioning between phases for different synthetic two-phase microstructures. The results suggest that ferropericlase may control deformation in the lower mantle and reduce CPO in bridgmanite, which implies a less viscous lower mantle and helps to explain why the lower mantle is fairly isotropic.

Spawning superplumes from the midmantle: The impact of spin transitions in the mantle

AbstractThe formation of large‐scale upwellings with lateral extents of several hundreds of kilometers, reaching up to ∼10,000 km or more, still remains a hotly debated topic. Some seismic imaging studies based on high‐resolution data suggest that the main superplumes underneath Africa and South‐central Pacific are clusters, composed of several individual plumes rather than being a single large mantle upwelling. The iron spin transition in the lower mantle minerals may present a new idea on the origin and the formation of such superplumes, notably sourcing such features in the midmantle. Stagnation of both cold sinking slabs and hot rising plumes can be caused by density and viscosity variation due to the spin transition in iron in ferropericlase (Fp) and a possible spin‐dependent bulk modulus hardening in bridgmanite silicate perovskite (Pv). This process produces intermittent downward spin transition‐induced midmantle avalanches (SIMMA) of the cold sinking flow as well as upward spin transition‐induced midmantle superplume avalanches (SIMMSA) of the rising hot plumes, triggered at the spin transition‐induced thermal boundary layer at around 1600 km depth. Our high‐resolution axi‐symmetric models reveal that the hot upwellings, trapped below ∼1600 km depth, can suddenly penetrate into the upper levels in the mantle and spread laterally for hundreds of kilometres. Owing to the upward penetration of the midmantle‐rooted superplumes, as broad as ∼1500 km across, a large amount of heat can be delivered to the upper mantle and base of the lithosphere with implications for large volcanic episodes.

Effects of chemical, mineralogical, and temperature variations on the density and bulk sound velocity of the bottom lower mantle

In this study, we have modeled the density (ρ) and bulk sound velocity (V Φ) profiles of the bottom lower mantle using the experimental thermal equation of state (EoS) parameters of lower-mantle minerals, including bridgmanite, ferropericlase, CaSiO3-perovskite, and post-perovskite. We re-evaluated the literature pressure-volume-temperature relationships of these minerals using a self-consistent pressure scale in order to avoid the long-standing pressure scale problem and to provide more reliable constraints on the thermal EoS parameters. With the obtained thermal EoS parameters, we have constructed the ρ and V Φ profiles of the bottom lower mantle in different composition, mineralogy, and temperature models. Our modelling results show that the variations of chemistry, mineralogy, and temperature have different seismic signatures from each other. The Fe and Al enrichment at the bottom lower mantle can cause an increase in ρ but greatly lower V Φ. A change in mineralogy needs to be considered with the lateral variation in temperature. The cold slabs will be shown as denser regions compared to the normal mantle because of the combined effect of a lower temperature and the presence of a denser post-perovskite at a shallower depth, whereas the hot regions will have a 1–2% lower ρ than the normal mantle. V Φ of both cold slabs and hot regions will be lower than the normal mantle when bridgmanite is the dominant phase in the normal mantle, yet they will be greater once bridgmanite transforms into post-perovskite in the normal mantle. Our modeling also shows that the presence of a (Fe, Al)-enriched bridgmanite thermal pile above the core-mantle boundary will exhibit a seismic signature of enhanced ρ and V Φ, but a reduced V S, which is consistent with the observed seismic anomalies in the large-low-shear-velocity-provinces (LLSVPs). The existence of such a (Fe, Al)-enriched bridgmanite thermal pile thus can help to understand the origin of the LLSVPs. These results provide new insights for the chemical and structure of the deepest lower mantle.

