An SMP critical state model for methane hydrate‐bearing sands

Mechanical properties of methane hydrate‐bearing soils are complex. Their behavior undergoes a significant change when hydrates dissociate and become methane gas. On the other hand, methane hydrates are ice‐like compounds and, depending on the hydrate accumulation habits and the degree of hydrate saturation, may cement soil particles into stronger and stiffer soils. A new constitutive model is proposed that is capable of capturing essential characteristics of hydrate‐bearing soils. The core of the model includes the spatial mobilized plane concept; a transformed stress, t_ij; the critical state; and the subloading framework. The proposed model gives soil responses due to stress changes or hydrate saturation changes or both. The performance of the model has been found satisfactory, over a range of hydrate saturation and confining pressures, using triaxial test data from laboratory‐synthesized samples and from field samples extracted from Nankai Trough, Japan. Copyright © 2015 John Wiley & Sons, Ltd.     

Chloride transfer in cement‐based materials. Part 1. Theoretical basis and modelling

In this first part of the work, we develop macroscopic models for migration and diffusion–migration of ionic species in saturated porous media, based on periodic homogenization. The prior application is chloride transport in cementitious materials. The dimensional analysis of Nernst–Planck equation lets appear to dimensionless numbers characterizing the ionic transfer in the porous medium. Using experimental data obtained from electrodiffusion tests on cement‐based materials (Part II), these dimensionless numbers are linked to the perturbation parameter ?. For a strong imposed electrical field, the asymptotic expansion of Nernst–Planck equation leads to a macroscopic model where the migration is predominant. For a weak imposed electrical field or in natural diffusion, we obtain a macroscopic model coupling diffusion and migration at the same order. In both models, the expression of the homogenized diffusion tensor is identical and only involves the geometric properties of the material microstructure. Copyright © 2012 John Wiley & Sons, Ltd.     

Anisotropic viscoplastic modeling of rate‐dependent behavior of clay

The objective of this study is to derive an effective stress‐based constitutive law capable of predicting rate‐dependent stress–strain, stress path and undrained shear strength and creep behavior. The flow rule used in the MIT‐E3 model and viscoplasticity theory is employed in the derivation. The model adopts the yield surface capable of representing the yield behavior of the Taipei silty clay and assumes that it is initially symmetric about the K₀‐line. A method is then developed to compute the gyration and expansion of the loading surface to simulate the anisotropic behavior due to the principal stress rotation after shear. There are 11 parameters required for the model to describe the soil behavior and six of them are exactly the same as those used in the Modified Cam‐clay model. The five additional parameters can be obtained by parametric studies or conventional soil tests, such as consolidation tests, triaxial compression and extension tests. Finally, verification of the model for the anisotropic behavior, creep behavior and the rate‐dependent undrained stress–strain and shear strength of the Taipei silty clay is conducted. Copyright © 2010 John Wiley & Sons, Ltd.     

Numerical modelling of the hydro‐chemo‐mechanical behaviour of geomaterials in the context of CO2 injection

Safety assessment of geosequestration of CO₂ into deep saline aquifers requires a precise understanding of the study of hydro‐chemo‐mechanical couplings occurring in the rocks and the cement well. To this aim, a coupled chemo‐poromechanical model has been developed and implemented into a research code well‐suited to the resolution of fully coupled problems. This code is based on the finite volume methods. In a 1D axisymmetrical configuration, this study aims to simulate the chemo‐poromechanical behaviour of a system composed by the cement well and the caprock during CO₂ injection. Major chemical reactions of carbonation occurring into cement paste and rocks are considered in order to evaluate the consequences of the presence of CO₂ on the amount of dissolved matrix and precipitated calcium carbonates. The dissolution of the solid matrix is taken into account through the use of a chemical porosity. Matrix leaching and carbonation lead, as expected, to important variations of porosity, permeability and to alterations of transport properties and mechanical stiffness. These results justify the importance of considering a coupled analysis accounting for the main chemical reactions. It is worth noting that the modelling framework proposed in the present study could be extended to model the chemo‐poromechanical behaviour of the reservoir rock and the caprock when subjected to the presence of an acidic pore fluid (CO₂‐rich brine). Copyright © 2013 John Wiley & Sons, Ltd.     

