Analysis of the FEBEX multi‐barrier system including thermoplasticity of unsaturated bentonite

Deep geological repository involving a multibarrier system constitutes one of the most promising options for isolating high‐level radioactive waste from the human environment. To certify the efficiency of waste isolation, it is essential to understand the behaviour of confining geomaterial under a variety of environmental conditions. To this end, results from a near‐to‐real experiment, the full‐scale engineered barriers in situ experiment, are studied by means of a thermo–hydro–mechanical finite element approach, including a consistent thermoplastic constitutive model for unsaturated soils. Laboratory tests are simulated to calibrate model parameters. The results of the numerical simulations are compared with sensor measurements and show the ability of the model to reproduce the main behavioural features of the system. The influence of the hysteretic and temperature‐dependent retention of water on the mechanical response is exhibited. Finally, those results are interpreted in the light of thermoplasticity of unsaturated soils, which reveals the highly coupled and non‐linear characters of the processes encountered. Copyright © 2011 John Wiley & Sons, Ltd.     

An X-ray absorption fine structure and nuclear magnetic resonance spectroscopy study of gallium-silica complexes in aqueous solution

The influence of aqueous silica on gallium(III) hydrolysis in dilute (2 × 10⁻⁴ ≤ m_Ga ≤ 5 × 10⁻³) and moderately concentrated (0.02 ≤ m_Ga ≤ 0.3) aqueous solutions was studied at ambient temperature, using high resolution X-ray absorption fine structure (XAFS) and nuclear magnetic resonance (NMR) spectroscopies, respectively. Results show that, in Si-free acidic solutions (pH < 3), Ga is hexa-coordinated with oxygens of H₂O molecules and/or OH groups in the first coordination sphere of the metal. With increasing pH, these hydroxyl groups are progressively replaced by bridging oxygens (-O-), and polymerized Ga-hydroxide complexes form via Ga-O-Ga chemical bonds. In the 2.5-3.5 pH range, both XAFS and NMR spectra are consistent with the dominant presence of the Ga₁₃ Keggin polycation, which has the same local structure as A1₁₃. Under basic pH (pH > 8), Ga exhibits a tetrahedral coordination, corresponding to Ga(OH)₄⁻ species, in agreement with previous NMR and potentiometric studies. Major changes in Ga hydrolysis have been detected in the presence of aqueous silica. Ga is tetra-coordinated, both in basic and acid (i.e., at pH > 2.7) Si-bearing solutions (0.01 ≤ m_Si ≤ 0.2), and forms stable gallium-silicate complexes. In these species, Ga binds via bridging oxygen to 2 ± 1 silicons, with an average Ga-Si distance of 3.16 ± 0.05 Å, and to 2 ± 1 silicons, with an average Ga-Si distance of 3.39 ± 0.03 Å. These two sets of Ga-Si distances imply the formation of two types of Ga-silicate aqueous complex, cyclic Ga-Si_2-3 species (formed by the substitution of Si in its tri-, tetra- or hexa-cyclic polymers by Ga atoms), and chainlike GaSi_2-4 species (similar to those found for A1), respectively. The increase in the number of Si neighbors (a measure of the complex concentration and stability), in alkaline media, with increasing SiO₂(aq) content and decreasing pH is similar to that for A1-Si complexes found in neutral to basic solutions. At very acid pH and moderate silica concentrations, the presence of another type of Ga-Si complex, in which Ga remains hexa-coordinated and binds to the silicon tetrahedra via the GaO₆ octahedron corners, has also been detected. These species are similar to those found for Al³⁺ in acid solutions. Thus, as for aluminum, silicic acid greatly hampers Ga hydrolysis and enhances Ga mobility in natural waters via the formation of gallium-silicate complexes.     

The origin of the high-K latites from Camp Creek,Arizona: constraints from experiments with variable fO2 and a_{{\text{H}}_{\text{2}} {\text{O}}}

Near-liquidus melting experiments were performed on a high-K latite at fO₂'s ranging from iron-wustite-graphite (IWG) to nickel-nickel oxide (NNO) in the presence of a C-O-H fluid phase. Clinopyroxene is a liquidus phase under all conditions. At IWG , the liquidus at 10 kb is about 1,150° C but is depressed to 1,025° C at NNO and . Phlogopite and apatite are near-liquidus phases, with apatite crystallizing first at pressures below 10 kb. Phlogopite is a liquidus phase only at NNO and high . Under all conditions the high-K latites show a large crystallization interval with phlogopite becoming the dominant crystalline phase with decreasing temperature. Increasing fO₂ affects phlogopite crystallization but the liquidus temperature is essentially a function of . The chemical compositions of the near-liquidus phases support formation of the high-K latites under oxidizing conditions (NNO or higher) and high . It is concluded from the temperature of the H₂O-saturated liquidus at 10 kb, the groundmass: crystal ratio and presence of chilled latite margins around some xenoliths that the Camp Creek high-K latite magma passed thru the lower crust at temperatures of 1,000° C or more.     