Electrical conductivity as a constraint on lower mantle thermo-chemical structure

Electrical conductivity of the Earth's mantle depends on both temperature and compositional parameters. Radial and lateral variations in conductivity are thus potentially a powerful means to investigate its thermo-chemical structure. Here, we use available electrical conductivity data for the major lower mantle minerals, bridgmanite and ferropericlase, to calculate 3D maps of lower mantle electrical conductivity for two possible models: a purely thermal model, and a thermo-chemical model. Both models derive from probabilistic seismic tomography, and the thermo-chemical model includes, in addition to temperature anomalies, variations in volume fraction of bridgmanite and iron content. The electrical conductivity maps predicted by these two models are clearly different. Compared to the purely thermal model, the thermo-chemical model leads to higher electrical conductivity, by about a factor 2.5, and stronger lateral anomalies. In the lowermost mantle (2000–2891 km) the thermo-chemical model results in a belt of high conductivity around the equator, whose maximum value reaches ∼120% of the laterally-averaged value and is located in the low shear-wave velocity provinces imaged in tomographic models. Based on our electrical conductivity maps, we computed electromagnetic response functions (C-responses) and found, again, strong differences between the C-responses for purely thermal and thermo-chemical models. At periods of 1 year and longer, C-responses based on thermal and thermo-chemical models are easily distinguishable. Furthermore, C-responses for thermo-chemical model vary geographically. Our results therefore show that long-period (1 year and more) variations of the magnetic field may provide key insights on the nature and structure of the deep mantle.

Confirming a pyrolitic lower mantle using self‐consistent pressure scales and new constraints on CaSiO3 perovskite

AbstractIn this study, we have examined the lower mantle composition and mineralogy by modeling the density (ρ), bulk sound velocity (VΦ), and dlnρ/dlnVΦ profiles of candidate lower mantle minerals using literature and new experimental equation of state (EoS) results. For CaSiO3 perovskite, complimentary synchrotron X‐ray diffraction measurements in a laser‐heated diamond anvil cell were conducted up to 156 GPa between 1200 K and 2600 K to provide more reliable constraints on the thermal EoS parameters. These new experimental results as well as literature P‐V‐T data sets are systematically analyzed using an internally self‐consistent pressure scale. We have modeled ρ, VΦ, and dlnρ/dlnVΦ profiles of the lower mantle with representative pyrolitic and chondritic compositional models in which the effect of Fe spin transition in ferropericlase is also taken into account. Our modeling results show that a pyrolitic lower mantle with an aggregate mineralogy of 75 vol % bridgmanite, 17 vol % ferropericlase, and 8 vol % CaSiO3 perovskite produces ρ and VΦ profiles in better agreement with preliminary reference Earth model than a lower mantle with a chondritic composition. The modeled ρ, VΦ, and dlnρ/dlnVΦ are mainly affected by the relative ratio of bridgmanite and ferropericlase but are not sensitive to the variation of the CaSiO3 perovskite content. In addition, the spin crossover of Fe in ferropericlase can greatly raise the value of dlnρ/dlnVΦ in the middle lower mantle, which is useful in detecting the presence of ferropericlase in the region. Based on these new mineral physical constraints and radial seismic structure, our study suggests the lower mantle is pyrolitic, which is chemically indistinguishable from the upper mantle.

Reduced radiative conductivity of low spin FeO6-octahedra in FeCO3 at high pressure and temperature

The ability of Earth's mantle to conduct heat by radiation is determined by optical properties of mantle phases. Optical properties of mantle minerals at high pressure are accessible through diamond anvil cell experiments, but because of the intense thermal radiation at T>1000 K such studies are limited to lower temperatures. Accordingly, radiative thermal conductivity at mantle conditions has been evaluated with the assumption of the temperature-independent optical properties. Particularly uncertain is the temperature-dependence of optical properties of lower mantle minerals across the spin transition, as the spin state itself is a strong function of temperature. Here we use laser-heated diamond anvil cells combined with a pulsed ultra-bright supercontinuum laser probe and a synchronized time-gated detector to examine optical properties of high and low spin ferrous iron at 45–73 GPa up to 1600 K in an octahedral crystallographic unit (FeO6), one of the most abundant building blocks in the mantle. Siderite (FeCO3) is used as a model for FeO6-octahedra as it contains no ferric iron and exhibits a sharp optically apparent pressure-induced spin transition at 44 GPa, simplifying data interpretation. We find that the optical absorbance of low spin FeO6 increases with temperature due to the partially lifted Laporte selection rule. The temperature-induced low-to-high spin transition, however, results in a dramatic drop in absorbance of the FeO6 unit in siderite. The absorption edge (Fe–O charge transfer) red-shifts (∼1 cm−1/K) with increasing temperature and at T>1600 K and P>70 GPa becomes the dominant absorption mechanism in the visible range, suggesting its superior role in reducing the ability of mantle minerals to conduct heat by radiation. This implies that the radiative thermal conductivity of analogous FeO6-bearing minerals such as ferropericlase, the second most abundant mineral in the Earth's lower mantle, is substantially reduced approaching the core–mantle boundary conditions.