Settlement‐time behaviour of granular embankments

Creep settlements are the main cause of deterioration of road pavement and impervious elements of dams, and therefore a method to calculate them is needed. Viscoelastic models (e.g. the standard linear solid) have been chosen to represent the creep of granular materials (Figure 1). Finite element calculations show that quasi‐oedometric conditions exist near the centre of embankments. Explicit expressions for one‐dimensional viscoelastic settlements of an embankment during and after construction have been obtained for any loading law and drawn for a linear load. The three viscoelastic parameters, E_o, R_c and T_r can be determined through laboratory or field testing, and the results can be adjusted by using settlement records. Good agreement has been found between measured and calculated settlements at several dams. Copyright © 2000 John Wiley & Sons, Ltd.     

A Flux‐Free Fusion Technique for Rapid Determination of Major and Trace Elements in Silicate Rocks by LA‐ICP‐MS

A simple flux‐free fusion technique was developed to analyse major and trace element compositions of silicate rocks. The sample powders were melted in a molybdenum capsule sealed in a graphite tube to make a homogenous glass in a temperature‐controlled one‐atmosphere furnace. The glass was then measured for both major and trace element concentrations by LA‐ICP‐MS using a calibration strategy of total metal‐oxide normalisation. The optimum conditions (i.e., temperature and duration) to make homogeneous glasses were obtained by performing melting experiments using a series of USGS reference materials including BCR‐2, BIR‐1, BHVO‐2, AGV‐1, AGV‐2, RGM‐1, W‐2 and GSP‐2 with SiO₂ contents from 47 to 73% m/m. Analytical results of the USGS reference materials using our method were generally consistent with the recommended values within a discrepancy of 5–10% for most elements. The routine precision of our method was generally better than 5–10% RSD. Compared with previous methods of LA‐ICP‐MS whole‐rock analyses, our flux‐free fusion method is convenient and efficient in making silicate powder into homogeneous glass. Furthermore, it limits contamination and loss of volatile elements during heating. Therefore, our new method has great potential to provide reliable and rapid determinations of major and trace element compositions for silicate rocks.     

Subduction metamorphism of serpentinite‐hosted carbonates beyond antigorite‐serpentinite dehydration (Nevado‐Filábride Complex,Spain)