Groundwater metering: revisiting a ubiquitous ‘best practice’

Hydrogeology Journal - It is often taken for granted that metering is an unarguable ‘best practice’ when it comes to the quantitative management of groundwater resources. This paper...     

Late Quaternary vegetation and climate dynamics in central-eastern Brazil: insights from a ~35k cal a bp peat record in the Cerrado biome

The late Quaternary evolution of central-eastern Brazil has been under-researched. Questions remain as to the origin of the Cerrado, a highly endangered biome, and other types of vegetation, such as the Capões – small vegetation islands of semi-deciduous and mountain forests. We investigated the factors that influenced the expansion and contraction of the Cerrado and Capões during the late Quaternary (last ~35 ka), using a multi-proxy approach: stable isotopes (δ¹³C, δ¹⁵N), geochemistry, pollen and multivariate statistics derived from a peat core (Pinheiro mire, Serra do Espinhaço Meridional). Five major shifts in precipitation, temperature, vegetation and landscape stability occurred at different timescales. Our study revealed that changes in the South Atlantic Convergence Zone (SACZ) seem to have been coeval with these shifts: from the Late Glacial Maximum to mid-Holocene the SACZ remained near (~29.6 to ~16.5k cal a bp ) and over (~16.5 to ~6.1 k cal a bp ) the study area, providing humidity to the region. This challenges previous research which suggested that climate was drier for this time period. At present, the Capões are likely to be a remnant of a more humid climate; meanwhile, the Cerrado biome seems to have stablished in the late Holocene, after ~3.1 k cal a bp .     

Laboratory condensation of refractory dust in protosolar and circumstellar conditions

In order to better understand condensation processes that took place in the solar nebula and to evaluate the effect of kinetics on the condensed matter, we have built an experimental apparatus for studying condensation of multi-elemental refractory gases at high-temperature and low-pressure. The condensation of a Mg-Si-rich gas, with solar interelement ratios of Ca, Al, Mg and Si, and of a Ca-Al-rich gas under a total pressure of ∼4 × 10⁻³ bar at temperatures from 1045 to 1285 °C and for run times of 4-60 min results in direct formation of crystalline oxides or silicates such as corundum, spinel, anorthite, melilite, Al-diopside, forsterite and enstatite. The mineralogy of the condensates, close to that predicted at equilibrium, varies with the duration of an experiment and the temperature of condensation. The chemical reactions between gas and condensates are rapid enough to attain a steady state in less than one hour. The condensation results in chemical fractionation of the gas, i.e. a depletion of the gas in refractory elements at high temperature. Finally, besides revealing the textures of refractory crystals, which condense from a gas of complex chemical composition, this study shows that certain phases, such as spinel, have favored kinetics of condensation. Our experimental results confirm that refractory inclusions in primitive meteorites could have formed by condensation from a hot nebular gas. Similarly, we confirm that crystalline grains can condense at high temperature in the outflows of evolved stars. In both cases, our results indicate that kinetic processes certainly influence grain mineralogy. Kinetic processes must thus be taken into account in modeling the pressure-temperature conditions of circumstellar environments.     

Effects of sinuosity factor on hydrodynamic parameters estimation in karst systems: a dye tracer experiment from the Beyyayla sinkhole (Eskişehir,Turkey)

The sinuosity factor (SF) is a critical value in karst systems in terms of estimating their hydrodynamic parameters including groundwater velocity, coefficient of dispersion, etc., through dye tracer experiments. SF has been used in a number of different dye tracer experiments in karstic systems to estimate a representative flow path. While knowing SF is crucially important in the estimation of hydrodynamic parameters, its calculation is associated with significant uncertainty due to the complexity of subsurface karstic features. And yet, only a few studies have discussed its uncertainties, which might lead some errors in estimation of hydrodynamic parameters from dye tracer experiment. In this study, dye tracer experiments were conducted in two consecutive years (2003 and 2004) representing low and high flow conditions in the Beyyayla sinkhole (Eski?ehir, Turkey) where the flow path is well known. Uranine was used in experiments as a tracer and QTRACER computer program was used to determine the hydrodynamic properties of the Beyyayla karst system as well as to gain insights into the effects of SF from dye tracer experiments on estimated parameters. The results showed that the breakthrough curve follows a unimodal and a bimodal distribution in low and high flow conditions, respectively. These different distributions stem from the water transport mechanisms, where velocities were calculated as 58.2 and 93.6 m h^?1 during low and high flow conditions observed in a spring emerging from the south side of the studied system. The results also show that the coefficient of dispersion, Reynolds number, and Peclet number increased and longitudinal dispersivity decreased with the higher flow rate. Furthermore, the estimated parameters did not vary with either the flow conditions or the tracer transit time, but they have shown some variations with SF. When SF was increased by 50 %, a change in these parameters was obtained in the range of 50–125 %.     

Hydrodynamics of Canal Istanbul and its impact in the northern Sea of Marmara under extreme conditions

Ocean Dynamics - The Bosphorus, located at the junction of Asia and Europe, controls the transports of water, material, and energy between the Black Sea (BS) and the Mediterranean Sea. The Canal...