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Ocean basins are formed when continents are broken apart. Adiabatic melt generation that is driven by rifting of continental lithosphere is strongly dependent on the rate of extension. Slow extension results in conductive heat loss from the upwelling mantle, whereas cooling is limited during fast extension and can result in the geotherm intersecting the peridotite solidus. However, there are few direct constraints on the rates of mantle upwelling during extension of continental lithosphere. Here, we use diffusion modelling of subsolidus REE re-equilibration between orthopyroxene and clinopyroxene to show that the Lanzo peridotite massif —lithospheric mantle exhumed during opening of the Ligurian Tethys—cooled at rates between 5 and 25°C/Myr across the spinel-to-plagioclase peridotite facies transition. We show that these rates are sufficiently slow to suppress significant adiabatic melt generation, providing an explanation for the magma-poor nature of the Alpine Tethys margin.

We have studied two samples of mantle diamond containing iron carbide inclusions from Jagersfontein kimberlite, South Africa. Syngenetic crystal growth is inferred using morphological characteristics. These samples provide an opportunity to investigate the isotopic partitioning of 13C in a terrestrial natural high-pressure and high-temperature (HPHT) system. The difference for the δ13C values between the diamond and coexisting iron carbide averaged 7.2 ± 1.3‰. These data are consistent with available data from the literature showing iron carbide to be 13C-depleted relative to elemental carbon (i.e., diamond). We infer that the minerals formed by crystallization of diamond and iron carbide at HPHT in the mantle beneath the Kaapvaal Craton. It is unclear whether crystallization occurred in subcratonic or sublithospheric mantle; in addition, the source of the iron is also enigmatic. Nonetheless, textural coherence between diamond and iron carbide resulted in isotopic partitioning of 13C between these two phases. These data suggest that significant isotopic fractionation of 13C/12C (Δ13C up to >7‰) can occur at HPHT in the terrestrial diamond stability field. We note that under reducing conditions at or below the iron-iron wustite redox buffer in a cratonic or deep mantle environment in Earth, the cogenesis of carbide and diamond may produce reservoirs of 13C-depleted carbon that have conventionally been interpreted as crustal in origin. Finally, the large Δ13C for diamond-iron carbide shown here demonstrates Δ13C for silicate-metallic melts is a parameter that needs to be constrained to better determine the abundance of carbon within the Earth's metallic core.

Diffusion of the divalent transition metals in the deep mantle is important for understanding length scales of mantle heterogeneity, transport across the core–mantle boundary, and the degree of equilibration during core formation. Here we report the results of experiments and theoretical calculations on Ni, Co, Fe and Mn diffusion in periclase, the primary repository of these elements in Earth’s lower mantle. The periclase used in the experiments was doped with 550 ppm Al 3 þ to fix the cation vacancy concentration, and the experiments were performed at 2 GPa and temperatures between 1673 and 2073 K. The variation in diffusion coefficients among the transition metals was ��

Experiments were performed to determine concentration-dependent diffusion coefficients of Cr3+ and Ga 3+ in periclase at temperatures of 1563–2273 K. Diffusion profiles measured in the quenched samples are consistent with a theoretical model in which the mobile species is a bound M 3+ -vacancy pair, and each profile was fitted to determine the binding energy and diffusion coefficient of the pair. Trivalent chromium-vacancy pairs diffuse more slowly than Ga 3+ -vacancy pairs, and with higher migration energy, 237 kJ/mol vs. 190 kJ/mol. Cation vacancies also bind less tightly to Cr3+ than to Ga3+, with average binding free energies of −22 and −83 kJ/mol, respectively. At all concentrations and temperatures, Cr 3+ diffuses much more slowly than Ga3+, by up to two orders of magnitude. The differences between Cr3+ and Ga3+ cannot be explained by differences in ionic radius or dipole polarizability, but are consistent with the influence of the crystal field on the partially occupied 3d orbitals of Cr 3+

