Pressure dependence of nickel partitioning between forsterite and aluminous silicate melts

Nickel partitioning between forsterite and aluminosilicate melt of fixed bulk composition has been determined at 1300°C to 20 kbar pressure. The value of the forsterite-liquid nickel partition coefficient is lowered from >20 at pressures equal to or less than 15 kbar to <10 at pressures above 15 kbar.Published data indicate that melts on the join Na₂O-Al₂O₃-SiO₂ become depolymerized in the pressure range 10–20 kbar as a result of Al shifting from four-coordination at low pressure to higher coordination as the pressure is increased. This coordination shift results in a decreasing number of bridging oxygens in the melt. It is suggested that the activity coefficient of nickel decreases with this decrease in the number of bridging oxygens. As a result, the nickel partition coefficient for olivine and liquid is lowered.Magma genesis in the upper mantle occurs in the pressure range where the suggested change in aluminum coordination occurs in silicate melts. It is suggested, therefore, that data on nickel partitioning obtained at low pressure are not applicable to calculation of the nickel distribution between crystals and melts during partial melting in the upper mantle. Application of high-pressure experimental data determined here for Al-rich melts to the partial melting process indicates that the melts would contain about twice as much nickel as indicated by the data for the low-pressure experiments. If, as suggested here, the polymerization with pressure is related to the Al content of the melt, the difference in the crystal-liquid partition coefficient for nickel at low and high pressure is reduced with decreasing Al content of the melt. Consequently, the change ofD_Ni^{ol-andesite melt} is greater than that ofD_Ni^{ol-basalt melt}, for example.     

Speciation of reduced C-O-H volatiles in coexisting fluids and silicate melts determined in-situ to ∼1.4 GPa and 800 °C

The structure of silicate melts in the system Na₂O·4SiO₂ saturated with reduced C-O-H volatile components and of coexisting silicate-saturated C-O-H solutions has been determined in a hydrothermal diamond anvil cell (HDAC) by using confocal microRaman and FTIR spectroscopy as structural probes. The experiments were conducted in-situ with the melt and fluid at high temperature (up to 800 °C) and pressure (up to 1435 MPa). Redox conditions in the HDAC were controlled with the reaction, Mo + H₂O = MoO₂ + H₂, which is slightly more reducing than the Fe + H₂O = FeO + H₂ buffer at 800 °C and less.The dominant species in the fluid are CH₄ + H₂O together with minor amounts of molecular H₂ and an undersaturated hydrocarbon species. In coexisting melt, CH₃ - groups linked to the silicate melt structure via Si-O-CH₃ bonding may dominate and possibly coexists with molecular CH₄. The abundance ratio of CH₃ - groups in melts relative to CH₄ in fluids increases from 0.01 to 0.07 between 500 and 800 °C. Carbon-bearing species in melts were not detected at temperatures and pressures below 400 °C and 730 MPa, respectively. A schematic solution mechanism is, Si-O-Si + CH₄?Si-O-CH₃+H-O-Si. This mechanism causes depolymerization of silicate melts. Solution of reduced (C-O-H) components will, therefore, affect melt properties in a manner resembling dissolved H₂O.     

Simulation of anisotropic heterogeneous near-well flow using MPFA methods on flexible grids

Control-volume multipoint flux approximations (MPFA) are discussed for the simulation of complex near-well flow using geometrically flexible grids. Due to the strong non-linearity of the near-well flow, a linear model will, in general, be inefficient. Instead, a model accounting for the logarithmic pressure behavior in the well vicinity is advocated. This involves a non-uniform refinement of the grid in the radial direction. The model accounts for both near-well anisotropies and heterogeneities. For a full simulation involving multiple wells, this single-well approach can easily be coupled with the reservoir model. Numerical simulations demonstrate the convergence behavior of this model using various MPFA schemes under different near-well conditions for single-phase flow regimes. Two-phase simulations support the results of the single-phase simulations.     

Solution mechanisms of silicate in aqueous fluid and H2O in coexisting silicate melts determined in-situ at high pressure and high temperature

The structure of H₂O-saturated silicate melts, coexisting silicate-saturated aqueous solutions, and supercritical silicate liquids in the system Na₂O·4SiO₂–H₂O has been characterized with the sample at high temperature and pressure in a hydrothermal diamond anvil cell (HDAC). Structural information was obtained with confocal microRaman and with FTIR microscopy. Fluids and melts were examined along pressure-temperature trajectories defined by the isochores of H₂O at nominal densities, ρ_fluid, (from EOS of pure H₂O) of 0.90 and 0.78 g/cm³. With ρ_fluid = 0.78 g/cm³, water-saturated melt and silicate-saturated aqueous fluid coexist to the highest temperature (800 °C) and pressure (677 MPa), whereas with ρ_fluid = 0.90 g/cm³, a homogeneous single-phase liquid phase exists through the temperature and pressure range (25–800 °C, 0.1–1033 MPa). Less than 5 vol% quartz precipitates near 650 °C in both experimental series, thus driving Na/Si-ratios of melt + fluid phase assemblages to higher values than that of the Na₂O·4SiO₂ starting material.Molecular H₂O (H₂O°) and structurally bonded OH groups were observed in coexisting melts and fluids as well as in supercritical liquids. Their OH/(H₂O)-ratio is positively correlated with temperature. The OH/(H₂O)° in melts is greater than in coexisting fluids. Structural units of Q³, Q², Q¹, and Q⁰ type are observed in all phases under all conditions. An expression of the form, 12Q³ + 13H₂O2Q² + 6Q¹ + 4Q⁰, describes the equilibrium among those structural units. This equilibrium shifts to the right with increasing pressure and temperature with a ΔH of the reaction near 425 kJ/mol.     

