Mantle Geotherm Research Articles

Electrical conductivity of siderite and the effect of the spin transition of iron

We have conducted electrical conductivity measurements of FeCO3 siderite under high pressure up to 63 GPa in order to understand the nature and effect of iron spin transition and its influence on the geophysical properties of siderite, which is an end-member of major carbonate minerals. The results from Raman and Mössbauer spectroscopic measurements show that the high- to low-spin transition of iron occurs at around 50 GPa in agreement with previous studies. A sharp decrease of the electrical conductivity was also observed at around 50 GP, which is associated with the spin transition in iron. Although the stability of FeCO3 siderite may be limited under high-temperature conditions along with the mantle geotherm, solid solutions in the MgCO3-FeCO3 system, Mg1-xFexCO3, could be stable up to the pressure-temperature condition of the lowermost mantle. The pressure-temperature range of the spin transition in Mg1-xFexCO3 is narrower than those of the major lower mantle minerals, ferropericlase and bridgmanite, and thus the drop of the electrical conductivity induced by the spin transition could be clearer under lower mantle conditions. Therefore, the existence of Mg1-xFexCO3 may affect the observed heterogeneity of electrical conductivity in the mid-lower mantle.

Continental Crust Rejuvenation Across the Paleo‐Mesoarchean Transition Resulted From Elevated Mantle Geotherms

AbstractThe increase in initial Hf isotopes identified in early Mesoarchean detrital zircon is commonly interpreted as a reflection of the geodynamic transition from stagnant‐lid to mobile‐lid tectonics. However, given the lack of petrogenetic context, interpreting detrital zircon may lead to spurious conclusions. In this contribution, we use zircon U‐Pb‐Hf‐O isotopic and bulk rock compositions of newly identified 3.05–2.9 Ga granitoids from the SW Yangtze Block to posit petrogenesis within an isotopically juvenile magmatic system. A statistical analysis of these data with a global igneous zircon Lu‐Hf isotopic compilation reveals an increase in average initial radiogenic Hf isotopes during the Paleoarchean to Mesoarchean transition. We posit that the Earth's continental crust underwent a global rejuvenation across the Paleo‐Mesoarchean transition. This rejuvenation can be explained by an independently observed increase in mantle temperatures resulting from mantle thermal evolution and does not require a change in tectonic style.

High-pressure single-crystal elasticity of corundum: Implication for multiple seismic structure of 660-km discontinuity

The complex multi-discontinuity structure at 660‐800 km depth is likely attributable to lateral mantle composition heterogeneities, which are closely related to the mid-ocean ridge basalts (MORB). To decipher the impact of varying composition on the seismic properties of MORB, detailed knowledge of the elasticity of candidate minerals is thus important. Here we employed Brillouin scattering coupled with diamond anvil cells to determine the single-crystal elasticity of corundum up to 14 GPa and 300 K. Using third-order finite strain equation of state, we calculate the pressure derivatives of adiabatic bulk modulus and shear modulus of corundum, which yields KS0’ = 3.8(1), G0’ = 1.8(1) with KS0 = 256(1) GPa and G0 = 163(1) GPa and ρ0 = 3.987(1) g/cm3. Combined with previous high-temperature data, the velocity and anisotropy of corundum have been calculated at 300 K or along normal geotherm. Our results are applied to model the density and velocity profiles of normal and alkali-depleted MORB. Our modeling demonstrates that varying the alkali content and temperature of MORB can significantly impact the discontinuity depth and velocity jump at 660–800 km depth. For normal MORB, reducing the temperature by 300 K from normal mantle geotherm results in a shift of the velocity jump from 670–710 to 650–710 km depth but hardly affects the magnitude of the velocity jump (5.8–6.8(3)% for VP and 10.0–10.8(5)% for VS). By contrast, in alkali-depleted MORB, the discontinuity will occur at a greater depth from 705–730 to 720–745 km depending on temperature with a VP jump of 3.8–4.6(2)% and VS jump of 6.3–7.4(4)%.

