Effect of oxygen fugacity on the storage of water in wadsleyite and olivine in H and H–C fluids and implications for melting atop the transition zone

This study aims to experimentally constrain the water storage capacities of olivine and wadsleyite at a depth near 410 km (12–14 GPa) under water-saturated conditions, as a function of temperature, oxygen fugacity, and the presence of carbon (molar H / C of 2). Experiments have been conducted in the multi-anvil press, with sealed double capsules to preserve fluids, at 1200 to 1400 ∘C and three different oxygen fugacities fixed at the rhenium–rhenium oxide buffer (RRO), nickel–nickel oxide buffer (NNO), and iron-wüstite (IW) for oxidizing, intermediate, and reducing conditions, respectively. The water contents of minerals were measured by Raman spectroscopy that allows a very small beam size to be used and were cross-checked on a few samples with NanoSIMS analyses. We observe an effect, although slight, of fO2 on the water storage capacity of both wadsleyite and olivine and also on their solidus temperatures. At 1200 ∘C, the storage capacity of the nominally anhydrous minerals (NAMS) increases with increasing oxygen fugacity (from the IW to the RRO buffer) from 1 wt % to 1.5 wt % H2O in wadsleyite and from 0.1 wt % to 0.2 wt % in olivine, owing to the increase in H2O / H2 speciation in the fluid, whereas at 1400 ∘C the storage capacity decreases from 1 wt % to 0.75 wt % H2O in wadsleyite and down to 0.03 wt % for olivine. At high temperature, the water storage capacity is lowered due to melting, and the more oxidized the conditions are the more the solidus is depressed. Still, at 1400 ∘C and IW, wadsleyite can store substantial amounts of water: 0.8 wt % to 1 wt % H2O. The effect of carbon is to decrease water storage capacity in both wadsleyite and olivine by an average factor 2 at 1300–1400 ∘C. The trends in water storage as a function of fO2 and C presence are confirmed by NanoSIMS measurements. The solidus at IW without C is located between 1300 and 1400 ∘C in the wadsleyite stability field and drops to temperatures below 1300 ∘C in the olivine stability field. With the addition of C, the solidus is found between 1200 and 1300 ∘C in both olivine and wadsleyite stability fields.</p

Melting phase relations in the systems Mg2SiO4-H2O and MgSiO3-H2O and the formation of hydrous melts in the upper mantle

High-pressure and high-temperature melting experiments were conducted in the systems Mg2SiO4–H2O and MgSiO3–H2O at 6 and 13 GPa and between 1150 and 1900 °C in order to investigate the effect of H2O on melting relations of forsterite and enstatite. The liquidus curves in both binary systems were constrained and the experimental results were interpreted using a thermodynamic model based on the homogeneous melt speciation equilibrium, H2O + O2− = 2OH−, where water in the melt is present as both molecular H2O and OH− groups bonded to silicate polyhedra. The liquidus depression as a function of melt H2O concentration is predicted using a cryoscopic equation with the experimental data being reproduced by adjusting the water speciation equilibrium constant. Application of this model reveals that in hydrous MgSiO3 melts at 6 and 13 GPa and in hydrous Mg2SiO4 melts at 6 GPa, water mainly dissociates into OH− groups in the melt structure. A temperature dependent equilibrium constant is necessary to reproduce the data, however, implying that molecular H2O becomes more important in the melt with decreasing temperature. The data for hydrous forsterite melting at 13 GPa are inconclusive due to uncertainties in the anhydrous melting temperature at these conditions. When applied to results on natural peridotite melt systems at similar conditions, the same model infers the presence mainly of molecular H2O, implying a significant difference in physicochemical behaviour between simple and complex hydrous melt systems. As pressures increase along a typical adiabat towards the base of the upper mantle, both simple and complex melting results imply that a hydrous melt fraction would decrease, given a fixed mantle H2O content. Consequently, the effect of pressure on the depression of melting due to H2O could not cause an increase in the proportion, and hence seismic visibility, of melts towards the base of the upper mantle

Water in cratonic lithosphere : calibrating laboratory-determined models of electrical conductivity of mantle minerals using geophysical and petrological observations