First-principles calculations of elasticity of minerals at high temperature and pressure

The elasticity of minerals at high temperature and pressure (PT) is critical for constraining the composition and temperature of the Earth’s interior and understand better the deep water cycle and the dynamic Earth. First-principles calculations without introducing any adjustable parameters, whose results can be comparable to experimental data, play a more and more important role in investigating the elasticity of minerals at high PT mainly because of (1) the quick increasing of computational powers and (2) advances in method. For example, the new method reduces the computation loads to one-tenth of the traditional method with the comparable precise as the traditional method. This is extraordinarily helpful because first-principles calculations of the elasticity of minerals at high PT are extremely time-consuming. So far the elasticity of most of lower mantle minerals has been investigated in detail. We have good idea on the effect of temperature, pressure, and iron concentration on elasticity of main minerals of the lower mantle and the unusual softening in bulk modulus by the spin crossover of iron in ferropericlase. With these elastic data the lower mantle has been constrained to have 10–15 wt% ferropericlase, which is sufficient to generate some visible effects of spin crossover in seismic tomography. For example, the spin crossover causes that the temperature sensitivity of P wave at the depth of ~1700 km is only a fraction of that at the depth of ~2300 km. The disruptions of global P wave structure and of P wave image below hotspots such as Hawaii and Iceland at similar depth are in consistence with the spin crossover effect of iron in ferropericlase. The spin crossover, which causes anomalous thermodynamic properties of ferropericlase, has also been found to play a control role for the two features of the large low shear velocity provinces (LLSVPs): the sharp edge and high elevation up to 1000 km above core-mantle boundary. All these results clearly suggest the spin crossover of iron in the lower mantle. The theoretical investigations for the elasticity of minerals at the upper mantle and water effect on elasticity of minerals at the mantle transition zone and subducting slab have also been conducted extensively. These researches are critical for understanding better the composition of the upper mantle and water distribution and transport in the Earth’s mantle. Most of these were static calculations, which did not include the vibrational (temperature) effect on elasticity, although temperature effect on elasticity is basic because of high temperature at the Earth’s interior and huge temperature difference between the ambient mantle and the subducting slab. Including temperature effect on elasticity of minerals should be important future work. New method developed is helpful for these directions. The elasticity of iron and iron-alloy with various light elements has also been calculated extensively. However, more work is necessary in order to meet the demand for constraining the types and amount of light elements at the Earth’s core.

The Lower Mantle Minerals in Ophiolite‐hosted Diamond

The Lower Mantle Minerals in Ophiolite‐hosted Diamond

The crystal structures of Mg2Fe2C4O13, with tetrahedrally coordinated carbon, and Fe13O19, synthesized at deep mantle conditions

We simulated the redox decomposition of magnesium-siderite at pressures and temperatures corresponding to the top of the Earth’s D″ layer (135 GPa and 2650 K). It transforms into new phases, with unexpected stoichiometry. We report their crystal structure, based on single-crystal synchrotron radiation diffraction on a multi-grain sample, using a charge-flipping algorithm. Mg2Fe2(C4O13) is monoclinic, a = 9.822(3), b = 3.9023(13), c = 13.154(5) A, β = 108.02(3)°, V = 479.4(3) A3 (at 135 GPa). It contains tetrahedrally coordinated carbon units, corner-shared in truncated C4O13 chains. Half of the cations are divalent, and half trivalent. The carbonate coexists with a new iron oxide, Fe13O19, monoclinic, a = 19.233(2), b = 2.5820(13), c = 9.550(11) A, β = 118.39(3)°, V = 417.2(5) A3 (at 135 GPa). It has a stoichiometry between hematite, Fe2O3, and magnetite, Fe3O4. The formation of these unquenchable phases indicates, indirectly, the formation of reduced-carbon species, possibly diamond. These structures suggest the ideas that the mineralogy of the lower mantle and D″ region may be more complex than previously estimated. This is especially significant concerning accessory phases of fundamental geochemical significance and their role in ultra-deep iron-carbon redox coupling processes, as well as the iron-oxygen system, which certainly play an important role in the lower mantle mineral phase equilibria.