Impact of reach geometry on stream channel sensitivity to extreme floods

Predicting spatial and temporal variations in bank erosion due to extreme floods presents a long‐standing challenge in geomorphology. We develop two methodologies for rapid, regional‐scale assessments of stream reaches susceptible to channel widening. The first proposes that channel widening occurs when unit stream power exceeds a critical threshold (300 W/m²). The second is motivated by the observation that widening often occurs at channel bends. We introduce a new metric, the bend stress parameter, which is proportional to the centripetal force exerted on a concave bank. We propose that high centripetal forces generate locally high bank shear forces and enhance channel bank erosion. We test both metrics using the geomorphic signature of Tropical Storm Irene (2011) on the White and the Saxtons Rivers, Vermont. Specifically, we test if reaches where significant channel widening occurred during Irene required one or both metrics to exceed threshold values. We observe two distinct styles of channel widening. Where unit stream power and bend stress parameter are high, widening is usually due to bank retreat. Elsewhere widening is usually due to the stripping of the upstream end of mid‐channel islands. Excluding widening associated with the stripping of the heads of mid‐channel islands, almost all the widening (> 98%) occurred along reaches identified as susceptible to widening. The combined metrics identify up to one‐quarter of the reaches lacking susceptibility to channel widening. Copyright © 2014 John Wiley & Sons, Ltd.     

Multidimensional upstream weighting for multiphase transport on general grids

The governing equations for multiphase flow in porous media have a mixed character, with both nearly elliptic and nearly hyperbolic variables. The flux for each phase can be decomposed into two parts: (1) a geometry- and rock-dependent term that resembles a single-phase flux; and (2) a mobility term representing fluid properties and rock–fluid interactions. The first term is commonly discretized by two- or multipoint flux approximations (TPFA and MPFA, respectively). The mobility is usually treated with single-point upstream weighting (SPU), also known as dimensional or donor cell upstream weighting. It is well known that when simulating processes with adverse mobility ratios, SPU suffers from grid orientation effects. An important example of this, which will be considered in this work, is the displacement of a heavy oil by water. For these adverse mobility ratio flows, the governing equations are unstable at the modeling scale, rendering a challenging numerical problem. These challenges must be addressed in order to avoid systematic biasing of simulation results. In this work, we present a framework for multidimensional upstream weighting for multiphase flow with buoyancy on general two-dimensional grids. The methodology is based on a dual grid, and the resulting transport methods are provably monotone. The multidimensional transport methods are coupled with MPFA methods to solve the pressure equation. Both explicit and fully implicit approaches are considered for time integration of the transport equations. The results show considerable reduction of grid orientation effects compared to SPU, and the explicit multidimensional approach allows larger time steps. For the implicit method, the total number of non-linear iterations is also reduced when multidimensional upstream weighting is used.     

Iron-bearing silicate melts: Relations between pressure and redox equilibria

Mossbauer spectroscopy has been used to determine the redox equilibria of iron and structure of quenched melts on the composition join Na₂Si₂O₅-Fe₂O₃ to 40 kbar pressure at 1400° C. The Fe³⁺/ΣFe decreases with increasing pressure. The ferric iron appears to undergo a gradual coordination transformation from a network-former at 1 bar to a network-modifier at higher (≧10 kbar) pressure. Ferrous iron is a network-modifier in all quenched melts. Reduction of Fe³⁺ to Fe²⁺ and coordination transformation of remaining Fe³⁺ result in depolymerization of the silicate melts (the ratio of nonbridging oxygens per tetrahedral cations, NBO/T, increases). It is suggested that this pressure-induced depolymerization of iron-bearing silicate liquids results in increasing NBO/T of the liquidus minerals. Furthermore, this depolymerization results in a more rapid pressure-induced decrease in viscosity and activation energy of viscous flow of iron-bearing silicate melts than would be expected for iron-free silicate melts with similar NBO/T.     

Nature of polymerization and properties of silicate melts and glasses at high pressure

The structures of sodium silicate and aluminosilicate glasses quenched from melts at high pressure (6-10 GPa) with varying degrees of polymerization (fractions of nonbridging oxygen) were explored using solid-state NMR [¹⁷O and ²⁷Al triple-quantum magic-angle spinning (3QMAS) NMR]. The bond connectivity in melts among four and highly coordinated network polyhedra, such as ^[4]Al, ^[5,6]Al, ^[4]Si, and ^[5,6]Si, at high pressure is shown to be significantly different from that at ambient pressure. In particular, in the silicate and aluminosilicate melts, the proportion of nonbridging oxygen (NBO) generally decreases with increasing pressure, leading to the formation of new oxygen clusters that include 5- and 6-coordinated Si and Al in addition to 4-coordinated Al and Si, such as ^[4]Si-O-^[5,6]Si, ^[4]Si-O-^[5,6]Al and Na-O-^[5,6]Si. While the fractions of ^[5,6]Al increase with pressure, the magnitude of this increase diminishes with increasing degrees of ambient-pressure polymerization under isobaric conditions. Incorporating the above structural information into models of melt properties reproduces the anomalous pressure-dependence of O²⁻ diffusivity and viscosity often observed in silicate melts.