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Register a new userBlocked radiative heat transport in the hot pyrolitic lower mantle
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The heat flux across the core-mantle boundary (QCMB) is the key parameter to understand the Earth/s thermal history and evolution. Mineralogical constraints of the QCMB require deciphering contributions of the lattice and radiative components to the thermal conductivity at high pressure and temperature in lower mantle phases with depth-dependent composition. Here we determine the radiative conductivity (krad) of a realistic lower mantle (pyrolite) in situ using an ultra-bright light probe and fast time-resolved spectroscopic techniques in laser-heated diamond anvil cells. We find that the mantle opacity increases critically upon heating to ~3000 K at 40-135 GPa, resulting in an unexpectedly low radiative conductivity decreasing with depth from ~0.8 W/m/K at 1000 km to ~0.35 W/m/K at the CMB, the latter being ~30 times smaller than the estimated lattice thermal conductivity at such conditions. Thus, radiative heat transport is blocked due to an increased optical absorption in the hot lower mantle resulting in a moderate CMB heat flow of ~8.5 TW, at odds with present estimates based on the mantle and core dynamics. This moderate rate of core cooling implies an inner core age of about 1 Gy and is compatible with both thermally- and compositionally-driven ancient geodynamo.
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The exceptional ability of carbon to form sp2 and sp3 bonding states leads to a great structural and chemical diversity of carbon-bearing phases at non-ambient conditions. Here we use laser-heated diamond anvil cells combined with synchrotron x-ray diffraction, Raman spectroscopy, and first-principles calculations to explore phase transitions in CaCO3 at P > 40 GPa. We find that post-aragonite CaCO3 transforms to the previously predicted P21/c-CaCO3 with sp3-hybridized carbon at 105 GPa (~30 GPa higher than the theoretically predicted crossover pressure). The lowest enthalpy transition path to P21/c-CaCO3 includes reoccurring sp2- and sp3-CaCO3 intermediate phases and transition states, as reveled by our variable-cell nudged elastic band simulation. Raman spectra of P21/c-CaCO3 show an intense band at 1025 cm-1, which we assign to the symmetric C-O stretching vibration based on empirical and first principles calculations. This Raman band has a frequency that is ~20 % lower than the symmetric C-O stretching in sp2-CaCO3, due to the C-O bond length increase across the sp2-sp3 transition, and can be used as a fingerprint of tetrahedrally-coordinated carbon in other carbonates.
Here, we provide a reappraisal of potential LLSVPs compositions based on an improved mineralogical model including, for instance, the effects of alumina. We also systematically investigate the effects of six parameters: FeO and Al$_{2}$O$_{3}$ content, proportion of CaSiO$_{3}$ and bridgmanite (so that the proportion of ferropericlase is implicitly investigated), Fe$^{3+}$/$sum$Fe and temperature contrast between far-field mantle and LLSVPs. From the 81 millions cases studied, only 79000 cases explain the seismic observations. Nevertheless, these successful cases involve a large range of parameters with, for instance, FeO content between 12--25~wt% and Al$_{2}$O$_{3}$ content between 3--17~wt%. We then apply a principal component analysis (PCA) to these cases and find two robust results: (i) the proportion of ferropericlase should be low ($<$6vol%); (ii) the formation of Fe$^{3+}$-bearing bridgmanite is much more favored than other iron-bearing phases. Following these results, we identify two end-member compositions, Bm-rich and CaPv-rich, and discuss their characteristics. Finally, we discuss different scenarios for the formation of LLSVPs and propose that investigating the mineral proportion produced by each scenario is the best way to evaluate their relevance. For instance, the solidification of a primitive magma ocean may produce FeO and Al$_{2}$O$_{3}$ content similar to those suggested by our analysis. However, the mineral proportion of such reservoirs is not well-constrained and may contain a larger proportion of ferropericlase than what is allowed by our results.
Earth/s lowermost mantle displays complex geological structures that likely result from heterogeneous thermal and electromagnetic interaction with the core. Geophysical models of the core-mantle boundary (CMB) region rely on the thermal and electrical conductivities of appropriate geomaterials which, however, have never been probed at representative pressure and temperature (P-T) conditions. Here we report on the opacity of single crystalline bridgmanite and ferropericlase, which is linked to both their radiative and electrical conductivity, measured in dynamically- and statically-heated diamond anvil cells as well as computed from first-principles at CMB conditions. Our results show that light absorption in the visible spectral range is enhanced upon heating in both minerals but the rate of change in opacity with temperature is a factor of six higher in ferropericlase. As a result, bridgmanite in the lowermost mantle is moderately transparent while ferropericlase is highly opaque. Our measurements suggest a very low (< 1 W/m/K) and largely temperature-independent radiative conductivity in the lowermost mantle, at odds with previous studies. This implies that the radiative mechanism has not contributed significantly to cooling the Earth/s core throughout the geologic time and points to a present-day CMB heat flow of 9-11 TW. Opaque ferropericlase is electrically conducting and mediates strong core-mantle electromagnetic coupling, explaining the intradecadal oscillations in the length of day, low secular geomagnetic variations in Central Pacific, and the preferred paths of geomagnetic pole reversals.
Carbonates are the main species that bring carbon deep into our planet through subduction. They are an important rock-forming mineral group, fundamentally distinct from silicates in Earths crust in that carbon binds to three oxygen atoms, while silicon is bonded to four oxygens. Here, we present experimental evidence that under the sufficiently high pressures and high temperatures existing in the lower mantle, ferromagnesian carbonates transform to a phase with tetrahedrally coordinated carbons. Above 80 GPa, in situ synchrotron infrared experiments show the unequivocal spectroscopic signature of the high-pressure phase of (Mg,Fe)CO$_3$. Using ab-initio calculations, we assign the new IR signature to C-O bands associated with tetrahedrally coordinated carbon with asymmetric C-O bonds. Tetrahedrally coordinated carbonates are expected to exhibit substantially different reactivity than low pressure three-fold coordinated carbonates, as well as different chemical properties in the liquid state. Hence this may have significant implications on carbon reservoirs and fluxes and the global geodynamic carbon cycle.
Scattering of seismic waves can reveal subsurface structures but usually in a piecemeal way focused on specific target areas. We used a manifold learning algorithm called the Sequencer to simultaneously analyze thousands of seismograms of waves diffracting along the core-mantle boundary and obtain a panoptic view of scattering across the Pacific region. In nearly half of the diffracting waveforms, we detected seismic waves scattered by three-dimensional structures near the core-mantle boundary. The prevalence of these scattered arrivals shows that the region hosts pervasive lateral heterogeneity. Our analysis revealed loud signals due to a plume root beneath Hawaii and a previously unrecognized ultralow-velocity zone beneath the Marquesas Islands. These observations illustrate how approaches flexible enough to detect robust patterns with little to no user supervision can reveal distinctive insights into the deep Earth.
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