Spin state transition and partitioning of iron: Effects on mantle dynamics

Experimental studies at pressure and temperature conditions of the Earth's lower mantle have shown that iron in ferropericlase (Fp) and in Mg-silicate perovskite (Pv) undergoes a spin state transition. This electronic transition changes elastic and transport properties of lower mantle minerals and can play an important role in mantle convection. Here we focus on the geodynamic effect of the spin-induced density modifications caused by the volume collapse of Fp and by the variation of Fe partitioning (KPv–Fp) between Fp and Pv. Since KPv–Fp behavior strongly depends on alumina content, we explore two end-member compositions, one Al-bearing (with 4.7 wt% Al2O3 in Pv) and the other Al-free. We use the theoretical model by Sturhahn et al. (2005) to calculate the spin configuration of Fp over a range of pressure–temperature conditions, and use experimental results to model Fe partitioning. We then apply the Mie–Grüneisen–Debye equation of state to obtain the density of the mineral assemblages. The calculated amplitude of the density change across the spin state transition is less than 1%, consistent with experiments by Mao et al. (2011); our density profiles differ from PREM by less than 1.5%. The spin-induced density variations are included in a three dimensional convection code (Stag3D) for a compressible mantle. We find small temperature differences between models with and without spin state transitions, since over billions of years the relative temperature difference is less than 50 K. However the relative RMS vertical velocity difference is up to 15% for an Al-free system, but only less than 6% for an Al-bearing system.

Phase transition of iron doped MgO under high pressure by first-principles study

The ( Mg, Fe ) O solid solution is one of the major lower mantle minerals, and studying its properties and structures under high pressure is a fundamental step toward understanding Earth's deep interior. Here within the framework of density functional theory, we first discuss the relationship between the total energy and iron doped positions of ( Mg, Fe ) O , and find that the doped iron favors to be dispersive. Then the pressure-induced phase transitions of ( Mg, Fe ) O from NaCl -type (B1) to CsCl -type (B2) are probed. It is found that the phase transition pressure of ( Mg, Fe ) O decreases with damped oscillation, as the increase of iron concentration. This phenomenon is essentially determined by the iron concentration as well as iron doped positions. The electronic structures of MgO and ( Mg 0.75 Fe 0.25) O at 436 GPa are calculated, and the results show that the doped irons play a crucial role in the metallicity of ( Mg 0.75 Fe 0.25) O . Our results are in agreement with the experimental counterparts. This study would provide some useful information for understanding the behavior of pressure-induced phase transition and geoscience.

First-principles study of intermediate-spin ferrous iron in the Earth's lower mantle

Spin crossover of iron is of central importance in solid Earth geophysics. It impacts all physical properties of minerals that altogether constitute $\sim 95$ vol\% of the Earth's lower mantle: ferropericlase [(Mg,Fe)O] and Fe-bearing magnesium silicate (MgSiO$_3$) perovskite. Despite great strides made in the past decade, the existence of intermediate-spin (IS) state in ferrous iron (Fe$^{2+}$) (with total electron spin $S=1$) and its possible role in the pressure-induced spin crossover in these lower-mantle minerals still remain controversial. Using density functional theory $+$ self-consistent Hubbard $U$ (DFT$+U_{sc}$) calculations, we investigate all possible types of IS states of Fe$^{2+}$ in (Mg,Fe)O and (Mg,Fe)SiO$_3$ perovskite. Among the possible IS states in these minerals, the most probable IS state has an electronic configuration that significantly reduces the electron overlap and the iron nuclear quadrupole splitting (QS). These most probable IS states, however, are still energetically disfavored, and their QSs are inconsistent with M\"{o}ssbauer spectra. We therefore conclude that IS Fe$^{2+}$ is highly unlikely in the Earth's lower mantle.