At sub‐arc depths, the release of carbon from subducting slab lithologies is mostly controlled by fluid released by devolatilization reactions such as dehydration of antigorite (Atg‐) serpentinite to prograde peridotite. Here we investigate carbonate–silicate rocks hosted in Atg‐serpentinite and prograde chlorite (Chl‐) harzburgite in the Milagrosa and Almirez ultramafic massifs of the palaeo‐subducted Nevado‐Filábride Complex (NFC, Betic Cordillera, S. Spain). These massifs provide a unique opportunity to study the stability of carbonate during subduction metamorphism at P–T conditions before and after the dehydration of Atg‐serpentinite in a warm subduction setting. In the Milagrosa massif, carbonate–silicate rocks occur as lenses of Ti‐clinohumite–diopside–calcite marbles, diopside–dolomite marbles and antigorite–diopside–dolomite rocks hosted in clinopyroxene‐bearing Atg‐serpentinite. In Almirez, carbonate–silicate rocks are hosted in Chl‐harzburgite and show a high‐grade assemblage composed of olivine, Ti‐clinohumite, diopside, chlorite, dolomite, calcite, Cr‐bearing magnetite, pentlandite and rare aragonite inclusions. These NFC carbonate–silicate rocks have variable CaO and CO₂ contents at nearly constant Mg/Si ratio and high Ni and Cr contents, indicating that their protoliths were variable mixtures of serpentine and Ca‐carbonate (i.e., ophicarbonates). Thermodynamic modelling shows that the carbonate–silicate rocks attained peak metamorphic conditions similar to those of their host serpentinite (Milagrosa massif; 550–600°C and 1.0–1.4 GPa) and Chl‐harzburgite (Almirez massif; 1.7–1.9 GPa and 680°C). Microstructures, mineral chemistry and phase relations indicate that the hybrid carbonate–silicate bulk rock compositions formed before prograde metamorphism, likely during seawater hydrothermal alteration, and subsequently underwent subduction metamorphism. In the CaO–MgO–SiO₂ ternary, these processes resulted in a compositional variability of NFC serpentinite‐hosted carbonate–silicate rocks along the serpentine‐calcite mixing trend, similar to that observed in serpentinite‐hosted carbonate‐rocks in other palaeo‐subducted metamorphic terranes. Thermodynamic modelling using classical models of binary H₂O–CO₂ fluids shows that the compositional variability along this binary determines the temperature of the main devolatilization reactions, the fluid composition and the mineral assemblages of reaction products during prograde subduction metamorphism. Thermodynamic modelling considering electrolytic fluids reveals that H₂O and molecular CO₂ are the main fluid species and charged carbon‐bearing species occur only in minor amounts in equilibrium with carbonate–silicate rocks in warm subduction settings. Consequently, accounting for electrolytic fluids at these conditions slightly increases the solubility of carbon in the fluids compared with predictions by classical binary H₂O–CO₂ fluids, but does not affect the topology of phase relations in serpentinite‐hosted carbonate‐rocks. Phase relations, mineral composition and assemblages of Milagrosa and Almirez (meta)‐serpentinite‐hosted carbonate–silicate rocks are consistent with local equilibrium between an infiltrating fluid and the bulk rock composition and indicate a limited role of infiltration‐driven decarbonation. Our study shows natural evidence for the preservation of carbonates in serpentinite‐hosted carbonate–silicate rocks beyond the Atg‐serpentinite breakdown at sub‐arc depths, demonstrating that carbon can be recycled into the deep mantle.     

High‐grade metamorphism and partial melting of basic and intermediate rocks

Rocks of basic and intermediate bulk composition occur in orogenic terranes from all geological time periods and are thought to represent significant petrological components of the middle and lower continental crust. However, the former lack of appropriate thermodynamic models for silicate melt, amphibole and clinopyroxene that can be applied to such lithologies at high temperature has inhibited effective phase equilibrium modelling of their petrological evolution during amphibolite‐ and granulite facies metamorphism. In this work, we present phase diagrams calculated in the Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–O₂ (NCKFMASHTO) compositional system for a range of natural basic and intermediate bulk compositions for conditions of 2–12 kbar and 600–1050 ^°C using newly parameterized activity–composition relationships detailed in a companion paper by Green et al. in this issue. Particular attention is given to mid‐ocean ridge basalt (MORB) and diorite protolith bulk compositions. Calculated subsolidus mineral assemblages in all basic and intermediate rock types are modally dominated by hornblende and plagioclase, with variable proportions of epidote, clinopyroxene, garnet, biotite, muscovite, quartz, titanite or ilmenite present at different pressures. The H₂O‐saturated (wet) solidus has a negative P?T slope and occurs between ～620–690 ^°C at mid‐ to lower‐crustal pressures of 5–10 kbar. The lowest‐T melts generated close to the wet solidus are calculated to have granitic major‐element oxide compositions. Melting at higher temperature is attributed primarily to multivariate hydrate‐breakdown reactions involving biotite and/or hornblende. Partial melt compositions calculated at 800–1050 ^°C for MORB show good correlation with analysed compositions of experimental glasses produced via hydrate‐breakdown melting of natural and synthetic basic protoliths, with Niggli norms indicating that they would crystallize to trondhjemite or tonalite. Diorite is shown to be significantly more fertile than MORB and is calculated to produce high‐T melts (>800 ^°C) of granodioritic composition. Subsolidus and suprasolidus mineral assemblages show no significant variation between different members of the basalt family, although the P?T conditions at which orthopyroxene stabilizes, thus defining the prograde amphibolite–granulite transition, is strongly dependent on bulk‐rock oxidation state and water content. The petrological effects of open‐ and closed‐system processes on the mineral assemblages produced during prograde metamorphism and preserved during retrograde metamorphism are also examined via a case‐study analysis of a natural Archean amphibolite from the Lewisian Complex, northwest Scotland.     

