Jeffrey S. Pigott

Dry (Mg,Fe)SiO3 perovskite in the Earth's lower mantle

Combined synthesis experiments and first-principles calculations show that MgSiO3-perovskite with minor Al or Fe does not incorporate significant OH under lower mantle conditions. Perovskite, stishovite, and residual melt were synthesized from natural Bamble enstatite samples (Mg/(Fe + Mg) = 0.89 and 0.93; Al2O3 < 0.1 wt % with 35 and 2065 ppm weight H2O, respectively) in the laser-heated diamond anvil cell at 1600–2000 K and 25–65 GPa. Combined Fourier transform infrared spectroscopy, X-ray diffraction, and ex situ transmission electron microscopy analysis demonstrates little difference in the resulting perovskite as a function of initial water content. Four distinct OH vibrational stretching bands are evident upon cooling below 100 K (3576, 3378, 3274, and 3078 cm−1), suggesting four potential bonding sites for OH in perovskite with a maximum water content of 220 ppm weight H2O, and likely no more than 10 ppm weight H2O. Complementary, Fe-free, first-principles calculations predict multiple potential bonding sites for hydrogen in perovskite, each with significant solution enthalpy (0.2 eV/defect). We calculate that perovskite can dissolve less than 37 ppm weight H2O (400 ppm H/Si) at the top of the lower mantle, decreasing to 31 ppm weight H2O (340 ppm H/Si) at 125 GPa and 3000 K in the absence of a melt or fluid phase. We propose that these results resolve a long-standing debate of the perovskite melting curve and explain the order-of-magnitude increase in viscosity from upper to lower mantle.

Hydrous ringwoodite to 5 K and 35 GPa: Multiple hydrogen bonding sites resolved with FTIR spectroscopy

Abstract Multiple substitution mechanisms for hydrogen in γ-(Mg,Fe)2SiO4, ringwoodite, lead to broad, overlapping, and difficult-to-interpret FTIR spectra. Through combined low-temperature, high-pressure synchrotron-based FTIR spectroscopy, the multiple bonding sites become evident, and can be traced as a function of temperature and compression. Multiple OH stretching bands can be resolved in iron-bearing and iron-free samples with 0.79-2.5(3) wt% H2O below 200 K at ambient pressure, with cooling to 5 K at 35 and 23 GPa resulting in the resolution of possibly as many as 5 OH stretching bands traceable at room temperature from 23 GPa down to 8 GPa. A distribution of defect mechanisms between ‴Mg″+2(H·) at 3100, 3270, and possibly 2654 cm-1, ‴Si″′+4(H·) at 3640 cm-1, and MgSi″+2(H·) at 2800 cm-1 can then be resolved. These multiple defect mechanisms can therefore explain the higher electrical and proton conductivity in ringwoodite when compared to wadsleyite, and therefore may be applied to resolve spatial variations in water storage in the Earth’s transition zone.

The role of carbon in extrasolar planetary geodynamics and habitability

The proportions of oxygen, carbon and major rock-forming elements (e.g. Mg, Fe, Si) determine a planets dominant mineralogy. Variation in a planets mineralogy subsequently affects planetary mantle dynamics as well as any deep water or carbon cycle. Through thermodynamic models and high pressure diamond anvil cell experiments, we demonstrate the oxidation potential of C is above that of Fe at all pressures and temperatures indicative of 0.1 - 2 Earth-mass planets. This means that for a planet with (Mg+2Si+Fe+2C)/O > 1, excess C in the mantle will be in the form of diamond. We model the general dynamic state of planets as a function of interior temperature, carbon composition, and size, showing that above a critical threshold of

Calculation of the energetics of water incorporation in majorite garnet

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Microfabrication of controlled-geometry samples for the laser-heated diamond-anvil cell using focused ion beam technology

3 atom% C, limited to no mantle convection will be present assuming an Earth-like geotherm. We assert then that in the C-(Mg+2Si+Fe)-O system, only a very small compositional range produce habitable planets. Planets outside of this habitable range will be dynamically sluggish or stagnant, thus having limited carbon or water cycles leading to surface conditions inhospitable to life as we know it.