Thermobarometry of diamond inclusions: Mantle structure and evolution beneath Archean cratons and mobile belts worldwide

Thermobarometric calculations for mineral inclusions in diamonds provide a systematic comparison of P-T-fO2 conditions for different cratons and mobile belts worldwide, using a database of 4440 mineral EPMA analyses. Beneath all cratons, the cold branch of the mantle geotherm (35-32 mWm−2) relates to PT estimates for sub-calcic garnets and rare omphacitic diamond inclusions, referring to major continental growth events in Archean. High-temperature plume-related geotherms are common in Proterozoic kimberlites such as Premier, Mesozoic-Roberts Victor etc. and are common in Slave and Siberian cratons. Eclogitic and pyroxenitic pyroxenes and garnets and Fe- and Ca-enriched pyrope diamond inclusions prevail in mobile belts like Limpopo, Magondi, Ural, Khapchan and in the marginal parts of cratons (Kimberly in Australia) They refer to diamondiferous eclogite-pyroxenite lens in the mididdle parts of lithospheric mantle. Eclogitic garnets and clinopyroxenes show trends of joint decreasing Mg# and pressures due to differentiation of rising melts. Dunitic Ca pyropes giving high-pressure estimates prevail in the central parts of cratons. The PT for the chromites reflect conditions just above the lithosphere-asthenosphere boundary formed due to interaction with the hydrous plume protokimberlite melts. Archean diamond Ca-enrich pyropes inclusions from Wawa province Canada give low-temperature conditions. Inclusions from younger kimberlites in Superior and Slave, Siberian and East European cratons show complex high-temperature geotherms due to plumes influence. Peridotite garnets beneath the Amazonian craton indicate complex layering in the lithosphere base and a pyroxene layer in the middle part of mantle lithosphere. Diamond inclusions from the Kimberley Craton of Australia show the greatest variations in the temperatures and composition. The mobile belts and marginal parts of cratons are favorable for the finding of the abundant colored diamonds. The huge plume influence for hydrated and eclogite-rich mantle like in Premier, Venetia and other kimberlites brings to the formation of giant diamonds. Diamond inclusion reveal the huge variations of PT conditions formed by different agents due to long complex stories of craton deciphered using thermobarometry and trace element and isotopic geochemistry.

MINERAL COMPOSITION AND PT PARAMETERS OF CRYSTALLIZATION OF MANTLE ROCKS UNDER KIMBERLITE FIELDS OF THE ANABAR REGION

The composition of barophilic minerals from mantle xenoliths and Cpx from concentrates of the Kuranakh, Luchakan, Dyuken, and Ary-Mastakh fields of the Anabar region has been studied. Under these fields, the lithospheric mantle compositions vary significantly. The PT parameters of crystallization were calculated using the composition of clinopyroxenes from xenoliths and heavy fraction of kimberlites. The lithospheric mantle rocks under the northern fields have higher values of Mg# of minerals and calculated mantle geotherm (35–48 mW/m2) compared to the parameters for the southern diamond fields. The pipes from the southwestern part of the Ary-Mastakh field are promising for the diamond potential, presenting Grt-bearing lherzolites and harzburgites with a high content of Cr2O3 (to 8.5 wt. %).

Textures Induced by the Coesite‐Stishovite Transition and Implications for the Visibility of the X‐Discontinuity

AbstractThe coesite‐stishovite phase transition is considered the most plausible candidate to explain the X‐discontinuity observed at around 300 km depth in a variety of tectonic settings. Here, we investigate the microstructure in SiO2 across the coesite‐stishovite transition in uniaxial compression experiments. We apply the multigrain crystallography technique (MGC) in a laser‐heated diamond‐anvil cell (LH‐DAC) to identify the seismic signature of the transition and the amount of SiO2 in the mantle. While coesite displays weak lattice‐preferred orientations (LPO) before the transition, stishovite develops strong LPO characterized by the alignment of [112] axes parallel to the compression direction. However, LPO has little effect on the impedance contrast across the transition, which is up to 8.8% for S‐waves in a mid‐ocean ridge basalt (MORB) composition at 300 km depth along a normal mantle geotherm, 10 GPa‐1700 K. Therefore, 10–50 vol.% of a MORB component, corresponding to 0.6–3.2 vol.% SiO2, mechanically mixed with the pyrolytic mantle would be required to explain the range of impedance (and velocity) contrasts observed for the X‐discontinuity. Based on the reflection coefficients computed for the coesite‐stishovite transition, we show that the incidence angle or epicentral distance is critical for the detection of silica‐containing lithologies in the upper mantle, with highest detection probabilities for small incidence angles. The intermittent visibility of the X‐discontinuity may thus be explained by the seismic detectability of the coesite‐stishovite transition rather than by absence of the transition or chemical heterogeneities in some specific tectonic settings.