Influence of shotcrete composition on load‐level estimation in NATM‐tunnel shells: Micromechanics‐based sensitivity analyses

Displacement measurement‐based estimations of loads and utilization degrees in shotcrete tunnel shells as part of the New Austrian Tunneling Method (NATM), have become standard tools in tunnel practice; their quality, however, may crucially depend on the knowledge of the actual shotcrete composition after spraying. To shed light on this issue, we here determine, based on experimentally validated micromechanical representations of shotcrete, the hydration degree‐dependent elastic, creep, and strength properties of different shotcretes, characterized by water cement ratios (w/c) between 0.4 and 0.6, aggregate cement ratios (a/c) between 3.5 and 5, and Young's modulus of aggregates (E_agg) between 40 and 80 GPa. These properties are fed into a structural shell model of the Sieberg tunnel, and this model is subjected to displacement fields approximated from daily displacement measurements at five selected points along the shell's inner surface. Resulting stresses and forces in the tunnel shell allow for analyzing the influence of shotcrete composition on load‐level estimation in NATM tunnel shells: The magnitudes of circumferential and longitudinal normal forces increase significantly with decreasing w/c, while a/c and E_agg have the inverse and relatively minor effect. The utilization degree is virtually insensitive to changes in w/c(especially at early ages), and only slightly decreases with decreasing a/c and E_agg. The location of maximum loading is unaffected by the shotcrete composition underlying the analysis. Conclusively, location and magnitude of maximum utilization degrees are very robust estimates (not affected by limited knowledge on the shotcrete composition), whereas realistic estimation of stresses and forces does require more accurate consideration of shotcrete composition. Copyright © 2011 John Wiley & Sons, Ltd.     

Thermodynamic and pore water halogen constraints on gas hydrate distribution at ODP Site 997 (Blake Ridge)

Marine sediment sequences with CH₄ hydrate are characterized by an atypical depth profile in dissolved Cl⁻ squeezed from pore space: a shallow subsurface Cl⁻ maximum overlies a lengthy and pronounced Cl⁻ minimum. This pore water Cl⁻ profile represents a combination of multiple processes including glacial–interglacial variations in ocean salinity, advection and diffusion of ions that are excluded during gas hydrate formation at depth, and release of fresh water from dissociation of hydrate during core recovery. In situ quantities of gas hydrate can be determined from a measured pore water Cl⁻ profile provided the in situ pore water signature prior to core recovery can be separated. Ocean Drilling Program (ODP) Site 997 was drilled into a large CH₄ hydrate reservoir on the Blake Ridge in the western Atlantic Ocean. Previously we have constructed a high-resolution pore water Cl⁻ profile at this location; here we present a `coupled chloride-hydrate' numerical model to explain basic trends in the Cl⁻ profile and to isolate in situ Cl⁻ concentrations. The model is based on thermodynamic and ecological considerations, and uses established equations for describing chemical behavior in marine sediment–pore water systems. The model incorporates four key concepts: (1) most gas hydrate is formed immediately below the SO₄²⁻ reduction zone; (2) fluid, dissolved ions and gas advect upward through the sediment column; (3) CH₄ hydrate dissociates at the base of hydrate stability conditions; and (4) seawater salinity fluctuates during glacial–interglacial cycles of the late Pliocene and Quaternary. Rates of upward advection in the model are sufficient to account for measured Br⁻ and I⁻ concentrations as well as CH₄ oxidation at the base of the SO₄²⁻ reduction zone. In situ pore water Cl⁻ inferred from the model is similar to that determined by limited direct sampling; in situ CH₄ hydrate amounts inferred from the model (an average of about 4% of porosity) are broadly consistent with those determined by direct gas sampling and indirect geophysical techniques. The model also predicts production of substantial quantities of free CH₄ gas bubbles (>2.5% of porosity) at a depth immediately below the lowest accumulation of CH₄ hydrate in the sediment column. Our explanation for the pore water Cl⁻ profile at Site 997 is important because it provides a theoretical mechanism for understanding the distribution of interstitial water Cl⁻, gas hydrate, and free gas in a marine sediment column.     