Physicochemical parameters of the material of mantle plumes: Evidence from the thermodynamic analysis of mineral inclusions in sublithospheric diamond

Thermodynamic analysis of equilibria involving minerals of the lower mantle of pyrolite composition and crystalline carbon-bearing compounds indicates that the range of oxygen fugacity values at which diamond can be formed is separated from the region in which Fe-rich metallic alloy is generated by a field in which Fe carbides are stable. This implies that diamond can be formed in the lower mantle under more oxidizing conditions than those thought to be dominant in this geosphere. The absence of a metallic phase from the lower-mantle diamond-bearing mineral assemblage is consistent with the high (approximately 1%) Ni concentration in the ferropericlase found as inclusions in diamonds (Fe-rich metallic alloy is able to intensely extract Ni). An elevated redox potential also follows from the occurrence of carbonate phases found among mineral inclusions in lower-mantle diamonds. The main reason for a local increase in oxygen fugacity in the lower mantle may be shifts of redox equilibria toward a decrease in the amount, and then the disappearance of the Fe-Ni alloy with increasing temperature. An important role in the formation of diamond may be played by the generation of carbonate-phosphate and silicate melts in high-temperature zones and the migration of these melts and their interaction with wall rocks.

Post-perovskite at ten

In 2004, a phase transition was discovered in the most abundant lower-mantle mineral. A decade of focused experiments, computations and seismic imaging stimulated by this discovery has revealed previously unknown complexities in Earth's deep mantle.

BurnMan: A lower mantle mineral physics toolkit

We present BurnMan, an open-source mineral physics toolbox to determine elastic properties for specified compositions in the lower mantle by solving an Equation of State (EoS). The toolbox, written in Python, can be used to evaluate seismic velocities of new mineral physics data or geodynamic models, and as the forward model in inversions for mantle composition. The user can define the composition from a list of minerals provided for the lower mantle or easily include their own. BurnMan provides choices in methodology, both for the EoS and for the multiphase averaging scheme. The results can be visually or quantitatively compared to observed seismic models. Example user scripts show how to go through these steps. This paper includes several examples realized with BurnMan: First, we benchmark the computations to check for correctness. Second, we exemplify two pitfalls in EoS modeling: using a different EoS than the one used to derive the mineral physical parameters or using an incorrect averaging scheme. Both pitfalls have led to incorrect conclusions on lower mantle composition and temperature in the literature. We further illustrate that fitting elastic velocities separately or jointly leads to different Mg/Si ratios for the lower mantle. However, we find that, within mineral physical uncertainties, a pyrolitic composition can match PREM very well. Finally, we find that uncertainties on specific input parameters result in a considerable amount of variation in both magnitude and gradient of the seismic velocities.

Spin transition, substitution, and partitioning of iron in lower mantle minerals

Spin transition and substitution of Fe3+ in Fe3+AlO3-bearing MgSiO3 perovskite (Pv) and post-perovskite (PPv) were examined up to 200 and 165GPa, respectively, at room temperature by X-ray emission spectroscopy (XES) and XRD. The results of XES and XRD indicate that in Pv high spin (HS) Fe3+ at the dodecahedral (A) site replaces Al at the octahedral (B) site and becomes low spin (LS) between 50 and 70GPa with pressure, while in PPv LS Fe3+ occupies the B-site and Al occupies the A-site above 80–100GPa. The Fe3+–Al coupled substitution seems to be at work in both Pv and PPv. Combining these results on Fe3+ with the recent first-principles calculations on Fe2+ in Pv and PPv, the spin transition and substitution of iron in pyrolitic lower mantle minerals are proposed. Further, their effects on iron-partitioning among the lower mantle minerals are discussed.