Phase Stability of Al‐Bearing Dense Hydrous Magnesium Silicates at Topmost Lower Mantle Conditions: Implication for Water Transport in the Mantle

AbstractIn this study, we investigated the phase stability of Al‐free and Al‐bearing superhydrous phase B (shy‐B) up to 55 GPa and 2500 K. In comparison with Al‐free shy‐B, the incorporation of 11.7 wt.% Al2O3 in shy‐B expands the stability by ∼400–800 K at 20–30 GPa. The determined dehydration boundary for Al‐bearing phase D indicates that it could be present even at normal mantle geotherm conditions at 30–40 GPa. Up to 23.8 mol.% Al2O3 can be dissolved into the structures of akimotoite and bridgmanite as a result of the decomposition reactions of Al‐bearing shy‐B and phase D between 20 and 40 GPa. Results of further experiments indicate that δ‐AlOOH is the stable hydrous phase coexisting with Al‐depleted bridgmanite at pressures above 52 GPa. This study shows that the incorporation of Al in dense hydrous magnesium silicates can have a profound impact on our picture of the water cycle in the deep Earth.

Anharmonic thermodynamic properties and phase boundary across the postperovskite transition in MgSiO3

To address the effects of lattice anharmonicity across the perovskite to post-perovskite transition in MgSiO$_3$, we conduct calculations using the phonon quasiparticle (PHQ) approach. The PHQ is based on \textit{ab initio} molecular dynamics and, in principle, captures full anharmonicity. Free energies in the thermodynamic limit ($N \rightarrow \infty$) are computed using temperature-dependent quasiparticle dispersions within the phonon gas model. Systematic results on anharmonic thermodynamic properties and phase boundary are reported. Both the local density approximation (LDA) and the generalized gradient approximation (GGA) calculations are performed to provide confident constraints on these properties. Anharmonic effects are demonstrated by comparing results with those obtained using the quasiharmonic approximation (QHA). The inadequacy of the QHA is indicated by its overestimation of thermal expansivity and thermodynamic Gr\"{u}neisen parameter and its converged isochoric heat capacity in the high-temperature limit. The PHQ phase boundary has a Clapeyron slope ($dP/dT$) that increases with temperature. This result contrasts with the nearly zero curvature of the QHA phase boundary. Anharmonicity bends the phase boundary to lower temperatures at high pressures. Implications for the double-crossing of the phase boundary by the mantle geotherm are discussed.

Broad Elastic Softening of (Mg,Fe)O Ferropericlase Across the Iron Spin Crossover and a Mixed‐Spin Lower Mantle

AbstractThe elastic bulk modulus softening of (Mg,Fe)O ferropericlase across the iron spin crossover induces dramatic changes in its physical properties, including seismic P‐velocities and viscosity. Here, we performed compression of powders of (Mg0.8‐0.9Fe0.2‐0.1)O in a piezo‐driven dynamic Diamond Anvil Cell (dDAC) and derive the bulk modulus by differentiation of pressure and volume data, providing first data on the broadness of the elastic softening for ferropericlase with mantle‐relevant compositions. We complement our experimental results with theoretical calculations that extend previous studies by considering multiple random configurations of iron, and going beyond treating high‐ and low‐spin iron as an ideal solution. Both experiments and computations show a broad and asymmetric softening of the bulk modulus, and suggest that the softening is sensitive to the distribution of iron in the ferropericlase structure. Our high‐temperature calculations show that mixed‐spin (Mg,Fe)O dominates the lower mantle at all depths below 1,000 km. In contrast to most previous works, we find that ferropericlase will not exist in pure low‐spin state along a typical mantle geotherm. Based on our model, the physical properties of ferropericlase will show significant lateral variation at depths below 1,400 km, with the strongest effects expected between 2,000 and 2,600 km.