Simulation of CO<Subscript>2</Subscript> hydrate formation in cold aquifers: nonequilibrium approach

In this paper, we focus on the geological storage of CO₂ in reservoirs with zones that are cold enough to facilitate CO₂ hydrate formation at local pressures. A 2D hydro-chemical mechanical model which has five layers (three layers with aquifers and two layers with cap rock in which we introduced two fractures) is created. We apply a reactive transport reservoir simulator, RetrasoCodeBright (RCB), in which hydrate is treated as a pseudo mineral. Following the recent modifications to account for hydrate dynamics in the code through a kinetic approach (Kvamme et al., Proceedings of the 7th International Conference on Gas Hydrates (ICGH 2011), 2011b), we have further improved the simulator to implement the nonequilibrium thermodynamic calculations. In the present study, we spot the light on the hydrate formation effects on porosity in different regions, as well as on the flow pattern. These simulations are based on classical relationships between porosity and permeability, but the outline of ongoing modifications is presented as well. A critical question in such systems is whether hydrate formation can contribute to stabilizing the storage, given that hydrates are pore filling and cannot be stable toward mineral surfaces. The implications of hydrate formation on the geo-mechanical properties of the model reservoir are other aspects addressed in this study.     

Rock alteration in alkaline cement waters over 15 years and its relevance to the geological disposal of nuclear waste

The interaction of groundwater with cement in a geological disposal facility (GDF) for intermediate level radioactive waste will produce a high pH leachate plume. Such a plume may alter the physical and chemical properties of the GDF host rock. However, the geochemical and mineralogical processes which may occur in such systems over timescales relevant for geological disposal remain unclear. This study has extended the timescale for laboratory experiments and shown that, after 15 years two distinct phases of reaction may occur during alteration of a dolomite-rich rock at high pH. In these experiments the dissolution of primary silicate minerals and the formation of secondary calcium silicate hydrate (C–S–H) phases containing varying amounts of aluminium and potassium (C–(A)–(K)–S–H) during the early stages of reaction (up to 15 months) have been superseded as the systems have evolved. After 15 years significant dedolomitisation (MgCa(CO₃)₂ + 2OH⁻ → Mg(OH)₂ + CaCO₃ + CO₃²⁻_(aq)) has led to the formation of magnesium silicates, such as saponite and talc, containing variable amounts of aluminium and potassium (Mg–(Al)–(K)–silicates), and calcite at the expense of the early-formed C–(A)–(K)–S–H phases. This occured in high pH solutions representative of two different periods of cement leachate evolution with little difference in the alteration processes in either a KOH and NaOH or a Ca(OH)₂ dominated solution but a greater extent of alteration in the higher pH KOH/NaOH leachate. The high pH alteration of the rock over 15 years also increased the rock’s sorption capacity for U(VI). The results of this study provide a detailed insight into the longer term reactions occurring during the interaction of cement leachate and dolomite-rich rock in the geosphere. These processes have the potential to impact on radionuclide transport from a geodisposal facility and are therefore important in underpinning any safety case for geological disposal.     

Calculation of partial melting equilibria in the system Na2O–CaO–K2O–FeO–MgO–Al2O3–SiO2–H2O (NCKFMASH)

A thermodynamic model for haplogranitic melts in the system Na₂O–CaO–K₂O–Al₂O₃–SiO₂–H₂O (NCKASH) is extended by the addition of FeO and MgO, with the data for the additional end‐members of the liquid incorporated in the Holland & Powell (1998) internally consistent thermodynamic dataset. The resulting dataset, with the software thermocalc , is then used to calculate melting relationships for metapelitic rock compositions. The main forms for this are P–T and T–X pseudosections calculated for particular rock compositions and composition ranges. The relationships in these full‐system pseudosections are controlled by the low‐variance equilibria in subsystems of NCKFMASH. In particular, the solidus relationships are controlled by the solidus relationships in NKASH, and the ferromagnesian mineral relationships are controlled by those in KFMASH. However, calculations in NCKFMASH allow the relationships between the common metapelitic minerals and silicate melt to be determined. In particular, the production of silicate melt and melt loss from such rocks allow observations to be made about the processes involved in producing granulite facies rocks, particularly relating to open‐system behaviour of rocks under high‐grade conditions.     