On origin of lower-mantle diamonds and their primary inclusions

Knowledge of mineralogy and petrology of unattainable lower mantle material is usually founded on high-pressure experiments with pyrolite (‘in situ’ material) and oceanic MORB basalt (subducted material). Primary inclusions in transition zone and lower-mantle ‘super-deep’ diamonds represent heterogeneous fragments of diamond-parental medium (not the unaltered lower mantle material). Inclusions of magnesiowustite and stishovite intergrowths (‘stishovite paradox’) give experimentally-supported evidence that stishovite, similarly to magnesiowustite, is not subducted but in situ lower mantle mineral. Primary Ca-, Mg-, Na-carbonate inclusions are symptomatic for multicomponent carbonatite (carbonate-oxide-silicate) parental melts for the lower-mantle diamonds and inclusions. We investigated melting phase relations of simple carbonates of Ca, Mg, Na and multicomponent Mg-Fe-Na-carbonate up to 60GPa and 3500–4000K (using multianvil press and diamond-anvil cell with laser heating) and determined a congruent melting of the carbonates and stability of PT-extended phase fields of the carbonate melts. ‘Super-deep’ diamonds are experimentally crystallized in melts of the lower mantle diamond-parental carbonate - magnesiowustite – Mg-perovskite – carbon system. Based on experimental and mineralogical evidence for the lower mantle diamonds inclusions, genetic links between diamonds and inclusions are determined and a generalized composition diagram of parental media for lower mantle diamonds and inclusions is constructed.

Conjecture with water and rheological control for subducting slab in the mantle transition zone

Seismic observations have shown structural variation near the base of the mantle transition zone (MTZ) where subducted cold slabs, as visualized with high seismic speed anomalies (HSSAs), flatten to form stagnant slabs or sink further into the lower mantle. The different slab behaviors were also accompanied by variation of the “660 km” discontinuity depths and low viscosity layers (LVLs) beneath the MTZ that are suggested by geoid inversion studies. We address that deep water transport by subducted slabs and dehydration from hydrous slabs could affect the physical properties of mantle minerals and govern slab dynamics. A systematic series of three-dimensional numerical simulation has been conducted to examine the effects of viscosity reduction or contrast between slab materials on slab behaviors near the base of the MTZ. We found that the viscosity reduction of subducted crustal material leads to a separation of crustal material from the slab main body and its transient stagnation in the MTZ. The once trapped crustal materials in the MTZ eventually sink into the lower mantle within 20–30 My from the start of the plate subduction. The results suggest crustal material recycle in the whole mantle that is consistent with evidence from mantle geochemistry as opposed to a two-layer mantle convection model. Because of the smaller capacity of water content in lower mantle minerals than in MTZ minerals, dehydration should occur at the phase transformation depth, ∼660 km. The variation of the discontinuity depths and highly localized low seismic speed anomaly (LSSA) zones observed from seismic P waveforms in a relatively high frequency band (∼1 Hz) support the hypothesis of dehydration from hydrous slabs at the phase boundary. The LSSAs which correspond to dehydration induced fluids are likely to be very local, given very small hydrogen (H+) diffusivity associated with subducted slabs. The image of such local LSSA zones embedded in HSSAs may not be necessarily captured in tomography studies. The high electrical conductivity in the MTZ beneath the northwestern Pacific subduction zone does not necessarily require a broad range of high water content homogeneously.

Theoretical Approaches to Structure and Spectroscopy of Earth Materials

The characterization of complex materials in terms of their structure, electronic, magnetic, vibrational, thermodynamic or other physical and chemical properties is often a challenging task that requires the combination of a number of complementary techniques. Experimental approaches such as diffraction or spectroscopic methods usually provide fingerprint information about the material under investigation. The interpretation of measured data is either done by reference to analogue materials or by constructing a theoretical (e.g., structural) model that fits the experimental data. For the latter, computational methods have become very powerful in recent years. For example, Rietveld refinement of powder diffraction data or curve fitting of various spectra is now done on a routine basis. The continuous improvement in hardware performance resulting in a huge and progressive increase of computing power by a factor of ~1000 per decade, as well as advanced algorithms and codes provide the basis for predictive modeling of material properties ab initio , i.e., from first principles using quantum chemical methods such as density functional theory (DFT). DFT enthalpy predictions for the major lower mantle minerals, MgSiO3 perovskite and post-perovskite, periclase (MgO) and CaSiO3 perovskite at zero temperature, over the relevant pressure range from the transition zone to the core-mantle boundary can be made in a few hours on an office PC. Free energy calculations for these phases at finite temperatures using lattice vibrational modes in the (quasi-)harmonic approximation require at most a couple of days. More realistic compositions of these mantle minerals with Fe substituting some of the Mg atoms in a solid solution are computationally more demanding but have also become accessible. The same is true for structural investigations of disordered phases, such as glasses, melts and fluids. Both first-principles and classical molecular dynamics simulations are useful methods for a statistically significant sampling of disordered structures. …