High-temperature phase relations of hydrous aluminosilicates at 22 GPa in the AlOOH-AlSiO3OH system

Abstract The stabilities of the minerals that can hold water are important for understanding water behavior in the Earth’s deep interior. Recent experimental studies have shown that the incorporation of aluminum enhances the thermal stabilities of hydrous minerals significantly. In this study, the phase relations of hydrous aluminosilicates in the AlOOH-AlSiO3OH system were investigated at 22 GPa and 1400–2275 K using a multi-anvil apparatus. Based on the X-ray diffraction measurements and composition analysis of the recovered samples, we found that the AlSiO4H phase Egg forms a solid solution with δ-AlOOH above 1500 K. Additionally, at temperatures above 1800 K, two unknown hydrous aluminosilicates with compositions Al2.03Si0.97O6H2.03 and Al2.11Si0.88O6H2.11 appeared, depend ing on the bulk composition of the starting materials. Both phases can host large amounts of water, at least up to 2275 K, exceeding the typical mantle geotherm. The extreme thermal stability of hydrous aluminosilicates suggests that deep-subducted crustal rocks could be a possible reservoir of water in the mantle transition zone and the uppermost lower mantle.

Thermal Equations of State of Corundum and Rh2O3 (II)‐Type Al2O3 up to 153 GPa and 3400 K

AbstractIn this study, we present new experimental constraints on the thermal equations of state of corundum and Rh2O3(II)‐type Al2O3 up to 153 GPa and 3400 K using synchrotron X‐ray diffraction in laser‐heated diamond anvil cells. Corundum was observed to transform into a mixture of corundum and Rh2O3(II)‐type Al2O3 at 106 GPa and 2300 K, accompanied by a strong kinetic barrier. The Rh2O3(II)‐type Al2O3 further transforms into the CaIrO3‐phase at 156 GPa and 3700 K. The transition from corundum to Rh2O3(II)‐type Al2O3 along a normal mantle geotherm could lead to a 1.9(5)% increase in density (ρ) but a 0.6(3)% decrease in bulk sound velocity (VΦ). Al2O3 is one of the major components of the anorthositic crust once this old crust was subducted to the deep mantle. Using the obtained thermoelastic parameters, we further modeled ρ and VΦ profiles of primordial anorthositic crust and found that the subducted fate of the primordial anorthositic crust depended strongly on its temperature. Our modeling reveals that primordial anorthositic crust along a normal mantle geotherm could descend to the transition zone but be trapped at the topmost lower mantle with a greater VΦ. Sinking of the anorthositic crust to the lower mantle can only occur along a 500–1000 K colder slab geotherm.

Aluminous hydrous magnesium silicate as a lower-mantle hydrogen reservoir: a role as an agent for material transport

The potential for storage of a large quantity of water/hydrogen in the lower mantle has important implications for the dynamics and evolution of the Earth. A dense hydrous magnesium silicate called phase D is a potential candidate for such a hydrogen reservoir. Its MgO–SiO2–H2O form has been believed to be stable at lower-mantle pressures but only in low-temperature regimes such as subducting slabs because of decomposition below mantle geotherm. Meanwhile, the presence of Al was reported to be a key to enhancing the thermal stability of phase D; however, the detailed Al-incorporation effect on its stability remains unclear. Here we report on Al-bearing phase D (Al-phase D) synthesized from a bridgmanite composition, with Al content expected in bridgmanite formed from a representative mantle composition, under over-saturation of water. We find that the incorporation of Al, despite smaller amounts, into phase D increases its hydrogen content and moreover extends its stability field not only to higher temperatures but also presumably to higher pressures. This leads to that Al-phase D can be one of the most potential reservoirs for a large quantity of hydrogen in the lower mantle. Further, Al-phase D formed by reaction between bridgmanite and water could play an important role in material transport in the lower mantle.