Non-silicate oxide minerals are minor but important constituents of many igneous and metamorphic rocks, a major component of Earth’s lower mantle, and are well represented in planetary and meteoritic materials. Oxide minerals also have important roles in technology, for example as semiconductors, thermal and electrical insulators, fuel cell components, substrates for thin films, photovoltaic materials, and as products of metal oxidation. Because of their technological applications, and their fundamental interest to geosciences, materials science, physics and chemistry, the diffusion properties of many oxide minerals have been studied intensively, using a wide range of experimental, analytical and computational approaches. In many cases, particular attention has been devoted to deciphering the atomic-level mechanisms involved in diffusion. With the possible exceptions of metals and halides, oxides have probably been studied in more detail with regard to their point defect and diffusion properties than any other group of minerals. The oxide minerals considered in this chapter are relatively simple in terms of their structure and chemistry, but nonetheless exhibit quite complicated diffusion behavior in many cases. Due to the simplicity of the minerals, and to the amount and quality of data available, the origin of many of these complicated behaviors is fairly well understood. In magnetite, for example, cation diffusion rates have a complex dependence on oxygen fugacity. This dependence is due to internal redox reactions, and to a transition from an interstitial diffusion mechanism at low oxygen fugacities to a vacancy mechanism under more oxidizing conditions. Oxygen and titanium diffusion rates in rutile also vary strongly with f O2, due to internal reduction of titanium and the associated production of oxygen vacancies and titanium interstitials. Some cations in rutile exhibit strong diffusional anisotropy, which is thought to result from rapid diffusion along interstitial “channels” that extend along the c direction in …

Trivalent cations in periclase are attracted to cation vacancies and these defects tend to associate on adjacent sites to form mobile pairs. A theory has been developed to describe the concentration-dependent diffusion of Al in the presence of Al-vacancy pairs, and has been applied to experiments conducted at 1577–2273 K and 1 atm to 25 GPa. In all but one experiment, the Gibbs free energy of binding, inferred from the diffusion profiles, is between −44 and −60 kJ/mol, with an average value of −50 kJ/mol. The absolute value of the entropy of binding is constrained to be less than 50 J mol −1 K −1 , and the volume of binding is constrained to be between −1.8 and 0 cm3/mol. The diffusion coefficient of the Al-vacancy pair can be described by the equation D2 = D2,0 exp(−(E + PV)/RT), with E =2 13± 32 kJ/mol, V = 3.22 ± 0.25 cm 3 /mol, and log10 D2,0 = −6.17 ± 0.99 (in m 2 /s; all uncertainties 2� ). Calculations are presented for the diffusion of Al and Mg as functions of Al concentration, temperature and pressure.

Double stage diamond anvil cells (DACs) of two designs have been assembled and tested. We used a standard symmetric DAC with flat or beveled culets as a primary stage and CVD microanvils machined by a focused ion beam as a second. We evaluated pressure, stress, and strain distributions in gold and a mixture of gold and iron as well as in secondary anvils using synchrotron x-ray diffraction with a micro-focused beam. A maximum pressure of 240 GPa was reached independent of the first stage anvil culet size. We found that the stress field generated by the second stage anvils is typical of conventional DAC experiments. The maximum pressures reached are limited by strains developing in the secondary anvil and by cupping of the first stage diamond anvil in the presented experimental designs. Also, our experiments show that pressures of several megabars may be reached without sacrificing the first stage diamond anvils.