Acidic Rocks as Aggregates in Concrete: Engineering Properties,Microstructures and Petrologic Characteristics

In this research, the possibility of replacing different portions of the normally used aggregate by acidic rocks was investigated. These rock types outcrop at the northern part of Eastern Desert, southwest Ras Gharib area where large quantities of good quality acidic rocks are available their. Portland cement concrete is a composite material made up of the hydrated cement matrix, fine aggregate and coarse aggregate. The scanning electron microscope equipped with an energy dispersive X-ray analysis system (EDX) has been applied to investigate several aspects of Portland cement concrete microstructure. The topics investigated so far include the influence of aggregate composition on the development of the cement paste-aggregate interface and the formation of calcium silicate hydrate CSH/calcium silicate aluminate CSA formation. The silicate gel coated the aggregates in the concrete paste and crystallized into well defined needle like shape, cotton shape as well as euhedral to subhedral crystals of silicate/alumiante and ettringite minerals with free lime librated from the hydrolysis process. The free lime can react again with the aggregates leading to the formation of cementing materials which increase strength and durability of the concrete paste by increasing the interfacial bonds between the used aggregates.     

Experimental creep tests and prediction of long-term creep behavior of grouting material

Rock reinforcement systems, such as resin-grouted rock bolts, display complex creep behavior because both grouting materials and bolts show time-dependent behavior. In this paper, only the time-dependent behavior of grouting material was investigated, in which creep tests of grouting material was conducted in triaxial compression apparatus at room temperature. The test specimens were provided from the Araldite epoxy resin used in rock reinforcement. We attempt to predict long-term creep parameter using triaxial creep tests and to define time-dependent characteristics of the bounding material. In short-term creep tests, three different axial and confining stress levels were applied in steps to each specimen. The transient creep for all the stress levels were described by power function which fit properly to time–strain curves. The maximum difference between the proposed model and experimental long-term creep strain was less than 7.1 %. It was observed that the creep rate of a grouting material specimen directly depends on the deviator of stress (i.e., σ₁–σ₃).     

Accurate Determination of Sr Isotopic Compositions in Clinopyroxene and Silicate Glasses by LA‐MC‐ICP‐MS

The low‐Sr content (generally < 100 μg g^?1) in clinopyroxene from peridotite makes accurate Sr isotopic determination by LA‐MC‐ICP‐MS a challenge. The effects of adding N₂ to the sample gas and using a guard electrode (GE) on instrumental sensitivity for Sr isotopic determination by LA‐MC‐ICP‐MS were investigated. Results revealed no significant sensitivity enhancement of Sr by adding N₂ to the ICP. Although using a GE led to a two‐fold sensitivity enhancement, it significantly increased the yield of polyatomic ion interferences of Ca‐related ions and TiAr⁺ on Sr isotopes. Applying the method established in this work, ⁸⁷Sr/⁸⁶Sr ratios (Rb/Sr < 0.14) of natural clinopyroxene from mantle and silicate glasses were accurately measured with similar measurement repeatability (0.0009–0.00006, 2SE) to previous studies but using a smaller spot size of 120 μm and low‐to‐moderate Sr content (30–518 μg g^?1). The measurement reproducibility was 0.0004 (2s, n = 33) for a sample with 100 μg g^?1 Sr. Destruction of the crystal structure by sample fusion showed no effect on Sr isotopic determination. Synthesised glasses with major element compositions similar to natural clinopyroxene have the potential to be adopted as reference materials for Sr isotopic determination by LA‐MC‐ICP‐MS.