Lower mantle geotherms, flux, and power from incorporating new experimental and theoretical constraints on heat transport properties in an inverse model

Abstract. An inverse method is devised to probe Earth's thermal state without assuming its mineralogy. This constrains thermal conductivity (κ) in the lower mantle (LM) by combining seismologic models of bulk modulus (B) and pressure (P) vs. depth (z) with a new result, ∂ln(κ) / ∂P ∼ 7.33/BT, and available high temperature (T) data on κ for lengths exceeding millimeters. Considering large samples accounts for the recently revealed dependence of heat transport properties on length scale. Applying separation of variables to seismologic ∂B/∂P vs. depth isolates changes with T. The resulting LM dT / dz depends on ∂2B/∂P2 and ∂B/∂T, which vary little among dense phases. Because seismic ∂B/∂P is discontinuous and model dependent ∼ 200 km above the core, unlike the LM, our results are extrapolated through this tiny layer (D′′). Flux and power are calculated from dT / dz for cases of high (oxide) and low (silicate) κ. Geotherm calculations are independent of κ, and thus of LM mineralogy, but require specifying a reference temperature at some depth: a wide range is considered. Limitations on deep melting are used to ascertain which of our geotherm, flux, and power curves best represent Earth's interior. Except for an oxide composition with miniscule ∂2B/∂P2, the LM heats the core, causing it to melt. Deep heating is attributed to cyclical stresses from > 1000 km daily and monthly fluctuations of the barycenter inside the LM.

Elastic properties of Fe-bearing Akimotoite at mantle conditions: Implications for composition and temperature in lower mantle transition zone

The pyrolite model, which can reproduce the upper-mantle seismic velocity and density profiles, was suggested to have significantly lower velocities and density than seismic models in the lower mantle transition zone (MTZ). This argument has been taken as mineral-physics evidence for a compositionally distinct lower MTZ. However, previous studies only estimated the pyrolite velocities and density along a one-dimension (1D) geotherm and never considered the effect of lateral temperature heterogeneity. Because the majorite-perovskite-akimotoite triple point is close to the normal mantle geotherm in the lower MTZ, the lateral low-temperature anomaly can result in the presence of a significant fraction of akimotoite in pyrolitic lower MTZ. In this study, we reported the elastic properties of Fe-bearing akimotoite based on first-principles calculations. Combining with literature data, we found that the seismic velocities and density of the pyrolite model can match well those in the lower MTZ when the lateral temperature heterogeneity is modeled by a Gaussian distribution with a standard deviation of ∼100 K and an average temperature of dozens of K higher than the triple point of MgSiO3. We suggest that a harzburgite-rich lower MTZ is not required and the whole mantle convection is expected to be more favorable globally.

Depressed 660-km discontinuity caused by akimotoite\u2013bridgmanite transition

The 660-kilometre seismic discontinuity is the boundary between the Earth’s lower mantle and transition zone and is commonly interpreted as being due to the dissociation of ringwoodite to bridgmanite plus ferropericlase (post-spinel transition)1–3. A distinct feature of the 660-kilometre discontinuity is its depression to 750 kilometres beneath subduction zones4–10. However, in situ X-ray diffraction studies using multi-anvil techniques have demonstrated negative but gentle Clapeyron slopes (that is, the ratio between pressure and temperature changes) of the post-spinel transition that do not allow a significant depression11–13. On the other hand, conventional high-pressure experiments face difficulties in accurate phase identification due to inevitable pressure changes during heating and the persistent presence of metastable phases1,3. Here we determine the post-spinel and akimotoite–bridgmanite transition boundaries by multi-anvil experiments using in situ X-ray diffraction, with the boundaries strictly based on the definition of phase equilibrium. The post-spinel boundary has almost no temperature dependence, whereas the akimotoite–bridgmanite transition has a very steep negative boundary slope at temperatures lower than ambient mantle geotherms. The large depressions of the 660-kilometre discontinuity in cold subduction zones are thus interpreted as the akimotoite–bridgmanite transition. The steep negative boundary of the akimotoite–bridgmanite transition will cause slab stagnation (a stalling of the slab’s descent) due to significant upward buoyancy14,15.