Author Posting. © American Geophysical Union, 2012. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geochemistry Geophysics Geosystems 13 (2012): Q06010, doi:10.1029/2012GC004055.Measurements of electrical conductivity of “slightly damp” mantle minerals from different laboratories are inconsistent, requiring geophysicists to make choices between them when interpreting their electrical observations. These choices lead to dramatically different conclusions about the amount of water in the mantle, resulting in conflicting conclusions regarding rheological conditions; this impacts on our understanding of mantle convection, among other processes. To attempt to reconcile these differences, we test the laboratory-derived proton conduction models by choosing the simplest petrological scenario possible – cratonic lithosphere – from two locations in southern Africa where we have the most complete knowledge. We compare and contrast the models with field observations of electrical conductivity and of the amount of water in olivine and show that none of the models for proton conduction in olivine proposed by three laboratories are consistent with the field observations. We derive statistically model parameters of the general proton conduction equation that satisfy the observations. The pre-exponent dry proton conduction term (σ0) and the activation enthalpy (ΔHwet) are derived with tight bounds, and are both within the broader 2σ errors of the different laboratory measurements. The two other terms used by the experimentalists, one to describe proton hopping (exponent r on pre-exponent water content Cw) and the other to describe H2O concentration-dependent activation enthalpy (term αCw1/3 added to the activation energy), are less well defined and further field geophysical and petrological observations are required, especially in regions of higher temperature and higher water content.The SAMTEX data were acquired through funding provided by the Continental Dynamics program of the U.S. National Science Foundation (grant EAR0455242 to RLE), the South African Department of Science and Technology (grant to South African Council for Geoscience), and Science Foundation Ireland (grant 05/RGP/GEO001 to AGJ) plus financial and/or logistical support provided by all members of the SAMTEX consortium. JF was initially supported by an IRCSET grant to AGJ for the TopoMed project (TopoMed: Plate reorganization in the western Mediterranean: Lithospheric causes and topographic consequences) within the European Science Foundation’s TOPOEUROPE EUROCORES (http://www.esf.org/activities/eurocores/ running-programmes/topo-europe.html), and subsequently by an SFI PI grant (10/IN.1/I3022) to AGJ for IRETHERM (www.iretherm.ie).2012-12-1

Dehydration of chlorite explains anomalously high electrical conductivity in the mantle wedges

Mantle wedge regions in subduction zone settings show anomalously high electrical conductivity ( 3c1 S/m) that has often been attributed to the presence of aqueous fluids released by slab dehydration. Laboratory-based measurements of the electrical conductivity of hydrous phases and aqueous fluids are significantly lower and cannot readily explain the geophysically observed anomalously high electrical conductivity. The released aqueous fluid also rehydrates the mantle wedge and stabilizes a suite of hydrous phases, including serpentine and chlorite. In this present study, we have measured the electrical conductivity of a natural chlorite at pressures and temperatures relevant for the subduction zone setting. In our experiment, we observe two distinct conductivity enhancements when chlorite is heated to temperatures beyond its thermodynamic stability field. The initial increase in electrical conductivity to 3c3 7 10-3 S/m can be attributed to chlorite dehydration and the release of aqueous fluids. This is followed by a unique, subsequent enhancement of electrical conductivity of up to 7 7 10-1 S/m. This is related to the growth of an interconnected network of a highly conductive and chemically impure magnetite mineral phase. Thus, the dehydration of chlorite and associated processes are likely to be crucial in explaining the anomalously high electrical conductivity observed in mantle wedges. Chlorite dehydration in the mantle wedge provides an additional source of aqueous fluid above the slab and could also be responsible for the fixed depth (120 \ub1 40 km) of melting at the top of the subducting slab beneath the subduction-related volcanic arc front

Deep and persistent melt layer in the Archaean mantle

The transition from the Archaean to the Proterozoic eon ended a period of great instability at the Earth's surface. The origin of this transition could be a change in the dynamic regime of the Earth's interior. Here we use laboratory experiments to investigate the solidus of samples representative of the Archaean upper mantle. Our two complementary in situ measurements of the melting curve reveal a solidus that is 200-250 K lower than previously reported at depths higher than about 100 km. Such a lower solidus temperature makes partial melting today easier than previously thought, particularly in the presence of volatiles (H2O and CO2). A lower solidus could also account for the early high production of melts such as komatiites. For an Archaean mantle that was 200-300 K hotter than today, significant melting is expected at depths from 100-150 km to more than 400 km. Thus, a persistent layer of melt may have existed in the Archaean upper mantle. This shell of molten material may have progressively disappeared because of secular cooling of the mantle. Crystallization would have increased the upper mantle viscosity and could have enhanced mechanical coupling between the lithosphere and the asthenosphere. Such a change might explain the transition from surface dynamics dominated by a stagnant lid on the early Earth to modern-like plate tectonics with deep slab subduction

Thermal expansion of liquid Fe-S alloy at high pressure

Co-auteur étrangerInternational audienceLocal structure and density of liquid Fe-S alloys at high pressure have been determined in situ by combined angle and energy dispersive X-ray diffraction experiments in a multi-anvil apparatus, covering a large temperature and compositional range. Precise density measurements collected for increasing temperature allowed us to directly derive the thermal expansion coefficients for liquid Fe-S alloys as a function of composition. In turn, thermal expansion has been used to refine thermodynamic models and to address the crystallization regime of telluric planetary cores by comparing the adiabatic temperature gradient and the slope of the liquidus in the Fe-FeS system.For Fe-S cores of asteroids and small planetesimals, top-down solidification is the dominant scenario as the compositional domain for which the slope of the liquidus is greater than the adiabatic gradient is limited to a narrow portion on the Fe-rich side. However, bottom-up growth of the inner core is expected for S-poor cases, with this compositional domain expanding to more S-rich compositions with increasing pressure (size of the planetary body). In particular, bottom-up crystallization cannot be excluded for the Moon and Ganymede