High-pressure, high-temperature equations of state using nanofabricated controlled-geometry Ni/SiO2/Ni double hot-plate samples

Abstract Interpretation of lateral variations in upper mantle seismic wave speeds requires constraints on the relationship between elasticity and water concentration at high pressure for all major mantle minerals, including the garnet component. We have calculated the structure and energetics of charge-balanced hydrogen substitution into tetragonal MgSiO3 majorite up to P = 25 GPa using both classical atomistic simulations and complementary first-principles calculations. At the pressure conditions of Earth’s transition zone, hydroxyl groups are predicted to be bound to Si vacancies (□) as the hydrogarnet defect, [□Si+4OHO]X, at the Si2 tetrahedral site or as the [□Mg+2OHO]X defect at the octahedral Mg3 site. The hydrogarnet defect is more favorable than the [□Mg+2OHO]X defect by 0.8-1.4 eV/H at 20 GPa. The presence of 0.4 wt% Al2O3 substituted into the octahedral sites further increases the likelihood of the hydrogarnet defect by 2.2-2.4 eV/H relative to the [□Mg+2OHO]X defect at the Mg3 site. OH defects affect the seismic ratio, R = dlnvs/dlnvp, in MgSiO3 majorite (ΔR = 0.9-1.2 at 20 GPa for 1400 ppm wt H2O) differently than ringwoodite at high pressure, yet may be indistinguishable from the thermal dlnvs/dlnvp for ringwoodite. The incorporation of 3.2 wt% Al2O3 also decreases R(H2O) by ~0.2-0.4. Therefore, to accurately estimate transition zone compositional and thermal anomalies, hydrous majorite needs to be considered when interpreting seismic body wave anomalies in the transition zone.

Stream geochemistry, chemical weathering and CO2 consumption potential of andesitic terrains, Dominica, Lesser Antilles

The pioneering of x-ray diffraction with in situ laser heating in the diamond-anvil cell has revolutionized the field of high-pressure mineral physics, expanding the ability to determine high-pressure, high-temperature phase boundaries and equations of state. Accurate determination of high-pressure, high-temperature phases and densities in the diamond-anvil cell rely upon collinearity of the x-ray beam with the center of the laser-heated spot. We present the development of microfabricated samples that, by nature of their design, will have the sample of interest in the hottest portion of the sample. We report initial successes with a simplified design using a Pt sample with dimensions smaller than the synchrotron-based x-ray spot such that it is the only part of the sample that absorbs the heating laser ensuring that the x-rayed volume is at the peak hotspot temperature. Microfabricated samples, synthesized using methods developed at The Ohio State Universitys Mineral Physics Laboratory and Campus Electron Optics Facility, were tested at high P-T conditions in the laser-heated diamond-anvil cell at beamline 16 ID-B of the Advanced Photon Source. Pt layer thicknesses of ≤0.8 μm absorb the laser and produce accurate measurements on the relative equations of state of Pt and PtC. These methods combined with high-purity nanofabrication techniques will allow for extension by the diamond-anvil cell community to multiple materials for high-precision high-pressure, high-temperature phase relations, equations of state, melting curves, and transport properties.

Equations of state and phase boundary for stishovite and CaCl2-type SiO2

We have fabricated novel controlled-geometry samples for the laser-heated diamond-anvil cell (LHDAC) in which a transparent oxide layer (SiO2) is sandwiched between two laser-absorbing layers (Ni) in a single, cohesive sample. The samples were mass manufactured (>104 samples) using a combination of physical vapor deposition, photolithography, and wet and plasma etching. The double hot-plate arrangement of the samples, coupled with the chemical and spatial homogeneity of the laser-absorbing layers, addresses problems of spatial temperature heterogeneities encountered in previous studies where simple mechanical mixtures of transparent and opaque materials were used. Here we report thermal equations of state (EOS) for nickel to 100 GPa and 3000 K and stishovite to 50 GPa and 2400 K obtained using the LHDAC and in situ synchrotron X-ray microdiffraction. We discuss the inner core composition and the stagnation of subducted slabs in the mantle based on our refined thermal EOS.