The effect of Ti on Ca-pv and Mg-pv phase stability

Magnesium silicate perovskite in the form of bridgmanite (bdg) and Calcium silicate perovskite (Ca-pv) have similar chemical structures and may mix into a single perovskite phase in the lower mantle which would have profound effects on many seismic properties. While we have previously found that this is unlikely to occur in pure bdg and ca-pv in this paper we examine whether phase mixing can be induced by Titanium.We predict that even small amounts of Ti can cause significant increases in mixing of the two phases. Miscibility of the phases has a strong dependence upon how Ti is partitioned between the two phases before mixing and thus the source and history of introduced Ti is important in determining miscibility.We predict basalts, even those with heavy Ti enrichment (10%), will not form a single phase in subducted slabs as their mixing temperatures remain above 2500 K for most compositions throughout lower mantle pressures. In pyrolytic mantle it is predicted that at shallow depths large amounts of Ti are needed to induce phase mixing (~40% Ti at 25 GPa and geotherm temperatures) but less Ti is needed to induce mixing with depth (~1% Ti at 125 GPa and geotherm temperatures). Thus we predict that enriched Ti regions will see perovskite mixing near the bottom of the lower mantle. These mixed perovskite regions partition Ti out of unmixed regions and thus provide a mechanism for Ti enriched regions to form in the deep lower mantle. Both ferrous iron and the Ca:Mg ratio are predicted to have a larger control on the mixing temperature of pyrolytic systems than Ti, however. For Ti and Ca rich pyroxene megacrysts we find that they should become a single phase along a lower mantle geotherm at around 40–115 GPa depending heavily upon Ti and Ca concentration.

Stability of Ca(OH)2 at Earth's deep lower mantle conditions

In this paper, we report that $\mathrm{Ca}{(\mathrm{OH})}_{2}$, portlandite, is predicted to be stable up to 100 GPa via an unbiased structural search method combined with first-principles calculations. Two pressure-induced structures with $P2{}_{1}/c$ and $Pnma$ symmetry are proposed at high pressure. The monoclinic $P2{}_{1}/c$ structure is the most stable phase after 23 GPa and will undergo a phase transition into a $Pnma$ phase at 78 GPa and 0 K. This phase transition is computed to occur at lower pressure as the temperature increases. The high-pressure phases of $\mathrm{Ca}{(\mathrm{OH})}_{2}$ that we proposed are stable against decomposition into CaO and ${\mathrm{H}}_{2}\mathrm{O}$ at the conditions corresponding to lower mantle geotherms. Our results shed light on the possible presence of $\mathrm{Ca}{(\mathrm{OH})}_{2}$ in the Earth's mantle as well as its water transportation in the Earth's interior.

High-pressure syntheses and crystal structure analyses of a new low-density CaFe2O4-related and CaTi2O4-type MgAl2O4 phases

AbstractThree single crystals of CaTi2O4 (CT)-type, CaFe2O4 (CF)-type, and new low-density CaFe2O4 (LD-CF) related MgAl2O4 were synthesized at 27 GPa and 2500 °C and also CT-type MgAl2O4 at 45 GPa and 1727 °C using conventional and advanced multi-anvil technologies, respectively. The structures of CT-type and LD-CF related MgAl2O4 were analyzed by single-crystal X-ray diffraction. The lattice parameters of the CT-type phases synthesized at 27 and 45 GPa were a = 2.7903(4), b = 9.2132(10), and c = 9.3968(12) Å, and a = 2.7982(6), b = 9.2532(15), and c = 9.4461(16) Å, respectively, (Z = 4, space group: Cmcm) at ambient conditions. This phase has an AlO6 octahedral site and an MgO8 bicapped trigonal prism with two longer cation-oxygen bonds. The LD-CF related phase has a novel structure with orthorhombic symmetry (space group: Pnma), and lattice parameters of a = 9.207(2), b = 3.0118(6), and c = 9.739(2) Å (Z = 4). The structural framework comprises tunnel-shaped spaces constructed by edge- and corner-sharing of AlO6 and a 4+1 AlO5 trigonal bipyramid, in which MgO5 trigonal bipyramids are accommodated. The CF-type MgAl2O4 also has the same space group of Pnma but a slightly different atomic arrangement, with Mg and Al coordination numbers of 8 and 6, respectively. The LD-CF related phase has the lowest density of 3.50 g/cm3 among MgAl2O4 polymorphs, despite its high-pressure synthesis from the spinel-type phase (3.58 g/cm3), indicating that the LD-CF related phase formed via back-transformation from a high-pressure phase during the recovery. Combined with the previously determined phase relations, the phase transition between CF-and CT-type MgAl2O4 is expected to have a steep Clapeyron slope. Therefore, CT-type phase may be stable in basaltic- and continental-crust compositions at higher temperatures than the average mantle geotherm in the wide pressure range of the lower mantle. The LD-CF related phase could be found in shocked meteorites and used for estimating shock conditions.