Knowledge of Fe composition in lower-mantle minerals (primarily perovskite and ferropericlase) is essential to a complete understanding of the Earth’s interior. Fe cation diffusion potentially controls many aspects of the distribution of Fe in the Earth’s lower mantle, including mixing of chemical heterogeneities, element partitioning, and the extent of core-mantle communications. Fe in ferropericlase has been shown to undergo a spin transition starting at about 40 GPa and exists in a mixture of high-spin and low-spin states over a wide range of pressures. Present experimental data on Fe transport in ferropericlase is limited to pressures below 35 GPa and provides little information on the pressure dependence of the activation volume and none on the impact of the spin transition on diffusion. Therefore, known experimental data on Fe diffusion cannot be reliably extrapolated to predict diffusion throughout the lower mantle. Here, first-principles and statistical modeling are combined to predict diffusion of Fe in ferropericlase over the entire lower mantle, including the effects of the Fe spin transition. A thorough statistical thermodynamic treatment is given to fully incorporate the coexistence of high- and low-spin Fe in the model of overall Fe diffusion in the lower mantle. Pure low-spin Fe diffuses approximately 10 4 times slower than high-spin Fe in ferropericlase but Fe diffusion of the mixed-spin state is only about 10 times slower than that of high-spin Fe. The predicted Fe diffusivities demonstrate that ferropericlase is unlikely to be rate limiting in transporting Fe in deep earth since much slower Fe diffusion in perovskite is predicted.

Pallasites are a unique group of meteorites consisting of a mixture of approximately equal proportions of olivine grains in a matrix of Fe-Ni metal. These meteorites provide physical samples of the interior of a differentiated planetary body. As such, they provide direct geochemical clues to planetary differentiation processes. In this study, one large collaborative effort is undertaken to analyze a suite of 14 main-group pallasite specimens by several different instrumental analytical techniques in an attempt to provide a comprehensive picture of formation processes, temperatures and timescales. The suite of specimens chosen come from both the main group pallasites and the Eagle Station trio, and encompass a range of fayalite composition and of olivine shape and distribution. Samples have been optically imaged and then mapped EDS using a JEOL JSM-6500F field-emission SEM equipped with an Oxford X-Max 80 mm 2 silicon drift detector to determine major element composition and distribution. The Oxford AZtec software allows large-format montaged mapping so that the entire specimen can be mapped to the same scale. Smaller region EDS mapping highlights minor mineral phases and the interfaces between the mineral grains and the metal phases. These maps quantitatively verify the mineral phases present and the Fe/Mg ratio of the olivine phase and the Fe/Ni ratio of the metal phase. Electron microprobe WDS analyses of mineral phases are being done on a JEOL 8900 to verify major and minor element composition in regions of interest. These analyses also highlight areas that are targeted for focused ion beam (FIB) analysis. The FIB is used to examine the interface between olivine and metal and create a 3-D reconstruction. Nano-scale phases are then highlighted for future TEM preparation. Between the SEM and microprobe results, areas were highlighted for mass spectrometry analysis. Several samples were analyzed with laser ablation ICPMS for trace element content. Pallasites can provide information about highly-siderophile elements (HSE) present in both mantle and core of differentiated bodies. Many differentiated planetary bodies show enrichment in HSE concentration in their mantle relative to their core. Our study indicates that both HSE concentrations and the O-isotope fractionation share a common trend with iron III-AB meteorites. The HSE concentrations are also comparable to Mars and the Angrite parent body. In addition, diffusion profiles are being obtained in the microprobe for both the metal and olivine phases, which indicate the cooling rates of these meteorites. The iron metal region contains regions of taenite interlaced with kamacite, in which Ni zonation and diffusion has traditionally been used to determine the metallographic cooling rate within the taenite [1]. More recently, zonation of the olivine rim has been used to determine cooling rates [2], however these indicate a much faster cooling rate than that estimated by the metallic rates. This study aims to examine diffusion in both phases to better

Extended abstract of a paper presented at Microscopy and Microanalysis 2013 in Indianapolis, Indiana, USA, August 4 – August 8, 2013.

Extended abstract of a paper presented at Microscopy and Microanalysis 2012 in Phoenix, Arizona, USA, July 29 – August 2, 2012.

Extended abstract of a paper presented at Microscopy and Microanalysis 2012 in Phoenix, Arizona, USA, July 29 – August 2, 2012.