Hervé Cardon

Equation of state of Al-bearing perovskite to lower mantle pressure conditions

Al2O3 is estimated to total 4 to 5 mol% in all mantle compositional models, and is believed to be incorporated into (Mg,Fe)SiO3-perovskite at lower mantle conditions. Using synchrotron X-ray diffraction, we have measured the 300 K equation of state of a perovskite with XAl=Al/(Al+Mg+Si)=.077, up to 32 GPa. A least squares refinement of two independent data sets yields the following equation of state parameters V0=163.52(3) A³, K0=229(4) GPa, and K0=2.5(4). These values allow us to assess the most probable substitution mechanism for aluminium into perovskite at pressure conditions of the shallow lower mantle. Al3+ is likely to be incorporated in place of Si4+ in the octahedral site of perovskite, hence requiring the creation of oxygen vacancies for charge balance. As a consequence, aluminous perovskites may have a high affinity for water. The enhanced compressibility of aluminous perovskite certainly has also strong geophysical and geochemical implications, as it may revive perovskite-rich lower mantle models.

Analytical transmission electron microscopy study of a natural MORB sample assemblage transformed at high pressure and high temperature

Abstract Natural mid-ocean ridge basalt (MORB) samples recovered from diamond-anvil cell (DAC) experiments performed between 33 to 89 GPa and 1700 to 2600 K were studied with a transmission electron microscope (TEM). We used the focused ion beam (FIB) lift-out technique to prepare the recovered high-pressure, laser-heated samples for TEM study. Observations of TEM sections show the presence of five phases for samples transformed at pressures ranging from 33 to 45 GPa: Al-bearing Mg-perovskite, Ca-silicate perovskite, stishovite, and two Al-rich phases. The Al-rich phases were identified by selected area electron diffraction (SAED) patterns and chemical composition analysis, and include the new aluminous (NAL) phase with hexagonal structure and the calcium ferrite (CF) type phase. Chemical analyses obtained by analytical transmission electron microscopy (ATEM) show that Mg-silicate perovskite is the major host for Al, with significant amounts also distributed between the CF-type and NAL phases, and less than 1 wt% in stishovite. Beyond pressures of ~40 GPa (~1100 km depth), the Al content of Mg-perovskite and CF-type phase increases. Between 45 and 50 GPa, the NAL phase disappears. This mineralogical change may explain reported seismic anomalies in subduction zones at mid-mantle depths.

Equations of state of ice VI and ice VII at high pressure and high temperature

High-pressure H2O polymorphs among which ice VI and ice VII are abundant in the interiors of large icy satellites and exo-planets. Knowledge of the elastic properties of these pure H2O ices at high-temperature and high-pressure is thus crucial to decipher the internal structure of icy bodies. In this study we assess for the first time the pressure-volume-temperature (PVT) relations of both polycrystalline pure ice VI and ice VII at high pressures and temperatures from 1 to 9 GPa and 300 to 450 K, respectively, by using in situ synchrotron X-ray diffraction. The PVT data are adjusted to a second-order Birch-Murnaghan equation of state and give V0 = 14.17(2) cm(3) mol(-1), K0 = 14.05(23) GPa, and α0 = 14.6(14) × 10(-5) K(-1) for ice VI and V0 = 12.49(1) cm(3) mol(-1), K0 = 20.15(16) GPa, and α0 = 11.6(5) × 10(-5) K(-1) for ice VII.

Constraints on the mobilization of Zr in magmatic-hydrothermal processes in subduction zones from in situ fluid-melt partitioning experiments

Abstract The partitioning of Zr between high P-T aqueous fluids and melts has been investigated in situ in the haplogranite-H2O and haplogranite-(F)-H2O systems to assess the mobilization of high field strength elements (HFSE) in magmatic-hydrothermal processes in subduction zones. The partition coefficients Df/Zmr were determined from Zr concentrations measured in situ by synchrotron X-ray fluorescence (SXRF) in both aqueous fluids and F-free or F-bearing hydrous haplogranite melts equilibrated in diamond-anvil cells at 575 to 800 °C and 0.3 to 2.4 GPa. This experimental approach eliminates the need for internal or external calibrations of the SXRF signal and/or post-mortem analysis of the melt phase, hence decreasing the total uncertainties on Df/Zmr below 16%. Above 0.6 GPa, Zr partitions favorably into the hydrous silicate melt in both F-free and F-bearing systems, with Df/Zmr that range between 0.19 ± 0.02 and 0.38 ± 0.03. However, the relatively high Df/Zmr values indicate that alkali-silica rich aqueous fluids generated by metamorphic devolatilization may contribute significantly to the recycling of HFSE in subduction zones. The efficient uptake of Zr (and likely other HFSE) by subduction zone fluids, regardless of their nature (aqueous fluid, hydrous melt, or supercritical fluid), supports the idea that the typical HFSE depletion recorded in arc magmas does not result from their incompatibility in water-rich slab-derived fluids but most probably originates from complex fluid-melt-rock interactions occurring at the slab interface and within the mantle wedge. At shallow crustal pressure conditions (800 °C and 0.3 GPa), Zr partitions reversely into the aqueous fluid in the presence of fluorine (Df/Zmr = 1.40 ± 0.10) as observed for Nb at similar conditions by Webster et al. (1989). The enrichment of the aqueous phase in HFSE (Zr, Nb) at shallow crustal conditions is likely related to the enhanced peralkalinity of low pressure, F-bearing aqueous fluid with temperature, that provides the favorable conditions for their mobilization via the formation of HFSE-O-Si/Na clusters. This mechanism may control the enrichment in HFSE (and plausibly other rare metals such as REE) in early magmatic fluids exsolved from granitic melts, leading to the formation of HFSE-enriched aggregates in shallow magmatic-hydrothermal environments (e.g., Strange Lake and Thor Lake Nechalacho deposit, Canada; Galineiro complex, Spain).

Monitoring microbial redox transformations of metal and metalloid elements under high pressure using in situ X-ray absorption spectroscopy

X-ray absorption spectroscopy is a well-established method for probing local structural and electronic atomic environments in a variety of systems. We used X-ray absorption near-edge structure (XANES) spectroscopy for monitoring in real-time conditions selenium reduction in situ in live cultures of Shewanella oneidensis MR-1 under high hydrostatic pressure. High-quality XANES data show that Shewanella oneidensis MR-1 reduces selenite Se(IV) to red elemental selenium Se(0) up to 150 MPa without any intermediate redox state. MR-1 reduces all selenite provided (5-10 mM) between 0.1 and 60 MPa. Above 60 MPa the selenite reduction yield decreases linearly with pressure and the activity is calculated to stop at 155 ± 5 MPa. The analysis of cultures recovered after in situ measurements showed that the decrease in activity is linked to a decrease in viability. This study emphasizes the promising potential of XANES spectroscopy for real-time probing in situ microbial redox transformations of a broad range of metal and metalloid elements in live samples, including under high hydrostatic pressure.