Phlogopite-pargasite coexistence in an oxygen reduced spinel-peridotite ambient

The occurrence of phlogopite and amphibole in mantle ultramafic rocks is widely accepted as the modal effect of metasomatism in the upper mantle. However, their simultaneous formation during metasomatic events and the related sub-solidus equilibrium with the peridotite has not been extensively studied. In this work, we discuss the geochemical conditions at which the pargasite-phlogopite assemblage becomes stable, through the investigation of two mantle xenoliths from Mount Leura (Victoria State, Australia) that bear phlogopite and the phlogopite + amphibole (pargasite) pair disseminated in a harzburgite matrix. Combining a mineralogical study and thermodynamic modelling, we predict that the P–T locus of the equilibrium reaction pargasite + forsterite = Na-phlogopite + 2 diopside + spinel, over the range 1.3–3.0 GPa/540–1500 K, yields a negative Clapeyron slope of -0.003 GPa K–1 (on average). The intersection of the P–T locus of supposed equilibrium with the new mantle geotherm calculated in this work allowed us to state that the Mount Leura xenoliths achieved equilibrium at 2.3 GPa /1190 K, that represents a plausible depth of ~ 70 km. Metasomatic K-Na-OH rich fluids stabilize hydrous phases. This has been modelled by the following equilibrium equation: 2 (K,Na)-phlogopite + forsterite = 7/2 enstatite + spinel + fluid (components: Na2O,K2O,H2O). Using quantum-mechanics, semi-empirical potentials, lattice dynamics and observed thermo-elastic data, we concluded that K-Na-OH rich fluids are not effective metasomatic agents to convey alkali species across the upper mantle, as the fluids are highly reactive with the ultramafic system and favour the rapid formation of phlogopite and amphibole. In addition, oxygen fugacity estimates of the Mount Leura mantle xenoliths [Δ(FMQ) = –1.97 ± 0.35; –1.83 ± 0.36] indicate a more reducing mantle environment than what is expected from the occurrence of phlogopite and amphibole in spinel-bearing peridotites. This is accounted for by our model of full molecular dissociation of the fluid and incorporation of the O-H-K-Na species into (OH)-K-Na-bearing mineral phases (phlogopite and amphibole), that leads to a peridotite metasomatized ambient characterized by reduced oxygen fugacity.

The relative behaviour of bulk and shear modulus as an indicator of the iron spin transition in the lower mantle

For a regular material, in a single state, the effect of increasing pressure is to produce a linear relation between shear modulus (G), bulk modulus (K) and pressure (p). Such a dependence on pressure fits the behaviour of individual mineral and mineral composites well. For the iron bearing minerals in the lower mantle, the transition from the high-spin state to the low-spin state with increasing pressure produces deviations from this simple behaviour, due to a much larger reduction of the bulk modulus than the shear modulus in the spin crossover. There are linear zones in the dependence of the modulus ratio G/K on pressure scaled by bulk modulus (p/K) above and below the transition, with a complex excursion to high ratios in between. With increasing temperature the spin transition is smoothed out in depth, and is expected to be smooth along a mantle geotherm. For the ak135 body-wave model of radial Earth structure there is a slight, but distinct, change of slope in the relation between the modulus ratio and scaled pressure corresponding to a depth range around 1550 km. This feature is strongly suggestive of a residual effect of a 3-D averaged spin transition in the ferropericlase component of the lower mantle.